JP2000136370A - Member exhibiting hydrophilicity in response to photoexcitation of optical semiconductor - Google Patents
Member exhibiting hydrophilicity in response to photoexcitation of optical semiconductorInfo
- Publication number
- JP2000136370A JP2000136370A JP11239567A JP23956799A JP2000136370A JP 2000136370 A JP2000136370 A JP 2000136370A JP 11239567 A JP11239567 A JP 11239567A JP 23956799 A JP23956799 A JP 23956799A JP 2000136370 A JP2000136370 A JP 2000136370A
- Authority
- JP
- Japan
- Prior art keywords
- sample
- optical semiconductor
- water
- contact angle
- photoexcitation
- 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.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 86
- 239000004065 semiconductor Substances 0.000 title claims abstract description 81
- 230000004044 response Effects 0.000 title claims abstract description 34
- 230000001443 photoexcitation Effects 0.000 title claims abstract description 24
- 230000001747 exhibiting effect Effects 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000000758 substrate Substances 0.000 claims abstract description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 230000003373 anti-fouling effect Effects 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 90
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 61
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 14
- 238000005406 washing Methods 0.000 abstract description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract 2
- 150000004706 metal oxides Chemical class 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 44
- 230000005284 excitation Effects 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 238000000576 coating method Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000010304 firing Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000005507 spraying Methods 0.000 description 13
- 230000008859 change Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000003981 vehicle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000003749 cleanliness Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012643 polycondensation polymerization Methods 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- -1 titanium alkoxide Chemical class 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- MZZINWWGSYUHGU-UHFFFAOYSA-J ToTo-1 Chemical compound [I-].[I-].[I-].[I-].C12=CC=CC=C2C(C=C2N(C3=CC=CC=C3S2)C)=CC=[N+]1CCC[N+](C)(C)CCC[N+](C)(C)CCC[N+](C1=CC=CC=C11)=CC=C1C=C1N(C)C2=CC=CC=C2S1 MZZINWWGSYUHGU-UHFFFAOYSA-J 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- DARFZFVWKREYJJ-UHFFFAOYSA-L magnesium dichloride dihydrate Chemical compound O.O.[Mg+2].[Cl-].[Cl-] DARFZFVWKREYJJ-UHFFFAOYSA-L 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229940047908 strontium chloride hexahydrate Drugs 0.000 description 3
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002772 conduction electron Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 150000003609 titanium compounds Chemical class 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
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZBZXIGONWYKEMZ-UHFFFAOYSA-N CCO[Ti] Chemical compound CCO[Ti] ZBZXIGONWYKEMZ-UHFFFAOYSA-N 0.000 description 1
- FLTYUJMFMHOICO-UHFFFAOYSA-N CO[Ti] Chemical compound CO[Ti] FLTYUJMFMHOICO-UHFFFAOYSA-N 0.000 description 1
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 1
- 229920000114 Corrugated plastic Polymers 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000001781 Xanthosoma sagittifolium Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001283 organosilanols Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
- F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
- F24F8/22—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Finishing Walls (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Prevention Of Fouling (AREA)
- Optical Elements Other Than Lenses (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Building Environments (AREA)
- Refuge Islands, Traffic Blockers, Or Guard Fence (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Road Signs Or Road Markings (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Rear-View Mirror Devices That Are Mounted On The Exterior Of The Vehicle (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Greenhouses (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Panels For Use In Building Construction (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Detergent Compositions (AREA)
- Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
- Bridges Or Land Bridges (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
- Joining Of Glass To Other Materials (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
- Refrigerator Housings (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、基材の表面を高度
の親水性になし、かつ、維持する技術に関する。より詳
しくは、本発明は、鏡、レンズ、板ガラスその他の透明
基材の表面を高度に親水化することにより、基材の曇り
や水滴形成を防止する防曇技術に関する。本発明は、ま
た、建物や窓ガラスや機械装置や物品の表面を高度に親
水化することにより、表面が汚れるのを防止し、又は表
面を自己浄化(セルフクリーニング)し若しくは容易に
清掃する技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for making a surface of a substrate highly hydrophilic and maintaining it. More specifically, the present invention relates to an antifogging technique for preventing the fogging and water droplet formation of a substrate by highly hydrophilizing the surface of a mirror, a lens, a sheet glass, or another transparent substrate. The present invention also provides a technique for preventing the surface from being soiled, or performing self-cleaning (self-cleaning) or easily cleaning the surface of a building, a window glass, a mechanical device, or an article by making the surface highly hydrophilic. About.
【0002】[0002]
【従来の技術】基材表面が親水化されると、付着水滴が
基材表面に一様に拡がるようになるので、ガラス、レン
ズ、鏡等の透明性部材の曇りを有効に防止でき、湿分に
よる失透防止、雨天時の視界性確保等に役立つ。さら
に、都市煤塵、自動車等の排気ガスに含有されるカーボ
ンブラック等の燃焼生成物、油脂、シーラント溶出成分
等の疎水性汚染物質が付着しにくく、付着しても降雨や
水洗により簡単に落せるようになるので便利である。2. Description of the Related Art When the surface of a substrate is hydrophilized, attached water droplets spread evenly on the surface of the substrate, so that it is possible to effectively prevent fogging of transparent members such as glass, lenses, mirrors, etc. It is useful for preventing devitrification due to the minute and for securing visibility in rainy weather. Furthermore, hydrophobic contaminants such as urban dust, combustion products such as carbon black contained in exhaust gas from automobiles, oils and fats, and components eluted from sealants are unlikely to adhere, and even if adhered, can easily be removed by rainfall or washing with water. This is convenient.
【0003】このような事情から特に防曇塗料、外装防
汚塗料の分野において、従来から親水性樹脂が提案され
ている(例えば、実開平5−68006号や、「高分
子」、44巻、1995年5月号、p.307)。ま
た、親水化するための表面処理方法も提案されている
(例えば、実開平3−129357号)。Under these circumstances, hydrophilic resins have been proposed in the field of antifogging paints and exterior antifouling paints in particular (for example, Japanese Utility Model Laid-Open No. 5-68006, "Polymer", Vol. May 1995, p. 307). Also, a surface treatment method for making the surface hydrophilic has been proposed (for example, Japanese Utility Model Laid-Open No. 3-129357).
【0004】しかしながら、従来提案されている親水性
樹脂は水との接触角に換算して30〜50゜程度までし
か親水化されず、充分な曇り防止効果が発揮できない。
また無機粘土質からなる汚染物質の付着及び降雨、水洗
による清浄性が充分でない。また従来提案されている親
水化するための表面処理方法(エッチング処理、プラズ
マ処理等)では、一時的に高度に親水化できてもその状
態を長期間維持することができない。[0004] However, the conventionally proposed hydrophilic resin can be made hydrophilic only up to about 30 to 50 ° in terms of the contact angle with water, and cannot exhibit a sufficient fogging prevention effect.
Further, the adhesion of contaminants composed of inorganic clay, and the cleanliness by rainfall and washing with water are not sufficient. In the surface treatment methods (hydrophobic treatment, etching treatment, plasma treatment, etc.) that have been conventionally proposed, the state cannot be maintained for a long time even if the surface can be temporarily made highly hydrophilic.
【0005】本発明者は、PCT/JP96/0073
3号において、基材表面に光半導体含有層を形成する
と、光半導体の光励起に応じて表面が高度に親水化され
ることを発明し、この技術をガラス、レンズ、鏡、外装
材、水回り部材等の種々の複合材に適用すれば、これら
複合材に優れた防曇、防汚等の機能を付与できることを
提案した。この方法によれば、充分な曇り防止効果が発
揮され、疎水性汚染物質及び無機粘土質からなる汚染物
質の付着及び降雨、水洗による清浄性が飛躍的に向上す
る。また光半導体の光励起に応じて親水化された状態が
維持、回復される。The present inventor has proposed PCT / JP96 / 0073.
No. 3, invented that when an optical semiconductor-containing layer is formed on the substrate surface, the surface is highly hydrophilized in response to the optical excitation of the optical semiconductor, and this technology is applied to glass, lenses, mirrors, exterior materials, It has been proposed that when applied to various composite materials such as members, these composite materials can be provided with excellent functions such as antifogging and antifouling. According to this method, a sufficient antifogging effect is exhibited, and adhesion of hydrophobic contaminants and inorganic clay contaminants, and cleanliness by rainfall and water washing are remarkably improved. Further, the state of hydrophilization is maintained and recovered in response to the photoexcitation of the optical semiconductor.
【0006】[0006]
【発明が解決しようとする課題】しかしながら、実質的
に耐摩擦性に優れた光半導体のみからなる層を、施釉タ
イル基材やガラス基材等の平滑な表面を有する基材に直
接光半導体ゾル塗布法で塗布し、焼成する場合には、光
半導体の光励起に応じて10゜以下程度まで親水化され
ない。また、例えば光半導性酸化チタンのみからなる層
をガラス基材上に形成するのに、アルコキシド法、スパ
ッタリング法等にて無定型酸化チタン層を形成後、焼成
して無定型酸化チタンを結晶化させる方法等ならば、光
半導体の光励起に応じて10゜以下程度まで親水化され
るが、この場合もさらに親水化が進めばより高い防曇、
防汚等の性能が発揮されると考えられる。そこで、本発
明では、光半導体のみからなる層と比較して、光半導体
の光励起に応じて、より高度に親水化される部材、より
具体的には、より曇り防止性に優れた防曇性部材、より
汚染物質が付着しにくく、かつ降雨、水洗による清浄性
に優れた防汚性部材、より表面の乾燥しやすい部材を提
供することを目的とする。However, a layer composed of only an optical semiconductor having substantially excellent friction resistance is directly applied to a substrate having a smooth surface such as a glazed tile substrate or a glass substrate. When applied by a coating method and baked, it is not hydrophilized to about 10 ° or less according to the optical excitation of the optical semiconductor. Also, for example, to form a layer composed of only photoconductive titanium oxide on a glass substrate, an amorphous titanium oxide layer is formed by an alkoxide method, a sputtering method, or the like, and then fired to crystallize the amorphous titanium oxide. In the case of such a method, the hydrophilicity is reduced to about 10 ° or less in accordance with the photoexcitation of the optical semiconductor.
It is thought that performance such as antifouling is exhibited. Therefore, in the present invention, as compared with a layer composed of only an optical semiconductor, a member that is more highly hydrophilized in response to photoexcitation of the optical semiconductor, more specifically, an antifogging property that is more excellent in antifogging property It is an object of the present invention to provide a member, an antifouling member which is less likely to adhere contaminants, and has excellent cleanliness by rainfall and water washing, and a member whose surface is more easily dried.
【0007】[0007]
【課題を解決するための手段】本発明では、上記課題を
解決すべく、光半導体の光励起に応じて部材表面が親水
化される親水性部材、防曇性部材、防汚性部材、易乾燥
性部材において、基材表面に、光半導体と以外にアルカ
リ金属、アルカリ土類金属、亜鉛、アルミニウム、白
金、パラジウム、ルテニウム、アルミナ、ジルコニア、
セリア、イットリアの1群から選ばれた少なくとも1種
を含む層が形成されているようにした。本発明の好まし
い態様においては、上記部材表面は、光半導体の光励起
に応じ、水との接触角に換算して10゜以下、より好ま
しくは5゜以下まで親水化されるようにする。このよう
にすることで、特に防曇性、汚染物質の付着防止性及び
降雨、水洗による清浄性の飛躍的に優れた部材となる。According to the present invention, in order to solve the above-mentioned problems, a hydrophilic member, an antifogging member, an antifouling member, and an easy-drying member whose surface is hydrophilized in response to light excitation of an optical semiconductor. In the conductive member, on the surface of the base material, in addition to the optical semiconductor, an alkali metal, an alkaline earth metal, zinc, aluminum, platinum, palladium, ruthenium, alumina, zirconia,
A layer containing at least one selected from the group consisting of ceria and yttria was formed. In a preferred embodiment of the present invention, the surface of the member is made hydrophilic up to 10 ° or less, more preferably 5 ° or less in terms of a contact angle with water, in response to optical excitation of the optical semiconductor. By doing so, the member is particularly excellent in anti-fogging property, anti-adhesion property of contaminants, and cleanliness by rainfall and washing.
【0008】[0008]
【発明の実施の形態】次に、本発明の構成要素について
説明する。ここでいう光半導体とは、価電子帯中の電子
の励起によって生成する正孔或いは伝導電子を介する反
応により、おそらくは表面に極性を付与して吸着水層を
形成することにより、基材表面を親水化できるものをさ
し、より具体的には、アナターゼ型酸化チタン、ルチル
型酸化チタン、酸化錫、酸化亜鉛、三酸化二ビスマス、
三酸化タングステン、酸化第二鉄、チタン酸ストロンチ
ウム等が使用できる。Next, the components of the present invention will be described. The term “optical semiconductor” as used herein means that the surface of the base material is formed by a reaction through holes or conduction electrons generated by excitation of electrons in the valence band, probably by imparting polarity to the surface to form an adsorbed water layer. What can be made hydrophilic, more specifically, anatase type titanium oxide, rutile type titanium oxide, tin oxide, zinc oxide, bismuth trioxide,
Tungsten trioxide, ferric oxide, strontium titanate and the like can be used.
【0009】ここでいう親水化とは、水濡れ性が向上す
る状態の変化をいう。都市煤塵、自動車等の排気ガスに
含有されるカーボンブラック等の燃焼生成物、油脂、シ
ーラント溶出成分等の疎水性汚染物質が付着しにくく、
付着しても降雨や水洗により簡単に落せるようにするに
は、基材表面は水との接触角に換算して50゜以下、よ
り好ましくは30゜以下程度まで親水化するのがよい。
さらに無機粘土質汚染物質が付着しにくく、付着しても
降雨や水洗により簡単に落せるようにするには、基材表
面は水との接触角に換算して20゜以下、好ましくは1
0゜以下、より好ましくは5゜以下程度まで親水化する
のがよい。また透明基材や鏡基材表面に付着した水滴を
一様に拡がらせて、ガラス、レンズ、プリズム、鏡の曇
りを有効に防止し、湿分による失透防止、雨天時の視界
性確保を図るためには基材表面は10゜以下程度まで親
水化するのがよい。The term “hydrophilization” as used herein refers to a change in the state in which the water wettability is improved. Hydrophobic contaminants such as urban dust, combustion products such as carbon black contained in exhaust gas from automobiles, oils and fats, and sealant eluting components are unlikely to adhere,
In order to allow the substrate surface to be easily dropped by rainfall or washing with water even if it adheres, the surface of the substrate is preferably hydrophilized to a contact angle with water of 50 ° or less, more preferably about 30 ° or less.
Further, in order that inorganic clay contaminants are hardly adhered, and even if they are adhered, they can be easily dropped by rainfall or washing with water.
It is preferable to make the surface hydrophilic to 0 ° or less, more preferably to about 5 ° or less. In addition, it uniformly spreads water droplets adhering to the surface of the transparent or mirror substrate, effectively preventing fogging of glass, lenses, prisms, and mirrors, preventing devitrification due to moisture, and ensuring visibility in rainy weather In order to achieve this, the surface of the base material is preferably made hydrophilic to about 10 ° or less.
【0010】本発明に使用できる基材としては、防曇用
途においては、ガラス、透明プラスチック、レンズ、プ
リズム、鏡等の透明性の基材である。より具体的には、
浴室用又は洗面所用鏡、車両用バックミラー、歯科用歯
鏡、道路鏡のような鏡;眼鏡レンズ、光学レンズ、写真
機レンズ、内視鏡レンズ、照明用レンズ、半導体製造用
レンズのようなレンズ;プリズム;建物や監視塔の窓ガ
ラス;自動車、鉄道車両、航空機、船舶、潜水艇、雪上
車、ロープウエイのギンドラ、遊園地のゴンドラ、宇宙
船のような乗り物の窓ガラス;自動車、鉄道車両、航空
機、船舶、潜水艇、雪上車、スノーモービル、オートバ
イ、ロープウエイのギンドラ、遊園地のゴンドラ、宇宙
船のような乗り物の風防ガラス;防護用又はスポーツ用
ゴーグル又はマスク(潜水用マスクを含む)のシール
ド;ヘルメットのシールド;冷凍食品陳列ケースのガラ
ス;計測機器のカバーガラス、及びそれら物品に貼着可
能なフィルム等を含む。[0010] Substrates that can be used in the present invention include transparent substrates such as glass, transparent plastics, lenses, prisms and mirrors for anti-fog applications. More specifically,
Mirrors such as bathroom mirrors, bathroom mirrors, vehicle rearview mirrors, dental tooth mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, lenses for semiconductor manufacturing, etc. Lenses; Prisms; Windows of buildings and watchtowers; Vehicles, railcars, aircraft, ships, submersibles, snowmobiles, ropeway gindra, amusement park gondola, vehicle windows such as spacecraft; automobiles, railway vehicles Windshields for vehicles such as aircraft, ships, submersibles, snowmobiles, snowmobiles, motorcycles, ropeway gindra, amusement park gondola, spacecraft; protective or sports goggles or masks (including diving masks) Helmet shield; frozen food display case glass; measuring instrument cover glass; .
【0011】本発明に使用できる基材としては、降雨に
よる自己浄化が期待できる屋外用途においては、例え
ば、金属、セラミックス、ガラス、プラスチック、木、
石、セメント、コンクリート、繊維、布帛、紙、それら
の組合せ、それらの積層体、それらの塗装体等である。
より具体的には、外壁や屋根のような建物外装;窓枠;
自動車、鉄道車両、航空機、船舶、自転車、オートバイ
のような乗物の外装及び塗装;窓ガラス;看板、交通標
識、防音壁、ビニールハウス、碍子、乗物用カバー、テ
ント材、反射板、雨戸、網戸、太陽電池用カバー、太陽
熱温水器等の集熱器用カバー、街灯、舖道、屋外照明、
人工滝・人工噴水用石材・タイル、橋、温室、外壁材、
壁間や硝子間のシーラー、ガードレール、ベランダ、自
動販売機、エアコン室外機、屋外ベンチ、各種表示装
置、シャッター、料金所、料金ボックス、屋根樋、車両
用ランプ保護カバー、防塵カバー及び塗装、機械装置や
物品の塗装、広告塔の外装及び塗装、構造部材、及びそ
れら物品に貼着可能なフィルム等を含む。The base material usable in the present invention is, for example, metal, ceramics, glass, plastic, wood, and the like in outdoor applications where self-purification by rain can be expected.
Stone, cement, concrete, fiber, fabric, paper, combinations thereof, laminates thereof, coatings thereof, and the like.
More specifically, building exteriors such as exterior walls and roofs; window frames;
Exterior and coating of vehicles such as automobiles, railway vehicles, aircraft, ships, bicycles, and motorcycles; window glass; signboards, traffic signs, soundproof walls, greenhouses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors , Cover for solar cell, cover for heat collector such as solar water heater, street lamp, lining road, outdoor lighting,
Stones and tiles for artificial waterfalls and artificial fountains, bridges, greenhouses, exterior wall materials,
Sealers between walls and glass, guardrails, verandas, vending machines, outdoor units for air conditioners, outdoor benches, various display devices, shutters, toll booths, toll boxes, roof gutters, lamp protection covers for vehicles, dustproof covers and painting, machinery Includes painting of equipment and articles, exterior and painting of advertising towers, structural members, and films that can be attached to those articles.
【0012】本発明に使用できる基材としては、水洗に
よる清浄化が期待できる用途においては、例えば、金
属、セラミックス、ガラス、プラスチック、木、石、セ
メント、コンクリート、繊維、布帛、紙、それらの組合
せ、それらの積層体、それらの塗装体等である。より具
体的には、上記屋外用途部材が含まれることは勿論、そ
の他に、建物の内装材、窓ガラス、住宅設備、便器、浴
槽、洗面台、照明器具、台所用品、食器、食器乾燥器、
流し、調理レンジ、キッチンフード、換気扇、窓レー
ル、窓枠、トンネル内壁、トンネル内照明、及びそれら
物品に貼着可能なフィルム等を含む。The substrate which can be used in the present invention is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth, paper, and the like in applications where cleaning by water washing can be expected. Combinations, their laminates, their painted bodies, and the like. More specifically, not only the above-mentioned outdoor use members are included, but also other materials such as building interior materials, window glass, housing equipment, toilet bowls, bathtubs, washbasins, lighting fixtures, kitchenware, tableware, dish dryers,
Includes sinks, cooking ranges, kitchen hoods, ventilation fans, window rails, window frames, tunnel walls, tunnel lighting, films that can be attached to these items, and the like.
【0013】本発明に使用できる基材としては、乾燥促
進が期待できる用途においては、例えば、窓サッシ、熱
交換器用放熱フィン、舖道、浴室用洗面所用鏡、洗面化
粧台、ビニールハウス天井及びそれら物品に貼着可能な
フィルム等を含む。Examples of the base material usable in the present invention include, in applications in which drying acceleration can be expected, for example, window sashes, heat-dissipating fins for heat exchangers, bathrooms, bathroom mirrors, vanity tables, greenhouse ceilings and the like. Includes films and the like that can be attached to those articles.
【0014】本発明に使用できる基材は上記以外にも着
雪防止、気泡付着防止、生体親和性向上等に利用でき
る。着雪防止性は特に表面粗さ1μm以下の表面層を設
けると顕著に優れた特性が得られ、例えば、雪国用屋根
材、アンテナ、送電線及びそれら物品に貼着可能なフィ
ルム等を含む基材に適用可能である。The base material that can be used in the present invention can be used for prevention of snow accumulation, prevention of air bubble adhesion, improvement of biocompatibility, etc. in addition to the above. Particularly excellent snow-repelling properties can be obtained by providing a surface layer having a surface roughness of 1 μm or less. For example, roofing materials for snowy countries, antennas, power transmission lines, and base materials including films that can be attached to such articles, etc. Applicable to materials.
【0015】光半導体の光励起は、光半導体結晶の伝導
電子帯と価電子帯との間のエネルギーギャップよりも大
きなエネルギー(すなわち短い波長)を有する光を光半
導体に照射して行う。より具体的には、光半導体がアナ
ターゼ型酸化チタンの場合には波長387nm以下、ル
チル酸化チタンの場合には波長413nm以下、酸化錫
の場合には波長344nm以下、酸化亜鉛の場合には波
長387nm以下の光を含有する光線を照射する。上記
光半導体の場合は、紫外線光源により光励起されるの
で、光源としては、蛍光灯、白熱電灯、メタルハライド
ランプ、水銀ランプのような室内照明、太陽光や、それ
らの光源を低損失のファイバーで誘導した光源等を利用
できる。複合材表面の親水化に必要な、光半導体を光励
起するために必要な光の照度は、0.001mW/cm
2以上、より好ましくは0.01mW/cm2以上であ
る。Optical excitation of the optical semiconductor is performed by irradiating the optical semiconductor with light having an energy (that is, a shorter wavelength) larger than the energy gap between the conduction electron band and the valence band of the optical semiconductor crystal. More specifically, when the optical semiconductor is anatase type titanium oxide, the wavelength is 387 nm or less, when rutile titanium oxide is 413 nm or less, when tin oxide is 344 nm or less, and when zinc oxide is 387 nm. A light beam containing the following light is irradiated. In the case of the above-mentioned optical semiconductor, since the light is excited by an ultraviolet light source, the light source is indoor lighting such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, and a mercury lamp, sunlight, and the light source is guided by a low-loss fiber. A light source or the like can be used. The illuminance of light required for photoexcitation of the optical semiconductor required for hydrophilizing the surface of the composite material is 0.001 mW / cm.
2 or more, more preferably 0.01 mW / cm 2 or more.
【0016】本発明において、基材表面に、光半導体以
外に添加する物質にアルミナ又はイットリアを選ぶと、
0.01mW/cm2未満程度の微弱な励起光照射下、
あるいは暗所での親水維持性がよりよく発揮されるよう
になる。In the present invention, when alumina or yttria is selected as a substance to be added to the surface of the base material other than the optical semiconductor,
Under weak excitation light irradiation of less than about 0.01 mW / cm 2 ,
Alternatively, the hydrophilicity in a dark place is more effectively exhibited.
【0017】また、本発明における、さらに好ましい態
様においては、光半導体含有層にはさらに、シリカ、及
び/又はシリコン原子に結合された有機基の少なくとも
一部が水酸基に置換されたシリコーン樹脂が添加されて
いるようにする。こうすることにより光半導体の光励起
に応じて生じる複合材表面の親水化はより高度に進むよ
うになると共に、一旦親水化された複合材を暗所に放置
した場合でも、長期にわたり親水性が維持されるように
なる。In a further preferred aspect of the present invention, the optical semiconductor-containing layer further comprises silica and / or a silicone resin in which at least a part of the organic groups bonded to silicon atoms is substituted with hydroxyl groups. To have been. By doing so, the hydrophilicity of the composite material surface that occurs in response to the optical excitation of the optical semiconductor becomes more advanced, and the hydrophilicity is maintained for a long time even when the hydrophilic material is once left in a dark place. Will be done.
【0018】光半導体含有層の膜厚は0.2μm以下に
するのが好ましい。そうすれば、光の干渉による光半導
体含有層の発色を防止することができる。また光半導体
含有層の膜厚が薄ければ薄いほど基材の透明度を確保す
ることができる。更に、膜厚を薄くすれば光半導体含有
層の耐摩耗性が向上する。光半導体含有層上に、更に、
親水化可能な耐摩耗性又は耐食性の保護層や他の機能膜
を設けてもよい。The thickness of the optical semiconductor-containing layer is preferably set to 0.2 μm or less. This can prevent the optical semiconductor-containing layer from coloring due to light interference. Further, the thinner the thickness of the optical semiconductor-containing layer, the higher the transparency of the substrate can be secured. Further, when the film thickness is reduced, the wear resistance of the optical semiconductor-containing layer is improved. On the optical semiconductor containing layer,
A wear-resistant or corrosion-resistant protective layer or other functional film that can be made hydrophilic may be provided.
【0019】光半導体含有層の屈折率は、基材の屈折率
より小さいか、あまり大きくないほうがよい。例えば基
材がガラス基材(屈折率1.5)である場合は、光半導
体含有層の屈折率は2以下であるのが好ましい。そうす
れば、複合材表面での可視光の反射を防止でき、透明材
における視界確保、意匠性外装又は塗装におけるギラギ
ラ感の防止に役立つ。光半導体含有層の屈折率を2以下
にするには、例えば光半導体がアナターゼ型酸化チタン
(屈折率2.5)のように屈折率が2をこえる物質の場
合には、光半導体以外に屈折率2未満の物質を添加す
る。屈折率2未満の物質としては、例えば、アルミナ
(屈折率1.6)、シリカ(屈折率1.5)、酸化錫
(屈折率1.9)、シリコン原子に結合された有機基の
少なくとも一部が水酸基に置換されたシリコーン樹脂
(屈折率1.4〜1.6)が好適に利用できる。The refractive index of the optical semiconductor-containing layer is preferably smaller than or not so large as that of the substrate. For example, when the substrate is a glass substrate (refractive index 1.5), the refractive index of the optical semiconductor-containing layer is preferably 2 or less. By doing so, the reflection of visible light on the surface of the composite material can be prevented, which helps to secure the visibility of the transparent material and prevent glare in the decorative exterior or coating. In order to reduce the refractive index of the optical semiconductor-containing layer to 2 or less, for example, when the optical semiconductor is a substance having a refractive index of more than 2 such as anatase-type titanium oxide (refractive index 2.5), it is refracted other than the optical semiconductor. A substance with a rate of less than 2 is added. Examples of the substance having a refractive index of less than 2 include at least one of alumina (refractive index: 1.6), silica (refractive index: 1.5), tin oxide (refractive index: 1.9), and an organic group bonded to a silicon atom. A silicone resin in which a part is substituted with a hydroxyl group (refractive index: 1.4 to 1.6) can be suitably used.
【0020】基材表面に、光半導体と、それ以外にアル
カリ金属、アルカリ土類金属、亜鉛、アルミニウム、白
金、パラジウム、ルテニウム等の金属を含む層を形成す
る方法は以下のような方法がある。(1)基材表面に、
光半導体粒子層を形成後、上記金属含有物を塗布し、乾
燥固定する。(2)基材表面に、光半導体粒子層を形成
後、上記金属含有物を塗布し、さらに光半導体の光励起
により金属を還元固定する。(3)基材表面に、光半導
体粒子と上記金属含有物を塗布後焼成する。(4)基材
表面に、光半導体粒子と上記金属含有物と、光半導体の
光励起により親水化しうる硬化性結着剤とを塗布後、硬
化性結着剤を硬化させ、さらに光半導体の光励起により
結着剤を親水化させる。The following methods can be used to form a layer containing an optical semiconductor and a metal such as an alkali metal, an alkaline earth metal, zinc, aluminum, platinum, palladium and ruthenium on the surface of a substrate. . (1) On the substrate surface,
After forming the optical semiconductor particle layer, the above-mentioned metal-containing material is applied and dried and fixed. (2) After forming an optical semiconductor particle layer on the surface of the substrate, the above-mentioned metal-containing substance is applied, and the metal is reduced and fixed by photoexcitation of the optical semiconductor. (3) After applying the optical semiconductor particles and the above-mentioned metal-containing material on the surface of the base material, the mixture is fired. (4) After applying the optical semiconductor particles, the above-mentioned metal-containing material, and a curable binder that can be hydrophilized by photoexcitation of the optical semiconductor to the surface of the base material, the curable binder is cured, and the photoexcitation of the optical semiconductor is further performed. Makes the binder hydrophilic.
【0021】光半導体粒子層の形成方法は、例えば、ゾ
ル塗布焼成法、アルコキシド法、スパッタリング法等が
ある。ゾル塗布焼成法とは、光半導体ゾルを、スプレー
コーティング、スピンコーティング、ディップコーティ
ング、ロールコーティング、フローコーティングその他
のコーティング法により、基材表面に塗布し、焼成する
方法である。アルコキシド法とは、例えば光半導体が結
晶性酸化チタンの場合には、チタンのアルコキシド(例
えば、テトラエトキシチタン、テトライソプロポキシチ
タン、テトラn−プロポキシチタン、テトラブトキシチ
タン、テトラメトキシチタン)に、塩酸又はエチルアミ
ンのような加水分解抑制剤を添加し、エタノールやプロ
パノール等の希釈剤で希釈した後、部分的に加水分解を
進行させながら又は完全に加水分解を進行させた後、混
合物をスプレーコーティング、スピンコーティング、デ
ィップコーティング、ロールコーティング、フローコー
ティングその他のコーティング法により、基材表面に塗
布し、乾燥させて無定型酸化チタン層を形成し、その
後、焼成により無定型酸化チタンを、アナターゼ型酸化
チタン或いはルチル型酸化チタンに変換させる方法であ
る。尚、チタンのアルコキシドに代えて、チタンのキレ
ート又はチタンのアセテートのような他の有機チタン化
合物を用いてもよい。スパッタリング法とは、例えば光
半導体が結晶性酸化チタンの場合には、金属チタン又は
酸化チタンをターゲットとし、酸素雰囲気で、基材表面
に無定型酸化チタン層を形成し、その後、焼成により無
定型酸化チタンを、アナターゼ型酸化チタン或いはルチ
ル型酸化チタンに変換させる方法である。The method for forming the optical semiconductor particle layer includes, for example, a sol coating and firing method, an alkoxide method, and a sputtering method. The sol coating and firing method is a method in which an optical semiconductor sol is applied to the surface of a substrate by spray coating, spin coating, dip coating, roll coating, flow coating, or another coating method, and then fired. The alkoxide method means that, for example, when the optical semiconductor is crystalline titanium oxide, titanium alkoxide (eg, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium) is added to hydrochloric acid Or after adding a hydrolysis inhibitor such as ethylamine, and diluting with a diluent such as ethanol or propanol, and then partially or completely proceeding the hydrolysis, spray coating the mixture, Spin coating, dip coating, roll coating, flow coating and other coating methods are applied to the substrate surface, dried to form an amorphous titanium oxide layer, and then fired to convert the amorphous titanium oxide to anatase titanium oxide Or rutile type titanium oxide A method for converted. Instead of titanium alkoxide, another organic titanium compound such as titanium chelate or titanium acetate may be used. With the sputtering method, for example, when the optical semiconductor is crystalline titanium oxide, an amorphous titanium oxide layer is formed on the surface of the base material in an oxygen atmosphere, using a metal titanium or titanium oxide as a target, and then, the amorphous material is formed by firing. In this method, titanium oxide is converted into anatase-type titanium oxide or rutile-type titanium oxide.
【0022】また金属含有物とは、例えば、アルカリ金
属、アルカリ土類金属、亜鉛、アルミニウム、白金、パ
ラジウム、ルテニウム等の金属化合物(塩化リチウム、
硝酸ナトリウム、塩化カリウム、塩化マグネシウム二水
塩、硝酸カルシウム、塩化ストロンチウム六水塩、塩化
亜鉛、塩化アルミニウム、塩化白金酸六水塩、塩化パラ
ジウム、塩化ルテニウム水和塩等)を溶質とする溶液等
をさす。The metal-containing material includes, for example, metal compounds such as alkali metals, alkaline earth metals, zinc, aluminum, platinum, palladium and ruthenium (lithium chloride,
Solutions containing sodium nitrate, potassium chloride, magnesium chloride dihydrate, calcium nitrate, strontium chloride hexahydrate, zinc chloride, aluminum chloride, chloroplatinic acid hexahydrate, palladium chloride, ruthenium chloride hydrate, etc. Point out.
【0023】光半導体の光励起により親水化しうる硬化
性結着剤とは、シリコーン樹脂、脱水縮重合すればシリ
コーン樹脂になるオルガノシラノール、加水分解・脱水
縮重合すればシリコーン樹脂になるオルガノアルコキシ
シラン等が挙げられる。結着剤の親水化方法は光半導体
の光励起により行うことができる。The curable binder which can be hydrophilized by photoexcitation of an optical semiconductor includes a silicone resin, an organosilanol which becomes a silicone resin by dehydration-condensation polymerization, and an organoalkoxysilane which becomes a silicone resin by hydrolysis and dehydration-condensation polymerization. Is mentioned. The method for hydrophilizing the binder can be performed by photoexcitation of the optical semiconductor.
【0024】基材表面に、光半導体と、それ以外にアル
ミナ、ジルコニア、セリア、イットリア等の酸化物を含
む層を形成する方法は以下のような方法がある。(5)
基材表面に、光半導体粒子と上記酸化物を塗布後焼成す
る。(6)基材表面に、光半導体の前駆体と上記酸化物
を塗布後、焼成等の方法で光半導体の前駆体を光半導体
に変換させる。(7)基材表面に、光半導体粒子と上記
酸化物と、光半導体の光励起により親水化しうる硬化性
結着剤とを塗布後、硬化性結着剤を硬化させ、さらに光
半導体の光励起により結着剤を親水化させる。There are the following methods for forming a layer containing an optical semiconductor and an oxide such as alumina, zirconia, ceria, yttria, etc. on the surface of the base material. (5)
After applying the photosemiconductor particles and the above oxide to the surface of the base material, firing is performed. (6) After coating the precursor of the optical semiconductor and the oxide on the surface of the base material, the precursor of the optical semiconductor is converted into the optical semiconductor by a method such as baking. (7) After coating the optical semiconductor particles, the oxide, and the curable binder that can be hydrophilized by photoexcitation of the optical semiconductor on the surface of the base material, the curable binder is cured, and the photocurable semiconductor is further excited by photoexcitation of the optical semiconductor. The binder is made hydrophilic.
【0025】光半導体の前駆体とは、例えば光半導体が
結晶性酸化チタンの場合には、チタンのアルコキシド
(例えば、テトラエトキシチタン、テトライソプロポキ
シチタン、テトラn−プロポキシチタン、テトラブトキ
シチタン、テトラメトキシチタン)、チタンのキレート
又はチタンのアセテートのような他の有機チタン化合物
を用いてもよい。光半導体の前駆体を光半導体に変換す
るとは、光半導体が結晶性酸化チタンの場合には、加水
分解、脱水縮重合、焼成等の過程により、アナターゼ型
酸化チタン或いはルチル型酸化チタンに変換させる方法
である。The precursor of the optical semiconductor is, for example, an alkoxide of titanium (for example, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetrabutoxytitanium, when the optical semiconductor is crystalline titanium oxide). Other organic titanium compounds such as methoxytitanium), chelates of titanium or acetate of titanium may be used. To convert a precursor of an optical semiconductor into an optical semiconductor means that, when the optical semiconductor is crystalline titanium oxide, it is converted into anatase-type titanium oxide or rutile-type titanium oxide by processes such as hydrolysis, dehydration-condensation polymerization, and firing. Is the way.
【0026】[0026]
【実施例】比較例1 15cm角の施釉タイル(東陶機器製、AB02E0
1)表面に、アンモニア解膠型の酸化チタンゾル(石原
産業製、STS−11)をスプレー・コーティング法に
て塗布し、800℃で焼成し試料を得た。このときの酸
化チタン層の膜厚は0.3μmとなるようにした。焼成
直後の試料表面の水との接触角を接触角測定器(協和界
面科学製、形式CA−X150)により測定した。接触
角は、マイクロシリンジから試料表面に水滴を滴下した
後30秒後に測定した。焼成直後の試料表面の水との接
触角は8゜であった。この試料を暗所に1週間放置し、
その後再び試料表面の水との接触角を測定したところ、
21゜まで上昇した。この上昇は吸着水の試料表面から
の離脱や、大気中の汚れ物質の付着によると考えられ
る。この試料に紫外線照度0.3mW/cm2のBLB
蛍光灯(三共電気製、ブラックライトブルー、FL20
BLB)を2日間照射した後、水との接触角を測定した
ところ、光励起に応じて試料表面は15゜までしか親水
化しなかった。EXAMPLES Comparative Example 1 A glazed tile of 15 cm square (manufactured by TOTO CORPORATION, AB02E0)
1) Ammonia-peptized titanium oxide sol (STS-11, manufactured by Ishihara Sangyo Co., Ltd.) was applied to the surface by a spray coating method, and fired at 800 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was measured with a contact angle measuring instrument (manufactured by Kyowa Interface Science, Model CA-X150). The contact angle was measured 30 seconds after a water drop was dropped on the sample surface from the micro syringe. The contact angle with water on the sample surface immediately after firing was 8 °. Leave this sample in the dark for one week,
After that, when the contact angle with water on the sample surface was measured again,
It has risen to 21 ゜. This rise is considered to be due to detachment of the adsorbed water from the sample surface and adhesion of contaminants in the atmosphere. BLB with ultraviolet illuminance 0.3 mW / cm 2 was applied to this sample.
Fluorescent lamp (manufactured by Sankyo Electric, black light blue, FL20
BLB) was irradiated for 2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized only up to 15 ° in response to the light excitation.
【0027】実施例1(カルシウム添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にカルシウ
ム金属濃度50μmol/gの硝酸カルシウム水溶液を
0.3g塗布後、0.4mW/cm2のBLB蛍光灯を
10分照射して試料を得た。この試料作製直後の試料表
面の水との接触角は38゜であった。この試料を暗所に
1週間放置し、その後再び試料表面の水との接触角を測
定したところ、22゜になった。さらにこの試料に紫外
線照度0.3mW/cm2のBLB蛍光灯(三共電気
製、ブラックライトブルー、FL20BLB)を0.2
日間照射した後、水との接触角を測定したところ、光励
起に応じて試料表面は5゜まで親水化された。Example 1 (Addition of calcium, post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. After applying 0.3 g of an aqueous solution of calcium nitrate having a calcium metal concentration of 50 μmol / g to the surface of the sample, a BLB fluorescent lamp of 0.4 mW / cm 2 was irradiated for 10 minutes to obtain a sample. The contact angle with water on the sample surface immediately after the preparation of the sample was 38 °. This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Furthermore, a BLB fluorescent lamp (manufactured by Sankyo Electric Co., Ltd., black light blue, FL20BLB) having an ultraviolet illuminance of 0.3 mW / cm 2 was applied to this sample for 0.2 hours.
After irradiation for one day, when the contact angle with water was measured, the sample surface was hydrophilized to 5 ° in response to the light excitation.
【0028】実施例2(カルシウム添加、混合添加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、カルシウム金属濃度77μmol
/gの硝酸カルシウム水溶液27gとを混合し、15c
m角の施釉タイル表面に、スプレー・コーティング法に
て塗布し、800℃で焼成し試料を得た。このときの酸
化チタン層の膜厚は0.3μmとなるようにした。この
試料作製直後の試料表面の水との接触角は22゜であっ
た。この試料を暗所に1週間放置し、その後再び試料表
面の水との接触角を測定したところ、25゜になった。
さらにこの試料に紫外線照度0.15mW/cm2のB
LB蛍光灯(三共電気製、ブラックライトブルー、FL
20BLB)を0.2日間照射した後、水との接触角を
測定したところ、光励起に応じて試料表面は8゜まで親
水化された。Example 2 (Calcium addition, mixing addition) Ammonia-peptized titanium oxide sol (ST, manufactured by Ishihara Sangyo)
S-11) 18 g, calcium metal concentration 77 μmol
/ G of calcium nitrate aqueous solution (27 g)
The sample was applied to the m-square glazed tile surface by a spray coating method and fired at 800 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle with water on the sample surface immediately after the preparation of the sample was 22 °. This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again.
Further, the sample was irradiated with B light having an ultraviolet illuminance of 0.15 mW / cm 2 .
LB fluorescent lamp (manufactured by Sankyo Denki, black light blue, FL
After irradiation with 20BLB) for 0.2 days, the contact angle with water was measured, and the sample surface was hydrophilized to 8 ° in response to photoexcitation.
【0029】実施例3(カリウム添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にカリウム
金属濃度50μmol/gの塩化カリウム水溶液を0.
3g塗布後、0.4mW/cm2のBLB蛍光灯を10
分照射して試料を得た。この試料作製直後の試料表面の
水との接触角は37゜であった。この試料を暗所に1週
間放置し、その後再び試料表面の水との接触角を測定し
たところ、27゜になった。さらにこの試料に紫外線照
度0.15mW/cm2のBLB蛍光灯を0.2日間照
射した後、水との接触角を測定したところ、光励起に応
じて試料表面は8゜まで親水化された。Example 3 (addition of potassium and post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. An aqueous solution of potassium chloride having a potassium metal concentration of 50 μmol / g was added to the surface of the sample in an amount of 0.1 μm.
After applying 3 g, a 0.4 mW / cm 2 BLB fluorescent lamp was
The sample was obtained by irradiation for one minute. The contact angle of the sample surface with water immediately after the preparation of the sample was 37 °. The sample was allowed to stand in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.15 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 8 ° in response to the light excitation.
【0030】実施例4(ナトリウム添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にナトリウ
ム金属濃度50μmol/gの硝酸ナトリウム水溶液を
0.3g塗布後、0.4mW/cm2のBLB蛍光灯を
10分照射して試料を得た。この試料作製直後の試料表
面の水との接触角は37゜であった。この試料を暗所に
1週間放置し、その後再び試料表面の水との接触角を測
定したところ、26゜になった。さらにこの試料に紫外
線照度0.3mW/cm2のBLB蛍光灯を0.2日間
照射した後、水との接触角を測定したところ、光励起に
応じて試料表面は7゜まで親水化された。Example 4 (addition of sodium and post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. After applying 0.3 g of an aqueous solution of sodium nitrate having a sodium metal concentration of 50 μmol / g to the surface of the sample, the sample was irradiated with a 0.4 mW / cm 2 BLB fluorescent lamp for 10 minutes to obtain a sample. The contact angle of the sample surface with water immediately after the preparation of the sample was 37 °. The sample was allowed to stand in a dark place for one week, and then the contact angle of the sample surface with water was measured again to be 26 °. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 7 ° in response to the light excitation.
【0031】実施例5(ナトリウム添加、混合添加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、ナトリウム金属濃度77μmol
/gの硝酸ナトリウム水溶液27gとを混合し、15c
m角の施釉タイル表面に、スプレー・コーティング法に
て塗布し、800℃で焼成し試料を得た。このときの酸
化チタン層の膜厚は0.3μmとなるようにした。この
試料作製直後の試料表面の水との接触角は17゜であっ
た。この試料を暗所に1週間放置し、その後再び試料表
面の水との接触角を測定したところ、22゜になった。
さらにこの試料に紫外線照度0.15mW/cm2のB
LB蛍光灯(三共電気製、ブラックライトブルー、FL
20BLB)を0.2日間照射した後、水との接触角を
測定したところ、光励起に応じて試料表面は6゜まで親
水化された。Example 5 (addition of sodium and mixing) Ammonia-peptized titanium oxide sol (ST, manufactured by Ishihara Sangyo)
S-11) 18 g, sodium metal concentration 77 μmol
/ G of sodium nitrate aqueous solution 27g, and 15c
The sample was applied to the m-square glazed tile surface by a spray coating method and fired at 800 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle with water on the sample surface immediately after this sample preparation was 17 °. This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again.
Further, the sample was irradiated with B light having an ultraviolet illuminance of 0.15 mW / cm 2 .
LB fluorescent lamp (manufactured by Sankyo Denki, black light blue, FL
After irradiation with 20BLB) for 0.2 days, the contact angle with water was measured, and the sample surface was hydrophilized to 6 ° in response to the light excitation.
【0032】実施例6(マグネシウム添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にマグネシ
ウム金属濃度50μmol/gの塩化マグネシウム二水
塩水溶液を0.3g塗布後、0.4mW/cm2のBL
B蛍光灯を10分照射して試料を得た。この試料作製直
後の試料表面の水との接触角は37゜であった。この試
料を暗所に1週間放置し、その後再び試料表面の水との
接触角を測定したところ、22゜になった。さらにこの
試料に紫外線照度0.3mW/cm2のBLB蛍光灯を
0.2日間照射した後、水との接触角を測定したとこ
ろ、光励起に応じて試料表面は8゜まで親水化された。Example 6 (addition of magnesium and post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. After applying 0.3 g of a magnesium chloride dihydrate aqueous solution having a magnesium metal concentration of 50 μmol / g to the surface of the sample, a BL of 0.4 mW / cm 2 was applied.
A sample was obtained by irradiating with a B fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 37 °. This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 8 ° in response to the light excitation.
【0033】実施例7(マグネシウム添加、混合添加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、ナトリウム金属濃度77μmol
/gの塩化マグネシウム二水塩水溶液27gとを混合
し、15cm角の施釉タイル表面に、スプレー・コーテ
ィング法にて塗布し、800℃で焼成し試料を得た。こ
のときの酸化チタン層の膜厚は0.3μmとなるように
した。この試料作製直後の試料表面の水との接触角は2
0゜であった。この試料を暗所に1週間放置し、その後
再び試料表面の水との接触角を測定したところ、25゜
になった。さらにこの試料に紫外線照度0.15mW/
cm 2のBLB蛍光灯(三共電気製、ブラックライトブ
ルー、FL20BLB)を0.2日間照射した後、水と
の接触角を測定したところ、光励起に応じて試料表面は
7゜まで親水化された。Example 7 (magnesium added, mixed added) Ammonia-peptized titanium oxide sol (manufactured by Ishihara Sangyo, ST
S-11) 18 g, sodium metal concentration 77 μmol
/ G of magnesium chloride dihydrate aqueous solution 27g
And a 15cm square glazed tile surface with a spray coater
The sample was applied by a coating method and baked at 800 ° C. to obtain a sample. This
In this case, the thickness of the titanium oxide layer should be 0.3 μm.
did. The contact angle with water on the sample surface immediately after the sample preparation was 2
It was 0 °. Leave this sample in the dark for one week and then
When the contact angle of the sample surface with water was measured again, 25 °
Became. Furthermore, the sample was irradiated with an ultraviolet illuminance of 0.15 mW /
cm TwoBLB fluorescent lamp (manufactured by Sankyo Electric Co., Ltd.
Lou, FL20BLB) for 0.2 days
When the contact angle of the sample was measured, the sample surface
It was hydrophilized to 7 °.
【0034】実施例8(リチウム添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にリチウム
金属濃度50μmol/gの塩化リチウム水溶液を0.
3g塗布後、0.4mW/cm2のBLB蛍光灯を10
分照射して試料を得た。この試料作製直後の試料表面の
水との接触角は36゜であった。この試料を暗所に1週
間放置し、その後再び試料表面の水との接触角を測定し
たところ、28゜になった。さらにこの試料に紫外線照
度0.3mW/cm2のBLB蛍光灯を0.2日間照射
した後、水との接触角を測定したところ、光励起に応じ
て試料表面は8゜まで親水化された。Example 8 (addition of lithium, post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. An aqueous solution of lithium chloride having a lithium metal concentration of 50 μmol / g was added to the surface of this sample in an amount of 0.
After applying 3 g, a 0.4 mW / cm 2 BLB fluorescent lamp was
The sample was obtained by irradiation for one minute. The contact angle of the sample surface with water immediately after the preparation of the sample was 36 °. The sample was allowed to stand in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 8 ° in response to the light excitation.
【0035】実施例9(亜鉛添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面に亜鉛金属
濃度50μmol/gの塩化亜鉛水溶液を0.3g塗布
後、0.4mW/cm2のBLB蛍光灯を10分照射し
て試料を得た。この試料作製直後の試料表面の水との接
触角は43゜であった。この試料を暗所に1週間放置
し、その後再び試料表面の水との接触角を測定したとこ
ろ、23゜になった。さらにこの試料に紫外線照度0.
15mW/cm2のBLB蛍光灯を0.2日間照射した
後、水との接触角を測定したところ、光励起に応じて試
料表面は8゜まで親水化された。Example 9 (addition of zinc, post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. After applying 0.3 g of an aqueous zinc chloride solution having a zinc metal concentration of 50 μmol / g to the surface of the sample, the sample was irradiated with a 0.4 mW / cm 2 BLB fluorescent lamp for 10 minutes to obtain a sample. The contact angle with water on the sample surface immediately after the preparation of the sample was 43 °. The sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with an ultraviolet light of 0.
After irradiation with a 15 mW / cm 2 BLB fluorescent lamp for 0.2 days, the contact angle with water was measured, and the sample surface was hydrophilized to 8 ° in response to the light excitation.
【0036】実施例10(ストロンチウム添加、後添
加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にストロン
チウム金属濃度50μmol/gの塩化ストロンチウム
六水塩水溶液を0.3g塗布後、0.4mW/cm2の
BLB蛍光灯を10分照射して試料を得た。この試料作
製直後の試料表面の水との接触角は33゜であった。こ
の試料を暗所に1週間放置し、その後再び試料表面の水
との接触角を測定したところ、23゜になった。さらに
この試料に紫外線照度0.3mW/cm2のBLB蛍光
灯を0.2日間照射した後、水との接触角を測定したと
ころ、光励起に応じて試料表面は7゜まで親水化され
た。Example 10 (Strontium added, post-added) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. After applying 0.3 g of a strontium chloride hexahydrate aqueous solution having a strontium metal concentration of 50 μmol / g to the surface of the sample, the sample was irradiated with a 0.4 mW / cm 2 BLB fluorescent lamp for 10 minutes to obtain a sample. The contact angle of the sample surface with water immediately after the preparation of the sample was 33 °. The sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 7 ° in response to the light excitation.
【0037】実施例11(ストロンチウム添加、混合添
加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、ストロンチウム金属濃度77μm
ol/gの塩化ストロンチウム六水塩水溶液27gとを
混合し、15cm角の施釉タイル表面に、スプレー・コ
ーティング法にて塗布し、700℃で焼成し試料を得
た。このときの酸化チタン層の膜厚は0.3μmとなる
ようにした。この試料作製直後の試料表面の水との接触
角は8゜であった。この試料を暗所に1週間放置し、そ
の後再び試料表面の水との接触角を測定したところ、1
4゜になった。さらにこの試料に紫外線照度0.15m
W/cm2のBLB蛍光灯(三共電気製、ブラックライ
トブルー、FL20BLB)を0.2日間照射した後、
水との接触角を測定したところ、光励起に応じて試料表
面は5゜まで親水化された。Example 11 (Addition of strontium, mixed addition) Ammonia-peptized titanium oxide sol (STI, manufactured by Ishihara Sangyo)
S-11) 18 g, strontium metal concentration 77 μm
ol / g of an aqueous strontium chloride hexahydrate solution (27 g) was mixed, applied to the surface of a 15 cm square glazed tile by a spray coating method, and fired at 700 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 8 °. The sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured.
It became 4 ゜. Further, the sample was irradiated with an ultraviolet illuminance of 0.15 m.
After irradiation with a W / cm 2 BLB fluorescent lamp (manufactured by Sankyo Electric Co., Ltd., black light blue, FL20BLB) for 0.2 days,
When the contact angle with water was measured, the sample surface was hydrophilized to 5 ° in response to the light excitation.
【0038】実施例12(白金添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面に白金金属
濃度50μmol/gの塩化白金酸六水塩水溶液を0.
3g塗布後、0.4mW/cm2のBLB蛍光灯を10
分照射して試料を得た。この試料作製直後の試料表面の
水との接触角は42゜であった。この試料を暗所に1週
間放置し、その後再び試料表面の水との接触角を測定し
たところ、18゜になった。さらにこの試料に紫外線照
度0.3mW/cm2のBLB蛍光灯を0.2日間照射
した後、水との接触角を測定したところ、光励起に応じ
て試料表面は6゜まで親水化された。その後、さらにこ
の試料に紫外線照度0.01mW/cm2の白色灯を9
日間照射し、室内照明下での親水維持性を調べた。その
結果、試料表面は9゜程度に維持された。Example 12 (Platinum added, post-added) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. An aqueous solution of chloroplatinic acid hexahydrate having a platinum metal concentration of 50 μmol / g was added to the surface of this sample in an amount of 0.
After applying 3 g, a 0.4 mW / cm 2 BLB fluorescent lamp was
The sample was obtained by irradiation for one minute. The contact angle of the sample surface with water immediately after the preparation of the sample was 42 °. This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 6 ° in response to the light excitation. Thereafter, a white lamp having an ultraviolet illuminance of 0.01 mW / cm 2 was further applied to the sample for 9 hours.
Irradiation was carried out for one day, and the hydrophilicity retention under indoor lighting was examined. As a result, the surface of the sample was maintained at about 9 °.
【0039】実施例13(白金添加、混合添加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、白金金属濃度77μmol/gの
塩化白金酸六水塩水溶液27gとを混合し、15cm角
の施釉タイル表面に、スプレー・コーティング法にて塗
布し、700℃で焼成し試料を得た。このときの酸化チ
タン層の膜厚は0.3μmとなるようにした。この試料
作製直後の試料表面の水との接触角は21゜であった。
この試料を暗所に1週間放置し、その後再び試料表面の
水との接触角を測定したところ、22゜になった。さら
にこの試料に紫外線照度0.15mW/cm2のBLB
蛍光灯(三共電気製、ブラックライトブルー、FL20
BLB)を0.2日間照射した後、水との接触角を測定
したところ、光励起に応じて試料表面は7゜まで親水化
された。Example 13 (Platinum addition, mixing addition) Ammonia-peptized titanium oxide sol (manufactured by Ishihara Sangyo, ST
S-11) 18 g and 27 g of an aqueous solution of chloroplatinic acid hexahydrate having a platinum metal concentration of 77 μmol / g were mixed, applied to the surface of a 15 cm square glazed tile by a spray coating method, and baked at 700 ° C. I got At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 21 °.
This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. In addition, a BLB having an ultraviolet illuminance of 0.15 mW / cm 2 was applied to this sample.
Fluorescent lamp (manufactured by Sankyo Electric, black light blue, FL20
(BLB) was irradiated for 0.2 days, and the contact angle with water was measured. The sample surface was hydrophilized to 7 ° in response to the light excitation.
【0040】実施例14(パラジウム添加、後添加) 比較例1と同様の方法で、膜厚0.3μmの酸化チタン
層被覆施釉タイル試料を得た。この試料表面にパラジウ
ム金属濃度50μmol/gの塩化パラジウム水溶液を
0.3g塗布後、0.4mW/cm2のBLB蛍光灯を
10分照射して試料を得た。この試料作製直後の試料表
面の水との接触角は47゜であった。この試料を暗所に
1週間放置し、その後再び試料表面の水との接触角を測
定したところ、18゜になった。さらにこの試料に紫外
線照度0.3mW/cm2のBLB蛍光灯を0.2日間
照射した後、水との接触角を測定したところ、光励起に
応じて試料表面は6゜まで親水化された。Example 14 (addition of palladium and post-addition) In the same manner as in Comparative Example 1, a glazed tile sample coated with a titanium oxide layer having a thickness of 0.3 μm was obtained. After applying 0.3 g of an aqueous solution of palladium chloride having a palladium metal concentration of 50 μmol / g to the surface of the sample, the sample was irradiated with a 0.4 mW / cm 2 BLB fluorescent lamp for 10 minutes to obtain a sample. The contact angle with water on the sample surface immediately after the preparation of the sample was 47 °. This sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again. Further, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 0.2 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 6 ° in response to the light excitation.
【0041】実施例15(パラジウム添加、混合添加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、パラジウム金属濃度77μmol
/gの塩化パラジウム水溶液27gとを混合し、15c
m角の施釉タイル表面に、スプレー・コーティング法に
て塗布し、700℃で焼成し試料を得た。このときの酸
化チタン層の膜厚は0.3μmとなるようにした。この
試料作製直後の試料表面の水との接触角は15゜であっ
た。この試料を暗所に1週間放置し、その後再び試料表
面の水との接触角を測定したところ、20゜になった。
さらにこの試料に紫外線照度0.15mW/cm2のB
LB蛍光灯(三共電気製、ブラックライトブルー、FL
20BLB)を0.2日間照射した後、水との接触角を
測定したところ、光励起に応じて試料表面は7゜まで親
水化された。Example 15 (addition of palladium and addition of mixture) Ammonia-peptized titanium oxide sol (STI, manufactured by Ishihara Sangyo)
S-11) 18 g, palladium metal concentration 77 μmol
/ G of an aqueous palladium chloride solution of 15 g
The sample was applied to the m-square glazed tile surface by a spray coating method and baked at 700 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 15 °. The sample was left in a dark place for one week, and then the contact angle of the sample surface with water was measured again.
Further, the sample was irradiated with B light having an ultraviolet illuminance of 0.15 mW / cm 2 .
LB fluorescent lamp (manufactured by Sankyo Denki, black light blue, FL
After irradiation with 20BLB) for 0.2 days, the contact angle with water was measured, and the sample surface was hydrophilized to 7 ° in response to the light excitation.
【0042】実施例16(ルテニウム添加、混合添加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)18gと、ルテニウム金属濃度77μmol
/gの塩化ルテニウム水和塩水溶液27gとを混合し、
15cm角の施釉タイル表面に、スプレー・コーティン
グ法にて塗布し、700℃で焼成し試料を得た。このと
きの酸化チタン層の膜厚は0.3μmとなるようにし
た。この試料作製直後の試料表面の水との接触角は15
゜であった。 この試料を暗所に1週間放置し、その後
再び試料表面の水との接触角を測定したところ、18゜
になった。さらにこの試料に紫外線照度0.15mW/
cm 2のBLB蛍光灯(三共電気製、ブラックライトブ
ルー、FL20BLB)を0.2日間照射した後、水と
の接触角を測定したところ、光励起に応じて試料表面は
7゜まで親水化された。Example 16 (addition of ruthenium and mixed addition) Ammonia-peptized titanium oxide sol (manufactured by Ishihara Sangyo, ST
S-11) 18 g, ruthenium metal concentration 77 μmol
/ G of ruthenium chloride hydrate aqueous solution 27 g,
Spray coating on 15cm square glazed tile surface
The sample was applied by a coating method and baked at 700 ° C. to obtain a sample. This and
The thickness of the titanium oxide layer should be 0.3 μm.
Was. The contact angle with water on the sample surface immediately after this sample preparation was 15
Was ゜. Leave this sample in the dark for one week and then
When the contact angle of the sample surface with water was measured again, the contact angle was 18 °.
Became. Furthermore, the sample was irradiated with an ultraviolet illuminance of 0.15 mW /
cm TwoBLB fluorescent lamp (manufactured by Sankyo Electric Co., Ltd.
Lou, FL20BLB) for 0.2 days
When the contact angle of the sample was measured, the sample surface
It was hydrophilized to 7 °.
【0043】実施例17(アルミニウム添加、混合添
加) アンモニア解膠型の酸化チタンゾル(石原産業製、ST
S−11)と、アルミニウム金属濃度50μmol/g
の塩化アルミニウム水溶液とを、酸化チタンとアルミニ
ウム金属量のモル比が87:13となるように混合し、
15cm角の施釉タイル表面に、スプレー・コーティン
グ法にて塗布し、700℃で焼成し試料を得た。このと
きの酸化チタン層の膜厚は0.7μmとなるようにし
た。この試料作製直後の試料表面の水との接触角は11
゜であった。この試料を暗所に1日放置し、その後再び
試料表面の水との接触角を測定したところ、13゜にな
った。さらにこの試料に紫外線照度0.15mW/cm
2のBLB蛍光灯(三共電気製、ブラックライトブル
ー、FL20BLB)を1日間照射した後、水との接触
角を測定したところ、光励起に応じて試料表面は3゜ま
で親水化された。Example 17 (addition of aluminum, addition of mixture) Ammonia-peptized titanium oxide sol (ST, manufactured by Ishihara Sangyo)
S-11) and an aluminum metal concentration of 50 μmol / g
Aluminum chloride aqueous solution is mixed so that the molar ratio of titanium oxide and aluminum metal is 87:13,
A 15 cm square glazed tile surface was applied by a spray coating method and baked at 700 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.7 μm. The contact angle with water on the sample surface immediately after this sample preparation was 11
Was ゜. The sample was left in a dark place for one day, and then the contact angle of the sample surface with water was measured. Further, the sample was irradiated with an ultraviolet illuminance of 0.15 mW / cm.
After irradiation with BLB fluorescent lamp No. 2 (manufactured by Sankyo Electric Co., Ltd., black light blue, FL20BLB) for one day, the contact angle with water was measured. The sample surface was hydrophilized to 3 ° in response to the light excitation.
【0044】実施例18(イットリア添加) 硝酸解膠型酸化チタンゾル(石原産業製、CS−N)と
酢酸解膠型酸化イットリウムゾル(多木化学製、溶質濃
度15重量%、平均結晶子径4nm、pH7.6)を、
酸化チタンと酸化イットリウムとのモル比が88:12
になるように混合した後、15cm角の施釉タイル表面
に、スプレーコーティング法にて塗布し、800℃で1
時間焼成し試料を得た。このときの膜厚は0.3μmに
なるようにした。焼成直後の試料表面の水との接触角は
21゜であった。得られた試料を、2週間暗所に放置し
た。その後再び試料表面の水との接触角を測定したとこ
ろ、25゜になった。その後、紫外線照度0.3mW/
cm2のBLB蛍光灯を13日間照射した後、水との接
触角を測定したところ、光励起に応じて試料表面は2゜
まで親水化された。その後紫外線照度0.004mW/
cm2の白色灯を4日間照射し、室内照明下での親水維
持性を調べた。その結果、試料表面は9゜程度に維持さ
れた。Example 18 (adding yttria) Nitrogen peptized titanium oxide sol (CS-N, manufactured by Ishihara Sangyo) and acetic acid peptized yttrium oxide sol (manufactured by Taki Kagaku, solute concentration: 15% by weight, average crystallite diameter: 4 nm) , PH 7.6)
The molar ratio of titanium oxide to yttrium oxide is 88:12
After that, the mixture was applied to the surface of a 15 cm square glazed tile by a spray coating method.
After sintering for a time, a sample was obtained. At this time, the film thickness was set to 0.3 μm. The contact angle with water on the sample surface immediately after firing was 21 °. The obtained sample was left in a dark place for 2 weeks. Thereafter, when the contact angle of the sample surface with water was measured again, it was 25 °. After that, UV illuminance 0.3mW /
After irradiating with a cm 2 BLB fluorescent lamp for 13 days, the contact angle with water was measured. The sample surface was hydrophilized to 2 ° in response to the light excitation. After that, UV illuminance 0.004mW /
A white light of 2 cm 2 was irradiated for 4 days, and the hydrophilicity retention under indoor lighting was examined. As a result, the surface of the sample was maintained at about 9 °.
【0045】実施例19(アルミナ添加) 硝酸解膠型酸化チタンゾル(石原産業製、CS−C)
と、酸化アルミニウムゾル(日産化学製、アルミナゾル
−100)を、酸化チタンと酸化アルミニウムとのモル
比が88:12になるように混合した後、15cm角の
施釉タイル表面に、スプレーコーティング法にて塗布
し、800℃で1時間焼成し試料を得た。このときの膜
厚は0.3μmになるようにした。焼成直後の試料表面
の水との接触角は2゜であった。得られた試料を、2週
間暗所に放置した。その後再び試料表面の水との接触角
を測定したところ、20゜になった。その後紫外線照度
0.3mW/cm2のBLB蛍光灯を13日間照射した
後、水との接触角を測定したところ、光励起に応じて試
料表面は再び2゜まで親水化された。その後紫外線照度
0.004mW/cm2の白色灯を2日間照射し、室内
照明下での親水維持性を調べた。その結果、試料表面は
9゜程度に維持された。Example 19 (addition of alumina) Nitric acid peptized titanium oxide sol (CS-C, manufactured by Ishihara Sangyo)
And aluminum oxide sol (alumina sol-100, manufactured by Nissan Chemical Industries, Ltd.) so that the molar ratio of titanium oxide and aluminum oxide is 88:12, and then spray-coated on the surface of a 15 cm square glazed tile. The sample was applied and baked at 800 ° C. for 1 hour to obtain a sample. At this time, the film thickness was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was 2 °. The obtained sample was left in a dark place for 2 weeks. Thereafter, when the contact angle of the sample surface with water was measured again, it was 20 °. Thereafter, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 13 days, and the contact angle with water was measured. The sample surface was again hydrophilized to 2 ° in response to the light excitation. Thereafter, a white light having an ultraviolet irradiance of 0.004 mW / cm 2 was irradiated for 2 days, and the hydrophilicity retention property under indoor lighting was examined. As a result, the surface of the sample was maintained at about 9 °.
【0046】実施例20(ジルコニア添加) アンモニア解膠型酸化チタンゾル(石原産業製、STS
−11)と、酸化ジルコニウムゾル印産化学製、NZS
−30B)を、酸化チタンと酸化ジルコニウムとのモル
比が88:12になるように混合した後、15cm角の
施釉タイル表面に、スプレーコーティング法にて塗布
し、800℃で1時間焼成し試料を得た。このときの膜
厚は0.3μmになるようにした。焼成直後の試料表面
の水との接触角は23゜であった。得られた試料を、1
週間暗所に放置した。その後再び試料表面の水との接触
角を測定したところ、35゜になった。その後紫外線照
度0.3mW/cm2のBLB蛍光灯を13日間照射し
た後、水との接触角を測定したところ、光励起に応じて
試料表面は4゜まで親水化された。Example 20 (Zirconia added) Ammonia peptized titanium oxide sol (STS, manufactured by Ishihara Sangyo)
-11) and zirconium oxide sol manufactured by Insan Chemical Industries, NZS
-30B) was mixed so that the molar ratio between titanium oxide and zirconium oxide was 88:12, applied to the surface of a 15 cm square glazed tile by a spray coating method, and baked at 800 ° C. for 1 hour. I got At this time, the film thickness was set to 0.3 μm. The contact angle with water on the sample surface immediately after firing was 23 °. The obtained sample was
Left for a week in the dark. After that, when the contact angle of the sample surface with water was measured again, it was 35 °. Thereafter, the sample was irradiated with a BLB fluorescent lamp having an ultraviolet illuminance of 0.3 mW / cm 2 for 13 days, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 4 ° in response to the light excitation.
【0047】実施例21(セリア添加) アンモニア解膠型酸化チタンゾル(石原産業製、STS
−11)と、酸化セリウムゾル(多木化学製W−15)
を、酸化チタンと酸化セリウムとのモル比が88:12
になるように混合した後、15cm角の施釉タイル表面
に、スプレーコーティング法にて塗布し、800℃で1
時間焼成し試料を得た。このときの膜厚は0.3μmに
なるようにした。焼成直後の試料表面の水との接触角は
22゜であった。得られた試料を、1週間暗所に放置し
た。その後再び試料表面の水との接触角を測定したとこ
ろ、38゜になった。その後紫外線照度0.3mW/c
m 2のBLB蛍光灯を13日間照射した後、水との接触
角を測定したところ、光励起に応じて試料表面は6゜ま
で親水化された。Example 21 (adding ceria) Ammonia peptized titanium oxide sol (STS, manufactured by Ishihara Sangyo)
-11) and cerium oxide sol (W-15 manufactured by Taki Kagaku)
With a molar ratio of titanium oxide to cerium oxide of 88:12
After mixing so that it becomes a glazed tile surface of 15 cm square
And spray coating at 800 ° C.
After sintering for a time, a sample was obtained. The film thickness at this time is 0.3 μm
I made it. The contact angle of the sample surface with water immediately after firing is
It was 22 ゜. Leave the sample in the dark for one week
Was. After that, the contact angle of the sample surface with water was measured again.
It was 38cm. After that, UV illuminance 0.3mW / c
m TwoContact with water after irradiating the BLB fluorescent lamp for 13 days
When the angle was measured, the sample surface was 6 mm depending on the light excitation.
Was made hydrophilic.
【0048】実施例22(水との接触角と防曇性との関
係) エタノールの溶媒86重量部に、テトラエトキシシラン
6重量部と純水6重量部とテトラエトキシシランの加水
分解抑制剤として36%塩酸2重量部を加えて混合し、
シリカコーティング溶液を調製した。混合により溶液は
発熱するので、混合液を約1時間放置冷却した。この溶
液をフローコーティング法により10cm角のソーダラ
イムガラス板の表面に塗布し、80℃の温度で乾燥させ
た。この間にテトラエトキシシランは加水分解を受けて
まずシラノールになり、続いてシラノールの脱水縮重合
により無定型シリカの薄膜がガラス板の表面に形成され
た。次に、テトラエトキシチタン(Merck社製)1
重量部とエタノール9重量部との混合物に加水分解抑制
剤として36%塩酸0.1重量部添加してチタニアコー
ティング溶液を調製し、この溶液を前記ガラス板の表面
に乾燥空気中でフローコーティング法により塗布した。
塗布量はチタニアに換算して45μg/cm 2とした。
次に、このガラスを10分間150℃の温度に保持する
ことにより、テトラエトキシチタンの加水分解を完了さ
せるとともに、生成した水酸化チタンを脱水縮重合に付
し、無定型チタニアを生成させた。こうして無定型シリ
カの上に無定型チタニアがコーティングされたガラス板
を得た。このガラス板を500℃の温度で焼成し、無定
型チタニアをアナターゼ型チタニアに変換した。得られ
た試料を数日間暗所に放置した。次に、BLB蛍光灯を
内蔵したデシケータ(温度24℃、湿度45〜50%)
内にこのガラス板を配置し、0.5mW/cm2の照度
で1日間紫外線を照射し、#1試料を得た。#1試料の
水との接触角を測定したところ0゜であった。次に、#
1試料をデシケータから取出して、60℃に保持した温
浴上に迅速に移し、15秒後に透過率を測定した。測定
された透過率を元の透過率で割り、水蒸気の凝縮により
生成した曇りに起因する透過率の変化を求めた。テトラ
エトキシチタン(Merck社製)1重量部とエタノー
ル9重量部との混合物に加水分解抑制剤として36%塩
酸0.1重量部添加してチタニアコーティング溶液を調
製し、この溶液を10cm角のガラス板の表面に乾燥空
気中でフローコーティング法により塗布した。塗布量は
チタニアに換算して45μg/cm2とした。次に、こ
のガラスを10分間150℃の温度に保持することによ
り、テトラエトキシチタンの加水分解を完了させるとと
もに、生成した水酸化チタンを脱水縮重合に付し、無定
型チタニアを生成させた。こうして無定型チタニアがコ
ーティングされたガラス板を得た。このガラス板を50
0℃の温度で焼成し、無定型チタニアをアナターゼ型チ
タニアに変換した。得られた試料を数日間暗所に放置し
た。次に、BLB蛍光灯を内蔵したデシケータ(温度2
4℃、湿度45〜50%)内にこのガラス板を配置し、
0.5mW/cm2の照度で水との接触角が3゜になる
まで紫外線を照射し、#2試料を得た。次に、#2試料
を暗所に放置した。異なる時間間隔で、#2試料を暗所
から取出し、水との接触角をその都度測定した。更に、
#2試料を一旦デシケータ(温度24℃、湿度45〜5
0%)内に移し、温度を平衡させた後、#1試料と同様
に、60℃に保持した温浴上に迅速に移し、15秒後に
透過率を測定し、水蒸気の凝縮により生成した曇りに起
因する透過率の変化を求めた。比較のため、市販の並板
ガラス、アクリル樹脂、ポリ塩化ビニル板、ポリカーボ
ネート板について、水との接触角を測定した。更に、こ
れらの板材を同じ条件のデシケータ内に移し、温度を平
衡させた後、同様に、60℃に保持した温浴上に迅速に
移し、15秒後に透過率を測定し、水蒸気の凝縮により
生成した曇りに起因する透過率の変化を求めた。得られ
た結果を表1に示す。表1の結果から、水との接触角が
10゜以下であれば、極めて高い防曇性が実現されるこ
とが確認された。上記実施例1〜21はいずれも光励起
に応じて水との接触角が10゜以下になることから、基
材に透明基材を選べば、いずれも優れた防曇性が発揮さ
れると考えられる。Example 22 (Relationship between contact angle with water and antifogging property)
Related) Tetraethoxysilane is added to 86 parts by weight of ethanol solvent.
6 parts by weight, 6 parts by weight of pure water and water of tetraethoxysilane
Add 2 parts by weight of 36% hydrochloric acid as a decomposition inhibitor and mix.
A silica coating solution was prepared. By mixing the solution
Due to heat generation, the mixture was left to cool for about 1 hour. This solution
Apply 10cm square sodara by flow coating method
Apply to the surface of the glass plate and dry at 80 ℃
Was. During this time, tetraethoxysilane undergoes hydrolysis.
First, it becomes silanol, followed by dehydration condensation polymerization of silanol.
Forms a thin film of amorphous silica on the surface of the glass plate
Was. Next, tetraethoxy titanium (Merck) 1
Hydrolysis inhibition in a mixture of 9 parts by weight of ethanol and 9 parts by weight
0.1% by weight of 36% hydrochloric acid
A preparing solution is prepared and the solution is placed on the surface of the glass plate.
Was applied by a flow coating method in dry air.
The coating amount is 45 μg / cm in terms of titania TwoAnd
Next, the glass is kept at a temperature of 150 ° C. for 10 minutes.
This completes the hydrolysis of tetraethoxytitanium.
And subject the generated titanium hydroxide to dehydration condensation polymerization.
Then, amorphous titania was produced. Thus, the amorphous silicon
Glass plate coated with amorphous titania on mosquito
I got This glass plate is fired at a temperature of 500 ° C.
Type titania was converted to anatase type titania. Obtained
The sample was left in the dark for several days. Next, the BLB fluorescent lamp
Built-in desiccator (temperature 24 ° C, humidity 45-50%)
Place this glass plate inside, 0.5mW / cmTwoIlluminance of
For 1 day to obtain a # 1 sample. # 1 sample
The measured contact angle with water was 0 °. next,#
One sample was taken out of the desiccator and kept at 60 ° C.
It was quickly transferred onto the bath and the transmittance was measured after 15 seconds. Measurement
Divided by the original transmittance, the condensation of water vapor
The change in transmittance due to the formed haze was determined. Tetra
1 part by weight of ethoxy titanium (Merck) and ethanol
36% salt as a hydrolysis inhibitor in a mixture with 9 parts by weight of
Add 0.1 part by weight of acid to prepare titania coating solution
And dry the solution on a 10 cm square glass plate surface.
It was applied by a flow coating method in the air. The application amount is
45 μg / cm in terms of titaniaTwoAnd Next,
By holding the glass at a temperature of 150 ° C. for 10 minutes.
When the hydrolysis of tetraethoxytitanium is completed,
In addition, the generated titanium hydroxide is subjected to dehydration polycondensation,
Form titania was produced. In this way, amorphous titania
A coated glass plate was obtained. 50 pieces of this glass plate
Firing at 0 ° C to convert amorphous titania to anatase type
Converted to Tania. Leave the sample in the dark for several days.
Was. Next, a desiccator with a built-in BLB fluorescent lamp (temperature 2
4 ° C, humidity 45-50%)
0.5mW / cmTwoContact angle with water is 3 ゜
Irradiation was carried out to obtain a # 2 sample. Next, sample # 2
Was left in the dark. # 2 samples in the dark at different time intervals
And the contact angle with water was measured each time. Furthermore,
The # 2 sample was once desiccated (temperature 24 ° C., humidity 45 to 5
0%) and equilibrate the temperature, then as in # 1 sample
Quickly on a warm bath maintained at 60 ° C. and after 15 seconds
The transmittance is measured, and the cloudiness generated by condensation of water vapor occurs.
The resulting change in transmittance was determined. For comparison, a commercially available plate
Glass, acrylic resin, polyvinyl chloride plate, polycarbonate
The contact angle of the nate plate with water was measured. In addition,
Transfer these plates into a desiccator under the same conditions,
After equilibration, also quickly place on a warm bath maintained at 60 ° C.
After 15 seconds, the transmittance is measured, and the water vapor is condensed.
The change in transmittance due to the formed haze was determined. Obtained
The results are shown in Table 1. From the results in Table 1, the contact angle with water is
If it is 10 ° or less, extremely high antifogging property can be realized.
Was confirmed. Examples 1 to 21 are all photoexcitation
The contact angle with water becomes 10 ° or less depending on the
If a transparent substrate is selected for the material, excellent anti-fog properties will be exhibited in all cases.
It is considered to be.
【0049】[0049]
【表1】 [Table 1]
【0050】実施例23 (水との接触角と防汚性との
関係) 種々の試料を以下に示す汚泥試験に付した。調べた試料
は、以下に示す#1〜#6試料である。#1試料:アナ
ターゼ型酸化チタンゾル(石原産業製、STS−11)
とコロイダルシリカゾル(スノーテックス20)との混
合物(固形分におけるシリカの割合が10重量%)を固
形分換算で4.5mgだけ、15cm四角の施釉タイル
(東陶機器製、AB02E01)に塗布し、880℃の
温度で10分焼成して、#0試料を得た。この#0試料
に、BLB蛍光灯を用いて0.5mW/cm2の紫外線
照度で3時間紫外線を照射して、#1試料を得た。#2
試料:#0試料に、さらに銅濃度50μmol/gの酢
酸銅一水塩水溶液を0.3g塗布後、BLB蛍光灯を用
いて0.4mW/cm2の紫外線照度で10分照射する
ことにより銅を固定した。その後、BLB蛍光灯を用い
て0.5mW/cm 2の紫外線照度で3時間紫外線を照
射して、#2試料を得た。#3試料:施釉タイル(東陶
機器製、AB02E01)。#4試料:アクリル樹脂
(PMMA)板。#5試料:人造大理石板(東陶機器
製、ML03)。#6試料:ポリテトラフルオロエチレ
ン(PTFE)板。汚泥試験は以下の要領で行った。ま
ず、汚泥スラリーを以下のようにして調製した。すなわ
ち、イエローオーカー64.3重量%、焼成関東ローム
21.4重量%、疎水性カーボンブラック4.8重量
%、シリカ粉4.8重量%、親水性カーボンブラック
4.7重量%を含む粉体混合物を1.05g/リッター
の濃度で水に懸濁させたスラリーを調製した。45度に
傾斜させた#1〜#6試料に、上記スラリー150ml
を流下させて15分間乾燥させ、次いで蒸留水150m
lを流下させて15分間乾燥させ、このサイクルを25
回反復した。試験前後の色差変化と光沢度変化を調べ
た。色差変化は、試験後の試料表面の色差から試験前の
試料表面の色差を引くことにより求めた。色差は日本工
業規格(JIS)H0201に従い、ΔE*表示を用い
た。光沢度の測定は日本工業規格(JIS)Z8741
の規定に従って行い、光沢度変化は試験後の試料表面の
光沢度を試験前の試料表面の光沢度で割ることにより求
めた。結果を表2に示す。Example 23 (Evaluation of contact angle with water and antifouling property)
Relationship) Various samples were subjected to the following sludge tests. The sample examined
Are samples # 1 to # 6 shown below. # 1 sample: Ana
Tase-type titanium oxide sol (STS-11, manufactured by Ishihara Sangyo)
With colloidal silica sol (Snowtex 20)
Compound (the proportion of silica in the solid content is 10% by weight)
Only 4.5mg in terms of shape, 15cm square glazed tile
(Manufactured by TOTO CORPORATION, AB02E01).
The sample was baked at a temperature for 10 minutes to obtain a # 0 sample. This # 0 sample
UV light of 0.5 mW / cm2 using a BLB fluorescent lamp
The sample was irradiated with ultraviolet light at an illuminance for 3 hours to obtain a # 1 sample. # 2
Sample: Vinegar with a copper concentration of 50 μmol / g was added to the # 0 sample.
After applying 0.3 g of aqueous acid copper monohydrate solution, use a BLB fluorescent lamp
0.4mW / cmTwoIrradiate with UV light for 10 minutes
This fixed the copper. Then, using a BLB fluorescent lamp
0.5mW / cm TwoUV light for 3 hours with UV light intensity
And a # 2 sample was obtained. # 3 sample: glazed tile (TOTO
AB02E01). # 4 sample: acrylic resin
(PMMA) plate. # 5 sample: artificial marble board
ML03). # 6 sample: polytetrafluoroethylene
(PTFE) plate. The sludge test was performed as follows. Ma
First, a sludge slurry was prepared as follows. Sand
64.3% by weight of yellow ocher, baked Kanto loam
21.4% by weight, 4.8% by weight of hydrophobic carbon black
%, Silica powder 4.8% by weight, hydrophilic carbon black
1.05 g / liter of powder mixture containing 4.7% by weight
To prepare a slurry suspended in water at a concentration of At 45 degrees
Add 150 ml of the above slurry to # 1 to # 6 samples
And let dry for 15 minutes, then 150m of distilled water
and allowed to dry for 15 minutes.
Repeated times. Examine the color difference change and gloss change before and after the test
Was. The color difference change is calculated from the color difference on the sample surface after the test.
It was determined by subtracting the color difference on the sample surface. Color difference is Nippon Kogyo
According to the industry standard (JIS) H0201, use ΔE * display
Was. The glossiness is measured according to Japanese Industrial Standard (JIS) Z8741.
The change in gloss is measured on the surface of the sample after the test.
The gloss is calculated by dividing the gloss by the gloss of the sample surface before the test.
I did. Table 2 shows the results.
【0051】[0051]
【表2】 [Table 2]
【0052】更に#1試料、#3試料、#4試料、#6
試料及び下記に示す#7試料について、屋外汚れ加速試
験を行った。#7試料:10cm角のアルミニウム基板
に、シリカゾル(日本合成ゴム製、グラスカA液)とト
リメトキシシラン(日本合成ゴム製、グラスカB液)
を、重量比が3:1となるように混合した液状物を塗布
し、150℃で硬化させ、膜厚3μmのシリコーン被覆
板(#7試料)を得た。屋外汚れ加速試験は、以下の要
領で行った。すなわち、茅ケ崎市所在の建物の屋上に図
1(a)及び図1(b)に示す屋外汚れ加速試験装置を
設置した。図1(a)及び図1(b)を参照するに、こ
の装置は、フレーム20に支持された傾斜した試料支持
面22を備え、試料24を取り付けるようになってい
る。フレームの頂部には前方に傾斜した屋根26が固定
してある。この屋根は波形プラスチック板からなり、集
まった雨が試料支持面22に取り付けた試料24の表面
に筋を成して流下するようになっている。この装置の試
料支持面22に上記#1試料、#3試料、#4試料、#
6試料及び#7試料を取り付け、1か月間屋外に暴露し
た。この試験における汚れの付着は雨天の流路である縦
筋部に多量の汚れが付着する傾向がある。そこで、試料
表面の汚れ具合を、試験後の縦筋汚れ部の色差から試験
前の色差を引くことにより評価した。結果を表3に示
す。Further, # 1, # 3, # 4, # 6
The sample and the # 7 sample shown below were subjected to an outdoor stain acceleration test. # 7 sample: Silica sol (Nippon Synthetic Rubber, Glaska A solution) and trimethoxysilane (Nippon Synthetic Rubber, Glaska B solution) on a 10 cm square aluminum substrate
Was coated at a weight ratio of 3: 1 and applied and cured at 150 ° C. to obtain a 3 μm-thick silicone-coated plate (# 7 sample). The outdoor dirt acceleration test was performed in the following manner. That is, the outdoor dirt acceleration test device shown in FIGS. 1A and 1B was installed on the roof of a building located in Chigasaki City. Referring to FIGS. 1 (a) and 1 (b), the apparatus has an inclined sample support surface 22 supported by a frame 20, and is adapted to mount a sample 24 thereon. A roof 26 inclined forward is fixed to the top of the frame. The roof is made of a corrugated plastic plate, and the collected rain flows down with streaks on the surface of the sample 24 attached to the sample support surface 22. The # 1 sample, # 3 sample, # 4 sample, #
Six and # 7 samples were mounted and exposed outdoors for one month. The adhesion of dirt in this test tends to cause a large amount of dirt to adhere to the vertical streak portion that is a flow path in rainy weather. Therefore, the degree of contamination on the sample surface was evaluated by subtracting the color difference before the test from the color difference of the vertical stripe stain after the test. Table 3 shows the results.
【0053】[0053]
【表3】 [Table 3]
【0054】理解を容易にするため、表2と表3に示し
た水との接触角及び色差変化を図2のグラフにプロット
した。図2のグラフにおいて、カーブAは汚れ加速試験
における大気中のカーボンブラックなどの燃焼生成物や
都市塵埃のような汚れによる色差変化と水との接触角と
の関係を示し、カーブBは汚泥試験における汚泥による
色差変化と水との接触角との関係を示す。図2のグラフ
を参照するに、カーブAから良く分かるように、基材の
水との接触角が増加するにつれて燃焼生成物や都市塵埃
による汚れが目立つようになる。これは、燃焼生成物や
都市塵埃のような汚染物質は基本的に疎水性であり、従
って、疎水性の表面に付着しやすいからである。これに
対して、カーブBは、汚泥による汚れは水との接触角が
20゜から50゜の範囲でピーク値を呈することを示し
ている。これは、泥や土のような無機物質は、本来、水
との接触角が20゜から50゜程度の親水性を有し、類
似の親水性を有する表面に付着しやすいからである。従
って、表面を水との接触角が20゜以下の親水性にする
か、或いは、水との接触角が60゜以上に疎水化すれ
ば、表面への無機物質の付着を防止することができるこ
とが分かる。水との接触角が20゜以下になると汚泥に
よる汚れが減少するのは、表面が水との接触角で20゜
以下の高度の親水性になると、無機物質に対する親和性
よりも水に対する親和性の方が高くなり、表面に優先的
に付着する水によって無機物質の付着が阻害されると共
に、付着しようとする無機物質が水によって容易に洗い
流されるからである。以上から、建物などの表面に疎水
性の汚れ物質と親水性の汚れ物質のいずれもが付着しな
いようにするため、或いは、表面に堆積した汚れが降雨
により洗い流されて表面がセルフクリーニングされるよ
うにするには、表面の水との接触角が20゜以下、好ま
しくは10゜以下、更に好ましくは5゜以下にすればよ
いことが分かる。上記実施例1〜21はいずれも光励起
に応じて水との接触角が10゜以下になることから、い
ずれも優れた降雨又は水洗による清浄性が発揮されると
考えられる。For easy understanding, the contact angles with water and the changes in color difference shown in Tables 2 and 3 were plotted on the graph of FIG. In the graph of FIG. 2, a curve A shows a relationship between a color difference change due to a combustion product such as carbon black in the atmosphere and a stain such as city dust in a stain acceleration test and a contact angle with water, and a curve B shows a sludge test. 2 shows the relationship between the change in color difference due to sludge and the contact angle with water. Referring to the graph of FIG. 2, as can be clearly understood from the curve A, as the contact angle of the base material with water increases, the contamination by combustion products and municipal dust becomes more conspicuous. This is because pollutants, such as combustion products and municipal dust, are basically hydrophobic and therefore easily adhere to hydrophobic surfaces. On the other hand, the curve B shows that the dirt due to the sludge exhibits a peak value when the contact angle with water is in the range of 20 ° to 50 °. This is because inorganic substances such as mud and soil originally have hydrophilicity with a contact angle with water of about 20 ° to 50 °, and easily adhere to surfaces having similar hydrophilicity. Therefore, if the surface is made hydrophilic so that the contact angle with water is 20 ° or less, or if the surface is made hydrophobic so that the contact angle with water is 60 ° or more, it is possible to prevent the adhesion of inorganic substances to the surface. I understand. When the contact angle with water is 20 ° or less, the dirt due to sludge decreases. When the surface becomes highly hydrophilic at a contact angle with water of 20 ° or less, affinity for water is higher than affinity for inorganic substances. This is because water is preferentially adhered to the surface, whereby the adhesion of the inorganic substance is hindered, and the inorganic substance to be adhered is easily washed away by the water. From the above, in order to prevent both hydrophobic and hydrophilic dirt substances from adhering to the surface of a building or the like, or to prevent dirt deposited on the surface from being washed away by rain and the surface to be self-cleaned. It can be seen that the contact angle with water on the surface should be 20 ° or less, preferably 10 ° or less, and more preferably 5 ° or less. In all of Examples 1 to 21, the contact angle with water becomes 10 ° or less in response to the light excitation, and it is considered that all of them exhibit excellent cleanliness by rainfall or washing with water.
【0055】[0055]
【発明の効果】基材表面に、光半導体以外にアルカリ金
属、アルカリ土類金属、亜鉛、アルミニウム、白金、パ
ラジウム、ルテニウム、アルミナ、ジルコニア、セリ
ア、イットリアのうちの少なくとも1種を含む層を形成
することにより、ゾル塗布焼成法で基材表面に光半導体
含有層を形成した場合においても、太陽光、室内照明等
の日常よく使用されている光源による光半導体の光励起
に応じて10゜以下まで親水化されるようになる。ま
た、ゾル塗布焼成法以外の、アルコキシド法、スパッタ
リング法、シリカ、シリコーンなどの結着剤の硬化を利
用した方法等で基材表面に光半導体含有層を形成した場
合においても、光半導体の光励起に応じた親水性能の向
上が期待できる。According to the present invention, a layer containing at least one of an alkali metal, an alkaline earth metal, zinc, aluminum, platinum, palladium, ruthenium, alumina, zirconia, ceria, and yttria is formed on the surface of a substrate. By doing so, even when the optical semiconductor-containing layer is formed on the substrate surface by the sol coating and firing method, up to 10 ° or less depending on the light excitation of the optical semiconductor by a light source that is commonly used, such as sunlight and indoor lighting. It becomes hydrophilic. In addition, even when the optical semiconductor-containing layer is formed on the substrate surface by a method other than the sol coating and firing method, such as an alkoxide method, a sputtering method, a method utilizing the curing of a binder such as silica or silicone, the optical excitation of the optical semiconductor Can be expected to improve the hydrophilic performance according to
【図1】屋外汚れ加速試験装置を示す図で、(a)は正
面図、(b)は側面図(寸法数値の単位はミリメート
ル)。BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view showing an outdoor dirt accelerating test apparatus, in which (a) is a front view and (b) is a side view (dimensions are in millimeters).
【図2】異なる親水性をもった表面が都市煤塵と汚泥に
よって汚れる度合いを示す図。FIG. 2 is a diagram showing the degree of contamination of surfaces having different hydrophilicities with urban dust and sludge.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C09D 201/00 C09D 201/00 C09K 3/18 C09K 3/18 101 101 (72)発明者 則本 圭一郎 福岡県北九州市小倉北区中島2丁目1番1 号 東陶機器株式会社内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 C09K 3/18 C09K 3/18 101 101 (72) Inventor Keiichiro Norimoto Fukuoka 2-1 Kitajima, Kokurakita-ku, Kitakyushu-shi
Claims (7)
ルカリ金属、アルカリ土類金属、亜鉛、アルミニウム、
白金、パラジウム、ルテニウム、アルミナ、ジルコニ
ア、セリア、イットリアの1群から選ばれた少なくとも
1種を含む層が形成されており、前記光半導体の光励起
に応じて部材表面が親水化されることを特徴とする親水
性材。1. An optical semiconductor and an alkali metal, an alkaline earth metal, zinc, aluminum,
A layer containing at least one selected from the group consisting of platinum, palladium, ruthenium, alumina, zirconia, ceria, and yttria is formed, and the surface of the member is hydrophilized in response to photoexcitation of the optical semiconductor. Hydrophilic material.
にアルカリ金属、アルカリ土類金属、亜鉛、アルミニウ
ム、白金、パラジウム、ルテニウム、アルミナ、ジルコ
ニア、セリア、イットリアの1群から選ばれた少なくと
も1種を含む層が形成されており、前記光半導体の光励
起に応じて部材表面が親水化されることを特徴とする防
曇性部材。2. On the surface of a transparent substrate, selected from the group consisting of an optical semiconductor and, in addition, an alkali metal, an alkaline earth metal, zinc, aluminum, platinum, palladium, ruthenium, alumina, zirconia, ceria, and yttria. An antifogging member, wherein a layer containing at least one kind is formed, and the surface of the member is hydrophilized in response to photoexcitation of the optical semiconductor.
アルカリ金属、アルカリ土類金属、亜鉛、アルミニウ
ム、白金、パラジウム、ルテニウム、アルミナ、ジルコ
ニア、セリア、イットリアの1群から選ばれた少なくと
も1種を含む層が形成されており、前記光半導体の光励
起に応じて部材表面が親水化されることを特徴とする防
曇性部材。3. The mirror substrate surface is selected from the group consisting of an optical semiconductor and an alkali metal, an alkaline earth metal, zinc, aluminum, platinum, palladium, ruthenium, alumina, zirconia, ceria, and yttria. An antifogging member, wherein a layer containing at least one kind is formed, and the surface of the member is hydrophilized in response to photoexcitation of the optical semiconductor.
ルカリ金属、アルカリ土類金属、亜鉛、アルミニウム、
白金、パラジウム、ルテニウム、アルミナ、ジルコニ
ア、セリア、イットリアの1群から選ばれた少なくとも
1種を含む層が形成されており、前記光半導体の光励起
に応じて部材表面が親水化され、水洗により表面付着堆
積物が洗い流されるようになる防汚性部材。4. An optical semiconductor and an alkali metal, an alkaline earth metal, zinc, aluminum,
A layer containing at least one selected from the group consisting of platinum, palladium, ruthenium, alumina, zirconia, ceria, and yttria is formed, and the surface of the member is hydrophilized in response to photoexcitation of the optical semiconductor, and the surface is washed with water. An antifouling member from which attached deposits can be washed away.
ルカリ金属、アルカリ土類金属、亜鉛、アルミニウム、
白金、パラジウム、ルテニウム、アルミナ、ジルコニ
ア、セリア、イットリアの1群から選ばれた少なくとも
1種を含む層が形成されており、前記光半導体の光励起
に応じて部材表面が親水化されて、付着水が一様に広が
って乾燥されやすくなる易乾燥性部材。5. An optical semiconductor and an alkali metal, an alkaline earth metal, zinc, aluminum,
A layer containing at least one member selected from the group consisting of platinum, palladium, ruthenium, alumina, zirconia, ceria, and yttria is formed, and the surface of the member is hydrophilized in response to the photoexcitation of the optical semiconductor, and the adhered water is formed. An easy-drying member that spreads uniformly and is easily dried.
の親水化は水との接触角に換算して10゜以下であるこ
とを特徴とする請求項1〜5に記載の部材。6. The member according to claim 1, wherein the hydrophilicity of the surface of the member in response to the photoexcitation of the optical semiconductor is 10 ° or less in terms of a contact angle with water.
の親水化は水との接触角に換算して5゜以下であること
を特徴とする請求項1〜5に記載の部材。7. The member according to claim 1, wherein a hydrophilization of the surface of the member according to the photoexcitation of the optical semiconductor is 5 ° or less in terms of a contact angle with water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23956799A JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35464995 | 1995-12-22 | ||
JP7-354649 | 1995-12-22 | ||
JP23956799A JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8195184A Division JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000227055A Division JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2000136370A true JP2000136370A (en) | 2000-05-16 |
JP3613084B2 JP3613084B2 (en) | 2005-01-26 |
Family
ID=18438979
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---|---|---|---|
JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
JP15017196A Expired - Lifetime JP3760509B2 (en) | 1995-12-22 | 1996-05-22 | Greenhouse ceiling and its condensation prevention method |
JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
JP8272814A Pending JPH09226041A (en) | 1995-12-22 | 1996-09-06 | Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member |
JP8272815A Pending JPH09224957A (en) | 1995-12-22 | 1996-09-06 | Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
JP8272808A Pending JPH09229724A (en) | 1995-12-22 | 1996-09-07 | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP08282811A Expired - Fee Related JP3075195B2 (en) | 1995-12-22 | 1996-09-18 | Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror |
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JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
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JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
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JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
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JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
JP8323516A Pending JPH09241038A (en) | 1995-12-22 | 1996-11-19 | Photocatalytic hydrophilic member and its production |
JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
JP23956799A Expired - Lifetime JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
JP34300999A Expired - Fee Related JP3844182B2 (en) | 1995-12-22 | 1999-12-02 | Hydrophilic film and method for producing and using the same |
JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
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JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Family Applications Before (59)
Application Number | Title | Priority Date | Filing Date |
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JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
JP15017196A Expired - Lifetime JP3760509B2 (en) | 1995-12-22 | 1996-05-22 | Greenhouse ceiling and its condensation prevention method |
JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
JP8272814A Pending JPH09226041A (en) | 1995-12-22 | 1996-09-06 | Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member |
JP8272815A Pending JPH09224957A (en) | 1995-12-22 | 1996-09-06 | Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
JP8272808A Pending JPH09229724A (en) | 1995-12-22 | 1996-09-07 | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
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JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP08282811A Expired - Fee Related JP3075195B2 (en) | 1995-12-22 | 1996-09-18 | Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
JP28453496A Expired - Lifetime JP3173391B2 (en) | 1995-12-22 | 1996-09-19 | Hydrophilic film, and method for producing and using the same |
JP28579796A Expired - Lifetime JP3697795B2 (en) | 1995-12-22 | 1996-09-20 | Display and cleaning method thereof |
JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
JP28895596A Expired - Lifetime JP3774955B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning handrail and handrail cleaning method |
JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
JP8323516A Pending JPH09241038A (en) | 1995-12-22 | 1996-11-19 | Photocatalytic hydrophilic member and its production |
JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
Family Applications After (11)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP34300999A Expired - Fee Related JP3844182B2 (en) | 1995-12-22 | 1999-12-02 | Hydrophilic film and method for producing and using the same |
JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
JP2002020533A Expired - Fee Related JP3882625B2 (en) | 1995-12-22 | 2002-01-29 | Sound insulation wall and cleaning method for sound insulation wall |
JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Country Status (1)
Country | Link |
---|---|
JP (71) | JPH09231821A (en) |
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WO2012014893A1 (en) | 2010-07-29 | 2012-02-02 | Toto株式会社 | Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material |
US9079155B2 (en) | 2010-07-29 | 2015-07-14 | Toto Ltd. | Photocatalyst coated body and photocatalyst coating liquid |
US9221031B2 (en) | 2010-07-29 | 2015-12-29 | Toto Ltd. | Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material |
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