JPH09224800A - Glassware and water-washing method - Google Patents
Glassware and water-washing methodInfo
- Publication number
- JPH09224800A JPH09224800A JP8307000A JP30700096A JPH09224800A JP H09224800 A JPH09224800 A JP H09224800A JP 8307000 A JP8307000 A JP 8307000A JP 30700096 A JP30700096 A JP 30700096A JP H09224800 A JPH09224800 A JP H09224800A
- Authority
- JP
- Japan
- Prior art keywords
- water
- surface layer
- photo
- photocatalyst
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005406 washing Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002344 surface layer Substances 0.000 claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 claims abstract description 48
- 239000010410 layer Substances 0.000 claims abstract description 16
- 239000000356 contaminant Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 13
- 230000001443 photoexcitation Effects 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 239000011973 solid acid Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 239000011241 protective layer Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 58
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 38
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 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
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- -1 Titanium alkoxide Chemical class 0.000 description 3
- 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 3
- 230000009471 action Effects 0.000 description 3
- 239000002772 conduction electron Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 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 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- YSALUHGLIBYTET-UHFFFAOYSA-N benzyl(dibutoxy)silane Chemical compound CCCCO[SiH](OCCCC)CC1=CC=CC=C1 YSALUHGLIBYTET-UHFFFAOYSA-N 0.000 description 1
- XSVRIICVXZBSCH-UHFFFAOYSA-N benzyl(dipropoxy)silane Chemical compound CCCO[SiH](OCCC)CC1=CC=CC=C1 XSVRIICVXZBSCH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MGQFVQQCNPBJKC-UHFFFAOYSA-N dibutoxy(diethyl)silane Chemical compound CCCCO[Si](CC)(CC)OCCCC MGQFVQQCNPBJKC-UHFFFAOYSA-N 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- BZCJJERBERAQKQ-UHFFFAOYSA-N diethyl(dipropoxy)silane Chemical compound CCCO[Si](CC)(CC)OCCC BZCJJERBERAQKQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、ガラス食器(ガラ
スコップも含む)のうち特に表面に付着した汚れを水洗
い等によって簡単に落とすことができる食器に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glass tableware (including glass cups), and particularly to tableware capable of easily removing dirt adhering to the surface thereof by washing with water or the like.
【0002】[0002]
【従来の技術】食器に付着した食物の油汚れは落しにく
い。特にガラス食器は透明なため、汚れが付着すると目
立つ。このため、中性洗剤等に食器を浸け、油分を表面
から浮かせてから水洗いする化学的な方法が一般家庭で
は行われている。2. Description of the Related Art Oily stains on food adhered to tableware are difficult to remove. In particular, glass tableware is transparent, so it stands out when dirt adheres. For this reason, a chemical method of immersing dishes in a neutral detergent or the like, floating oil on the surface, and then washing with water is used in ordinary households.
【0003】[0003]
【発明が解決しようとする課題】食器の油汚れを落とす
ために洗剤を使用すると、肌荒れの原因になる。また、
近年、家庭からの中性洗剤含有廃水が河川の水質汚濁の
原因として問題化している。そこで、本発明の目的は、
水で濯ぐ又は水に浸漬する程度で簡単に洗浄可能な表面
を有するガラス食器及びその洗浄方法を提供することに
ある。The use of detergents to remove oil stains on tableware causes rough skin. Also,
In recent years, wastewater containing neutral detergent from households has become a problem as a cause of water pollution in rivers. Therefore, the purpose of the present invention is to
It is an object of the present invention to provide a glass dish having a surface that can be easily washed by rinsing with water or immersing in water, and a method for washing the same.
【0004】[0004]
【課題を解決するための手段】本発明は、光触媒を含有
する表面層を形成した部材において、光触媒を光励起す
ると、部材の表面が高度に親水化されるという発見に基
づく。この現象は以下に示す機構により進行すると考え
られる。すなわち、光触媒の価電子帯上端と伝導帯下端
とのエネルギーギャップ以上のエネルギーを有する光が
光触媒に照射されると、光触媒の価電子帯中の電子が励
起されて伝導電子と正孔が生成し、そのいずれかまたは
双方の作用により、おそらく表面に極性が付与され、水
や水酸基等の極性成分が集められる。そして伝導電子と
正孔のいずれかまたは双方と、上記極性成分との協調的
な作用により、表面と前記表面に化学的に吸着した汚染
物質との化学結合を切断すると共に、表面に化学吸着水
が吸着し、さらに物理吸着水層がその上に形成されるの
である。また、一旦部材表面が高度に親水化されたなら
ば、部材を暗所に保持しても、表面の親水性はある程度
の期間持続する。SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst formed thereon, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the following mechanism. That is, when the photocatalyst is irradiated with light having an energy larger than the energy gap between the valence band upper end and the conduction band lower end of the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. The action of either or both of them probably imparts polarity to the surface and collects polar components such as water and hydroxyl groups. Then, one or both of conduction electrons and holes and the above-mentioned polar component cooperate with each other to cut off a chemical bond between the surface and the contaminant chemically adsorbed on the surface, and to cause a chemical adsorbed water on the surface. Is adsorbed, and a physically adsorbed water layer is formed thereon. Further, once the surface of the member is highly hydrophilized, the hydrophilicity of the surface is maintained for a certain period even if the member is kept in a dark place.
【0005】本発明では、ガラス食器基材の表面に、光
触媒粒子を含有する表面層を備えた易洗浄性ガラス食器
を提供する。光触媒を含有する表面層を備えることによ
り、光触媒の光励起に応じて、表面層の表面は親水性を
呈するので、ガラス食器の表面を水で濯ぐ又は水に浸漬
する程度で簡単に洗浄可能になる。The present invention provides easily washable glass tableware having a surface layer containing photocatalyst particles on the surface of a glass tableware substrate. By providing a surface layer containing a photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, so that the surface of the glass tableware can be easily washed by rinsing it with water or immersing it in water. Become.
【0006】本発明の好ましい態様においては、表面層
には、さらにシリカが含有されているようにする。シリ
カが含有されることにより、表面が水濡れ角0゜に近い
高度の親水性を呈しやすくなると共に、暗所に保持した
ときの親水維持性が向上する。その理由はシリカは構造
中に水を蓄えることができることと関係していると思わ
れる。In a preferred embodiment of the present invention, the surface layer further contains silica. By containing silica, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. The reason seems to be related to the ability of silica to store water in its structure.
【0007】本発明の好ましい態様においては、表面層
には、さらに固体酸が含有されているようにする。固体
酸が含有されることにより、表面が水濡れ角0゜に近い
高度の親水性を呈しやすくなると共に、暗所に保持した
ときの親水維持性が向上する。その理由は表面層に固体
酸が含有されると、表面の極性が、光の有無にかかわら
ず大きな状態にあるために、疎水性分子よりも極性分子
である水分子を選択的に吸着させやすい。そのため安定
な物理吸着水層が形成されやすく、暗所に保持しても、
表面の親水性をかなり長期にわたり高度に維持できる。In a preferred embodiment of the present invention, the surface layer further contains a solid acid. When the solid acid is contained, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when kept in a dark place is improved. The reason is that when a solid acid is contained in the surface layer, the polarity of the surface is large regardless of the presence or absence of light, so it is easier to selectively adsorb water molecules that are polar molecules than hydrophobic molecules. . Therefore, a stable physical adsorption water layer is easily formed, and even if it is kept in a dark place,
Surface hydrophilicity can be maintained at a high level for a fairly long time.
【0008】本発明の好ましい態様においては、表面層
には、さらにシリコーンが含有されているようにする。
シリコーンが含有されることにより、光触媒の光励起に
よって、シリコーン中のシリコン原子に結合する有機基
の少なくとも一部が水酸基に置換され、さらにその上に
物理吸着水層が形成されることにより、表面が水濡れ角
0゜に近い高度の親水性を呈するようになると共に、暗
所に保持したときの親水維持性が向上する。In a preferred embodiment of the present invention, the surface layer further contains silicone.
By containing silicone, by photoexcitation of the photocatalyst, at least a part of the organic group bonded to the silicon atom in the silicone is replaced with a hydroxyl group, and a physically adsorbed water layer is formed on the organic group, so that the surface is It exhibits a high degree of hydrophilicity close to a water wetting angle of 0 °, and improves the hydrophilicity maintaining ability when kept in a dark place.
【0009】[0009]
【発明の実施の形態】次に、本発明の具体的な構成につ
いて説明する。本発明におけるガラス食器の表面には、
図1又は図2に示すように、基材の表面に光触媒を含む
層が形成されている。このような表面構造をとること
で、ガラス食器の表面は、光触媒の光励起に応じて高度
に親水化されるのである。それにより、表面の親水性が
親油性より強まる。それにより、ガラス食器の表面を水
で洗浄するのが容易になる。BEST MODE FOR CARRYING OUT THE INVENTION Next, a specific structure of the present invention will be described. On the surface of the glass tableware in the present invention,
As shown in FIG. 1 or FIG. 2, a layer containing a photocatalyst is formed on the surface of the substrate. By taking such a surface structure, the surface of the glass tableware is highly hydrophilized in response to photoexcitation of the photocatalyst. Thereby, the hydrophilicity of the surface becomes stronger than the lipophilicity. This makes it easy to wash the surface of the glass tableware with water.
【0010】図1においては、表面層が光触媒のみから
なる場合には、光触媒は酸化物であることが好ましい。
そうすることにより、酸化物は環境中の汚染物質が吸着
していない状態では親水性を示すので、光励起作用によ
りその汚染物質を排斥させ、吸着水層を形成させること
で、親水性を呈しやすく、一様な水膜が形成できる。図
2において、Mは金属元素を示す。従って、図2の場
合、最表面は一般の無機酸化物からなる。この場合も、
酸化物は環境中の汚染物質が吸着していない状態では親
水性を示すので、上記無機酸化物以外に表面層に混入す
る光触媒の光励起作用によりその汚染物質を排斥させ、
吸着水層を形成させることで、一様な水膜が形成でき
る。In FIG. 1, when the surface layer comprises only a photocatalyst, the photocatalyst is preferably an oxide.
By doing so, the oxide shows hydrophilicity in the state where the pollutants in the environment are not adsorbed, so that the pollutants are rejected by the photoexcitation action and the adsorbed water layer is formed, so that the oxides easily exhibit hydrophilicity. A uniform water film can be formed. In FIG. 2, M represents a metal element. Therefore, in the case of FIG. 2, the outermost surface is made of a general inorganic oxide. Again,
Since the oxide shows hydrophilicity in a state where the pollutant in the environment is not adsorbed, the pollutant is rejected by a photoexcitation effect of a photocatalyst mixed into the surface layer other than the inorganic oxide,
By forming the adsorbed water layer, a uniform water film can be formed.
【0011】光触媒とは、その結晶の伝導帯と価電子帯
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)の光(励起光)を照射したとき
に、価電子帯中の電子の励起(光励起)が生じて、伝導
電子と正孔を生成しうる物質をいい、例えば、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好適に利用できる。こ
こで光触媒の光励起に用いる光源としては、蛍光灯、白
熱電灯、メタルハライドランプ、ブラックライトラン
プ、キセノンランプ、水銀灯、太陽光などが好適に利用
できる。光触媒の光励起により、基材表面が高度に親水
化されるためには、励起光の照度は、0.001mW/
cm2以上あればよいが、0.01mW/cm2以上だと
好ましく、0.1mW/cm2以上だとより好ましい。A photocatalyst is a photocatalyst of an electron in the valence band when irradiated with light (excitation light) having an energy (that is, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. A substance that is excited (photoexcited) to generate conduction electrons and holes. For example, anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, oxide trioxide. Diiron, strontium titanate and the like can be preferably used. Here, as a light source used for photoexcitation of the photocatalyst, a fluorescent lamp, an incandescent lamp, a metal halide lamp, a black light lamp, a xenon lamp, a mercury lamp, sunlight, and the like can be suitably used. In order to make the surface of the base material highly hydrophilic by photoexcitation of the photocatalyst, the illuminance of the excitation light is 0.001 mW /
cm 2 suffices above, but preferably that it 0.01 mW / cm 2 or more, and more preferably it 0.1 mW / cm 2 or more.
【0012】光触媒を含有する表面層の膜厚は、0.4
μm以下にするのが好ましい。そうすれば、光の乱反射
による白濁を防止することができ、表面層は実質的に透
明となる。さらに、光触媒を含有する表面層の膜厚を
0.2μm以下にすると一層好ましい。そうすれば、光
の干渉による表面層の発色を防止することができる。ま
た、表面層が薄ければ薄いほどその透明度は向上する。
更に、膜厚を薄くすれば、表面層の耐摩耗性が向上す
る。上記表面層の表面に、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良い。The thickness of the surface layer containing the photocatalyst is 0.4
It is preferable that the thickness is less than or equal to μm. Then, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. More preferably, the thickness of the surface layer containing the photocatalyst is 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved. The surface of the surface layer may be further provided with a wear-resistant or corrosion-resistant protective layer capable of being made hydrophilic and other functional films.
【0013】上記表面層は、基材と比較して屈折率があ
まり高くないのが好ましい。好ましくは表面層の屈折率
は2以下であるのがよい。そうすれば、基材と表面層と
の界面、及び表面層と空気との界面における光の反射を
抑制できる。表面層の屈折率を2以下にするには、光触
媒に2以下の屈折率を有する物質を用いるか、或いは光
触媒が屈折率2以上の場合には、屈折率2以下の他の物
質を表面層に添加する。2以下の屈折率を有する光触媒
としては、酸化錫(屈折率1.9)等が利用できる。2
以上の屈折率を有する光触媒としては、アナターゼ型酸
化チタン(屈折率2.5)やルチル型酸化チタン(屈折
率2.7)があるが、この場合には屈折率2以下の他の
物質、例えば、炭酸カルシウム(屈折率1.6)、ドロ
マイト(屈折率1.7)、炭酸マグネシウム(屈折率
1.5)、水酸化カルシウム(屈折率1.6)、炭酸ス
トロンチウム(屈折率1.5)、フッ化マグネシウム
(屈折率1.4)、フッ化カルシウム(屈折率1.
4)、シリカ(屈折率1.5)、アルミナ(屈折率1.
6)、ケイ砂(屈折率1.6)、カオリン(屈折率1.
6)、モンモリロナイト(屈折率1.5)、セリサイト
(屈折率1.6)、ゼオライト(屈折率1.6)、酸化
錫(屈折率1.9)等を表面層に添加すればよい。The surface layer preferably has a refractive index not so high as compared with the substrate. Preferably, the refractive index of the surface layer is 2 or less. Then, light reflection at the interface between the substrate and the surface layer and the interface between the surface layer and air can be suppressed. In order to reduce the refractive index of the surface layer to 2 or less, a substance having a refractive index of 2 or less is used for the photocatalyst, or if the photocatalyst has a refractive index of 2 or more, another substance having a refractive index of 2 or less is used for the surface layer. To be added. As a photocatalyst having a refractive index of 2 or less, tin oxide (refractive index: 1.9) or the like can be used. 2
As the photocatalyst having the above refractive index, there are anatase type titanium oxide (refractive index 2.5) and rutile type titanium oxide (refractive index 2.7). In this case, other substances having a refractive index of 2 or less, For example, calcium carbonate (refractive index 1.6), dolomite (refractive index 1.7), magnesium carbonate (refractive index 1.5), calcium hydroxide (refractive index 1.6), strontium carbonate (refractive index 1.5). ), Magnesium fluoride (refractive index 1.4), calcium fluoride (refractive index 1.
4), silica (refractive index 1.5), alumina (refractive index 1.
6), silica sand (refractive index 1.6), kaolin (refractive index 1.
6), montmorillonite (refractive index 1.5), sericite (refractive index 1.6), zeolite (refractive index 1.6), tin oxide (refractive index 1.9) and the like may be added to the surface layer.
【0014】上記表面層には、Ag、Cu、Znのよう
な金属を添加することができる。前記金属を添加した表
面層は、表面に付着した細菌や黴を暗所でも死滅させる
ことができる。A metal such as Ag, Cu, or Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.
【0015】上記表面層には、Pt、Pd、Ru、R
h、Ir、Osのような白金族金属を添加することがで
きる。前記金属を添加した表面層は、光触媒の酸化還元
活性を増強でき、脱臭浄化作用等が向上する。また、光
触媒以外に固体酸を添加した場合には、白金族金属の添
加により固体酸の酸度が向上するので、親水維持性も向
上し、付着水の水膜化がより促進されると共に、ある程
度長期間光触媒に励起光が照射されない場合の親水維持
性も向上する。上記表面層には、Moが添加されていて
もよい。この場合も光触媒以外に固体酸を添加した場合
に、固体酸の酸度が向上するので、親水維持性も向上
し、付着水の水膜化がより促進されると共に、ある程度
長期間光触媒に励起光が照射されない場合の親水維持性
も向上する。The surface layer includes Pt, Pd, Ru, R
A platinum group metal such as h, Ir, Os can be added. The surface layer to which the metal is added can enhance the oxidation-reduction activity of the photocatalyst and improve the deodorizing and purifying action and the like. In addition, when a solid acid is added in addition to the photocatalyst, the acidity of the solid acid is improved by the addition of a platinum group metal, so that the hydrophilicity is also improved, and the formation of a water film on the attached water is further promoted. The hydrophilicity when the excitation light is not irradiated to the photocatalyst for a long period of time is also improved. Mo may be added to the surface layer. Also in this case, when a solid acid is added in addition to the photocatalyst, the acidity of the solid acid is improved, so that the hydrophilicity retention property is also improved, the water film of the attached water is further promoted, and the photocatalyst is excited for a long period of time. Is also improved when not irradiated.
【0016】基材がナトリウムのようなアルカリ網目修
飾イオンを含むガラス(ソーダライムガラス、並板ガラ
ス等)の場合には、基材と表面層との間にシリカ等の中
間層を形成してもよい。そうすれば、焼成中にアルカリ
網目修飾イオンが基材から表面層へ拡散するのが防止さ
れ、光触媒機能がよりよく発揮される。When the substrate is glass containing alkali network modifying ions such as sodium (soda lime glass, parallel plate glass, etc.), an intermediate layer such as silica may be formed between the substrate and the surface layer. Good. Then, the diffusion of the alkali network modifying ions from the base material to the surface layer during the firing is prevented, and the photocatalytic function is more effectively exhibited.
【0017】親水性とは、表面に水を滴下したときにな
じみやすい性質をいい、一般に水濡れ角が90゜未満の
状態をいう。本発明における高度の親水性とは、表面に
水を滴下したときに非常になじみやすい性質をいい、よ
り具体的には水濡れ角が10゜以下程度になる状態をい
う。特に、水による易洗浄性にはPCT/JP96/0
0734に開示したように、水濡れ角が10゜以下であ
ると好ましく、5゜以下ではより好ましい。The term "hydrophilic" refers to the property of being easily conformed when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The term “high hydrophilicity” in the present invention refers to a property that is highly compatible when water is dropped on the surface, and more specifically, a state where the water wetting angle is about 10 ° or less. In particular, PCT / JP96 / 0 for easy cleaning with water
As disclosed in 0734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less.
【0018】本発明における固体酸とは、固体酸化物を
構成要素に含む酸をいい、具体的には、硫酸担持Al2
O3、硫酸担持TiO2、硫酸担持ZrO2、硫酸担持S
nO2、硫酸担持Fe2O3、硫酸担持SiO2、硫酸担持
HfO2、TiO2/WO3、WO3/SnO2、WO3/Z
rO2、WO3/Fe2O3、SiO2・Al2O3、TiO2
/SiO2、TiO2/ZrO2、TiO2/Al2O3等が
好適に利用できる。The solid acid in the present invention means an acid containing a solid oxide as a constituent element, specifically, sulfuric acid-supporting Al 2
O 3 , sulfuric acid supported TiO 2 , sulfuric acid supported ZrO 2 , sulfuric acid supported S
nO 2 , sulfuric acid supported Fe 2 O 3 , sulfuric acid supported SiO 2 , sulfuric acid supported HfO 2 , TiO 2 / WO 3 , WO 3 / SnO 2 , WO 3 / Z
rO 2, WO 3 / Fe 2 O 3, SiO 2 · Al 2 O 3, TiO 2
/ SiO 2 , TiO 2 / ZrO 2 , TiO 2 / Al 2 O 3 and the like can be preferably used.
【0019】次に、表面層の形成方法について説明す
る。まず表面層が光触媒のみからなる場合の製法につい
て、光触媒がアナターゼ型酸化チタンの場合を例にとり
説明する。この場合の方法は、大別して3つの方法があ
る。1つの方法はゾル塗布焼成法であり、他の方法は有
機チタネート法であり、他の方法は電子ビーム蒸着法で
ある。 (1)ゾル塗布焼成法 アナターゼ型酸化チタンゾルを、基材表面に、スプレー
コーティング法、ディップコーティング法、フローコー
ティング法、スピンコーティング法、ロールコーティン
グ法等の方法で塗布し、焼成する。 (2)有機チタネート法 チタンアルコキシド(テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等)、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤(塩酸、エチルアミン
等)を添加し、アルコール(エタノール、プロパノー
ル、ブタノール等)などの非水溶媒で希釈した後、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法、ディッ
プコーティング法、フローコーティング法、スピンコー
ティング法、ロールコーティング法等の方法で塗布し、
乾燥させる。乾燥により、有機チタネートの加水分解が
完遂して水酸化チタンが生成し、水酸化チタンの脱水縮
重合により無定型酸化チタンの層が基材表面に形成され
る。その後、アナターゼの結晶化温度以上の温度で焼成
して、無定型酸化チタンをアナターゼ型酸化チタンに相
転移させる。 (3)電子ビーム蒸着法 酸化チタンのターゲットに電子ビームを照射することに
より、基材表面に無定型酸化チタンの層を形成する。そ
の後、アナターゼの結晶化温度以上の温度で焼成して、
無定型酸化チタンをアナターゼ型酸化チタンに相転移さ
せる。Next, a method for forming the surface layer will be described. First, the production method in the case where the surface layer is composed only of the photocatalyst will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, there are roughly three methods. One method is a sol coating and firing method, the other method is an organic titanate method, and the other method is an electron beam evaporation method. (1) Sol-coating and firing method Anatase-type titanium oxide sol is applied to the surface of a substrate by a method such as spray coating, dip coating, flow coating, spin coating, or roll coating, and then fired. (2) Organic titanate method Titanium alkoxide (tetraethoxy titanium, tetramethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, etc.), titanium acetate, titanium chelate, etc. are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.). , After diluting with a non-aqueous solvent such as alcohol (ethanol, propanol, butanol, etc.), while partially or completely proceeding the hydrolysis, the mixture is spray-coated, dip-coated, Apply by methods such as flow coating method, spin coating method, roll coating method,
dry. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Electron beam evaporation method An amorphous titanium oxide layer is formed on the surface of a substrate by irradiating a titanium oxide target with an electron beam. After that, firing at a temperature higher than the crystallization temperature of anatase,
Phase transition of amorphous titanium oxide to anatase titanium oxide.
【0020】次に、表面層が光触媒とシリカからなる場
合について、光触媒がアナターゼ型酸化チタンの場合を
例にとり説明する。この場合の方法は、例えば、以下の
3つの方法がある。1つの方法はゾル塗布焼成法であ
り、他の方法は有機チタネート法であり、他の方法は4
官能性シラン法である。 (1)ゾル塗布焼成法 アナターゼ型酸化チタンゾルとシリカゾルとの混合液
を、基材表面にスプレーコーティング法、ディップコー
ティング法、フローコーティング法、スピンコーティン
グ法、ロールコーティング法等の方法で塗布し、焼成す
る。 (2)有機チタネート法 チタンアルコキシド(テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等)、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤(塩酸、エチルアミン
等)とシリカゾルを添加し、アルコール(エタノール、
プロパノール、ブタノール等)などの非水溶媒で希釈し
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
法、ディップコーティング法、フローコーティング法、
スピンコーティング法、ロールコーティング法等の方法
で塗布し、乾燥させる。乾燥により、有機チタネートの
加水分解が完遂して水酸化チタンが生成し、水酸化チタ
ンの脱水縮重合により無定型酸化チタンの層が基材表面
に形成される。その後、アナターゼの結晶化温度以上の
温度で焼成して、無定型酸化チタンをアナターゼ型酸化
チタンに相転移させる。 (3)4官能性シラン法 テトラアルコキシシラン(テトラエトキシシラン、テト
ラプロポキシシラン、テトラブトキシシラン、テトラメ
トキシシラン等)とアナターゼ型酸化チタンゾルとの混
合物を基材の表面にスプレーコーティング法、ディップ
コーティング法、フローコーティング法、スピンコーテ
ィング法、ロールコーティング法等の方法で塗布し、必
要に応じて加水分解させてシラノールを形成した後、加
熱等の方法でシラノールを脱水縮重合に付す。Next, the case where the surface layer is composed of a photocatalyst and silica will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, for example, there are the following three methods. One method is the sol coating firing method, the other is the organic titanate method, the other is 4
This is a functional silane method. (1) Sol coating and baking method A mixture of anatase-type titanium oxide sol and silica sol is applied to the substrate surface by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, and a roll coating method, and then fired. I do. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, and other organic titanates are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol. Add alcohol (ethanol,
After diluting with a non-aqueous solvent such as propanol, butanol, etc., and then allowing the hydrolysis to proceed partially or completely, the mixture is spray-coated, dip-coated, flow-coated,
It is applied by a method such as spin coating or roll coating and dried. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Tetrafunctional silane method A mixture of tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.) and anatase type titanium oxide sol is spray-coated or dip-coated on the surface of a substrate. , A flow coating method, a spin coating method, a roll coating method, or the like, and if necessary, hydrolyzing to form silanol, and then silanol is subjected to dehydration condensation polymerization by a method such as heating.
【0021】次に、表面層が光触媒と固体酸からなる場
合について、光触媒がアナターゼ型酸化チタン、固体酸
がTiO2/WO3の場合を例にとり説明する。この場合
の1つの方法は、タングステン酸のアンモニア溶解液と
アナターゼ型酸化チタンゾルとを混合し、必要に応じて
希釈液(水、エタノール等)で希釈した混合物を基材の
表面にスプレーコーティング法、ディップコーティング
法、フローコーティング法、スピンコーティング法、ロ
ールコーティング法等の方法で塗布し、焼成する。他の
方法は、電子ビーム蒸着や、チタンアルコキシド、チタ
ンアセテート、チタンキレート等の有機チタネートの加
水分解及び脱水縮重合等の方法により、無定型酸化チタ
ン被膜を形成後、タングステン酸を塗布し、その後、無
定型酸化チタンが結晶化し、かつTiO2/WO3複合酸
化物が生成する温度で熱処理する。Next, the case where the surface layer is composed of a photocatalyst and a solid acid will be described by taking as an example the case where the photocatalyst is anatase type titanium oxide and the solid acid is TiO 2 / WO 3 . One method in this case is a method in which an ammonia solution of tungstic acid and an anatase type titanium oxide sol are mixed, and if necessary, a mixture diluted with a diluent (water, ethanol, etc.) is spray-coated on the surface of the base material, It is applied by a method such as a dip coating method, a flow coating method, a spin coating method or a roll coating method, and baked. Other methods include electron beam evaporation, titanium alkoxide, titanium acetate, hydrolysis of organic titanates such as titanium chelates, and dehydration polycondensation to form an amorphous titanium oxide film, and then tungstic acid is applied. Heat treatment is performed at a temperature at which amorphous titanium oxide is crystallized and a TiO 2 / WO 3 composite oxide is formed.
【0022】次に、表面層が光触媒とシリコーンからな
る場合について、光触媒がアナターゼ型酸化チタンの場
合を例にとり説明する。この場合の方法は、未硬化の若
しくは部分的に硬化したシリコーン又はシリコーンの前
駆体からなる塗料とアナターゼ型酸化チタンゾルとを混
合し、シリコーンの前駆体を必要に応じて加水分解させ
た後、混合物を基材の表面にスプレーコーティング法、
ディップコーティング法、フローコーティング法、スピ
ンコーティング法、ロールコーティング法等の方法で塗
布し、加熱等の方法でシリコーンの前駆体の加水分解物
を脱水縮重合に付して、アナターゼ型酸化チタン粒子と
シリコーンからなる表面層を形成する。形成された表面
層は、紫外線を含む光の照射によりアナターゼ型酸化チ
タンが光励起されることにより、シリコーン分子中のケ
イ素原子に結合した有機基の少なくとも一部を水酸基に
置換され、さらにその上に物理吸着水層が形成されて、
高度の親水性を呈する。ここでシリコーンの前駆体に
は、メチルトリメトキシシラン、メチルトリエトキシシ
ラン、メチルトリブトキシシラン、メチルトリプロポキ
シシラン、エチルトリメトキシシラン、エチルトリエト
キシシラン、エチルトリブトキシシラン、エチルトリプ
ロポキシシラン、フェニルトリメトキシシラン、フェニ
ルトリエトキシシラン、フェニルトリブトキシシラン、
フェニルトリプロポキシシラン、ジメチルジメトキシシ
ラン、ジメチルジエトキシシラン、ジメチルジブトキシ
シラン、ジメチルジプロポキシシラン、ジエチルジメト
キシシラン、ジエチルジエトキシシラン、ジエチルジブ
トキシシラン、ジエチルジプロポキシシラン、フェニル
メチルジメトキシシラン、フェニルメチルジエトキシシ
ラン、フェニルメチルジブトキシシラン、フェニルメチ
ルジプロポキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、及びそれらの加水分解物、それらの混
合物が好適に利用できる。Next, the case where the surface layer is composed of a photocatalyst and silicone will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. The method in this case is to mix a coating composed of uncured or partially cured silicone or a precursor of silicone and anatase type titanium oxide sol, and hydrolyze the precursor of silicone as needed, and then mix the mixture. Spray coating method on the surface of the substrate,
It is applied by a method such as a dip coating method, a flow coating method, a spin coating method, a roll coating method, etc., and a hydrolyzate of a silicone precursor is subjected to dehydration polycondensation by a method such as heating to obtain anatase type titanium oxide particles. A surface layer made of silicone is formed. The formed surface layer, by photoexcitation of anatase type titanium oxide by irradiation with light including ultraviolet rays, at least a part of the organic group bonded to the silicon atom in the silicone molecule is substituted with a hydroxyl group, and further on it. A physically adsorbed water layer is formed,
It exhibits a high degree of hydrophilicity. Here, the precursor of silicone includes methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, and phenyl. Trimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,
Phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, a hydrolyzate thereof, and a mixture thereof can be suitably used.
【0023】[0023]
実施例1.テトラエトキシシラン(和光純薬)0.69
gとアナターゼ型酸化チタンゾル(日産化学、TA−1
5、平均粒径10nm)1.07gとエタノール29.
88gと、純水0.36gを混合し、コーティング液を
調製した。このコーティング液をフローコーティング法
により、10cm角のガラス基材上に塗布した。このガ
ラス板を約20分間約150℃の温度に保持することに
より、テトラエトキシシランを加水分解と脱水縮重合に
付し、アナターゼ型酸化チタン粒子が無定型シリカで結
着されたコーティングをガラス板表面に形成した。この
コーティング中の、酸化チタンとシリカとの重量比は1
であった。このガラス板を数日間暗所に放置した後、紫
外線光源(三共電気、ブラックライトブルー(BLB)
蛍光灯)を用いて試料の表面に0.5mW/cm2の紫
外線照度で約1時間紫外線を照射し、#1試料を得た。
比較のため、10cm角のガラス板を数日間暗所に放置
した#2試料も準備した。まず、#1試料と#2試料に
水滴を滴下し、滴下後の様子の観察及び水との接触角の
測定を行った。ここで水との接触角は接触角測定器(協
和界面科学、CA−X150)を用い、滴下後30秒後
の水との接触角で評価した。その結果#1試料はマイク
ロシリンジから試料表面に水滴を滴下されると、水滴が
一様に水膜状に試料表面を拡がる様子が観察された。ま
た30秒後の水との接触角は約0゜まで高度に親水化さ
れていた。それに対し、#2試料ではマイクロシリンジ
から試料表面に水滴を滴下されると、水滴は表面になじ
んでいくものの、一様に水膜状になるまでには至らなか
った。また30秒後の水との接触角は30゜であった。
次に、#1試料と#2試料に息を吹きかけ曇り発生の有
無を調べた。その結果#2試料では曇りが生じたのに対
し、#1試料では曇りは生じなかった。さらに、#1試
料を、その後2日間暗所に放置し、#3試料を得た。そ
して#3試料について、同様に水との接触角を接触角測
定器により測定した。その結果、#3試料にマイクロシ
リンジから試料表面に水滴を滴下されると、#1試料と
同様に、水滴が一様に水膜状に試料表面を拡がる様子が
観察された。また水との接触角は約3゜に維持された。
次に#3試料について息を吹きかけた後の曇り発生の有
無を観察した。その結果、曇りは観察されなかった。Embodiment 1 FIG. Tetraethoxysilane (Wako Pure Chemical Industries) 0.69
g and anatase type titanium oxide sol (NISSAN CHEMICAL, TA-1
5, average particle size 10 nm) 1.07 g and ethanol 29.
88 g and 0.36 g of pure water were mixed to prepare a coating liquid. This coating liquid was applied on a 10 cm square glass substrate by a flow coating method. By holding this glass plate at a temperature of about 150 ° C. for about 20 minutes, tetraethoxysilane is subjected to hydrolysis and dehydration polycondensation, and a coating in which anatase-type titanium oxide particles are bound with amorphous silica is applied to the glass plate. Formed on the surface. The weight ratio of titanium oxide to silica in this coating is 1
Met. After leaving this glass plate in the dark for several days, it is then exposed to an ultraviolet light source (Sankyo Denki, Black Light Blue (BLB)).
A # 1 sample was obtained by irradiating the surface of the sample with ultraviolet light for about 1 hour at a UV intensity of 0.5 mW / cm 2 using a fluorescent lamp.
For comparison, a # 2 sample in which a 10 cm square glass plate was left in the dark for several days was also prepared. First, a water drop was dropped on the # 1 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. As a result, when a water drop was dropped from the micro syringe onto the sample surface, it was observed that the water droplet spread uniformly on the sample surface in a water film shape. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °.
Next, the # 1 sample and the # 2 sample were blown to examine whether or not clouding occurred. As a result, fogging occurred in the # 2 sample, but no fogging occurred in the # 1 sample. Further, the # 1 sample was left in a dark place for two days thereafter, to obtain a # 3 sample. Then, for the # 3 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water drop was dropped on the sample surface from the microsyringe on the # 3 sample, it was observed that the water droplet spread uniformly on the sample surface like a # 1 sample. The contact angle with water was maintained at about 3 °.
Next, the presence or absence of fogging after spraying was observed for the # 3 sample. As a result, no fogging was observed.
【0024】次に#3試料と#2試料の表面にオレイン
酸を塗布し、試料表面を水平姿勢に保持しながら夫々の
試料を水槽に満たした水の中に浸漬した。その結果、#
2試料では、オレイン酸は表面に付着したままであり、
軽くこすってもオレイン酸は試料表面を伸びるだけであ
った。それに対し、#3試料では、オレイン酸は丸くな
り、軽くこすると表面から離脱した。Next, oleic acid was applied to the surfaces of the # 3 sample and the # 2 sample, and each sample was immersed in water filled in a water tank while keeping the sample surfaces in a horizontal posture. as a result,#
In the two samples, oleic acid remained attached to the surface,
Even with a slight rubbing, oleic acid only extended the sample surface. On the other hand, in the # 3 sample, the oleic acid became round, and when lightly rubbed, it separated from the surface.
【0025】次に、疎水性カーボンブラック1重量部、
親水性カーボンブラック1重量部からなる粉体混合物を
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#3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150ml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を、色差
計(東京電色)を用いて計測した。色差は日本工業規格
(JIS)H0201に従い、ΔE*表示を用いて評価
した。その結果、#3試料の試験前後の色差変化は0.
6とほとんど変化しなかった。Next, 1 part by weight of hydrophobic carbon black,
A slurry was prepared by suspending a powder mixture consisting of 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. 150 ml of the above slurry was made to flow down on a # 3 sample inclined at 45 degrees and dried for 15 minutes, then 150 ml of distilled water was made to flow down and dried for 15 minutes, and this cycle was repeated 25 times. The change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standards (JIS) H0201 using ΔE * notation. As a result, the color difference change of the # 3 sample before and after the test was 0.
There was almost no change from 6.
【0026】実施例2.10cm角のソーダライムガラ
ス板の表面に電子ビーム蒸着法により無定型酸化チタン
膜を被着し、その後500℃の温度で焼成することによ
り、無定型酸化チタンを結晶化させてアナターゼ型酸化
チタンを生成させた。アナターゼ型酸化チタン被膜の膜
厚は100nmであった。さらに、その上に25%アン
モニア水に溶解させたタングステン酸を、タングステン
酸重量に換算して0.6μg/cm2を塗布後、500
℃の温度で焼成した。 次に、このガラス板を数日間暗
所に放置した後、BLB蛍光灯を用いて試料の表面に
0.5mW/cm2の紫外線照度で約1時間紫外線を照
射し、#4試料を得た。比較のため、10cm角のガラ
ス板を数日間暗所に放置した実施例1の#2試料も準備
した。まず、#4試料と#2試料に水滴を滴下し、滴下
後の様子の観察及び水との接触角の測定を行った。ここ
で水との接触角は接触角測定器(協和界面科学、CA−
X150)を用い、滴下後30秒後の水との接触角で評
価した。その結果#4試料はマイクロシリンジから試料
表面に水滴を滴下されると、水滴が一様に水膜状に試料
表面を拡がる様子が観察された。また30秒後の水との
接触角は約0゜まで高度に親水化されていた。それに対
し、#2試料ではマイクロシリンジから試料表面に水滴
を滴下されると、水滴は表面になじんでいくものの、一
様に水膜状になるまでには至らなかった。また30秒後
の水との接触角は30゜であった。次に、#4試料と#
2試料に息を吹きかけ曇り発生の有無を調べた。その結
果#2試料では曇りが生じたのに対し、#4試料では曇
りは生じなかった。さらに、#4試料を、その後2日間
暗所に放置し、#5試料を得た。そして#5試料につい
て、同様に水との接触角を接触角測定器により測定し
た。その結果、#5試料にマイクロシリンジから試料表
面に水滴を滴下されると、#4試料と同様に、水滴が一
様に水膜状に試料表面を拡がる様子が観察された。また
水との接触角は約1゜に維持された。次に#5試料につ
いて息を吹きかけた後の曇り発生の有無を観察した。そ
の結果、曇りは観察されなかった。Example 2 Amorphous titanium oxide was crystallized by depositing an amorphous titanium oxide film on the surface of a 10 cm square soda lime glass plate by an electron beam vapor deposition method and then firing it at a temperature of 500 ° C. Then, anatase type titanium oxide was produced. The film thickness of the anatase type titanium oxide film was 100 nm. Further, tungstic acid dissolved in 25% ammonia water was applied thereon to convert the weight of tungstic acid to 0.6 μg / cm 2 , and then 500
Firing at a temperature of ° C. Next, after leaving this glass plate in the dark for several days, the surface of the sample was irradiated with ultraviolet rays for about 1 hour using a BLB fluorescent lamp at an ultraviolet illuminance of 0.5 mW / cm 2 to obtain a # 4 sample. . For comparison, a # 2 sample of Example 1 in which a 10 cm square glass plate was left in the dark for several days was also prepared. First, a water drop was dropped on the # 4 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water is measured using a contact angle measuring instrument (Kyowa Interface Science, CA-
X150) was used and the contact angle with water was evaluated 30 seconds after the dropping. As a result, it was observed that when water droplets were dropped from the microsyringe on the sample surface of the # 4 sample, the water droplets spread uniformly on the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °. Next, # 4 sample and #
Two samples were blown to examine whether or not clouding occurred. As a result, the # 2 sample generated haze, whereas the # 4 sample did not. Further, the # 4 sample was left in a dark place for two days thereafter to obtain a # 5 sample. Then, for the # 5 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water droplet was dropped on the sample surface from the microsyringe on the # 5 sample, it was observed that the water droplet spread uniformly over the sample surface in the form of a water film, similarly to the # 4 sample. The contact angle with water was maintained at about 1 °. Next, with respect to the # 5 sample, it was observed whether or not clouding occurred after the breathing. As a result, no fogging was observed.
【0027】次に#5試料と#2試料の表面にオレイン
酸を塗布し、試料表面を水平姿勢に保持しながら夫々の
試料を水槽に満たした水の中に浸漬した。その結果、#
2試料では、オレイン酸は表面に付着したままであり、
軽くこすってもオレイン酸は試料表面を伸びるだけであ
った。それに対し、#5試料では、オレイン酸は丸くな
り、軽くこすると表面から離脱した。Next, oleic acid was applied to the surfaces of the # 5 sample and the # 2 sample, and each sample was immersed in water filled in a water tank while keeping the sample surfaces in a horizontal posture. as a result,#
In the two samples, oleic acid remained attached to the surface,
Even with a slight rubbing, oleic acid only extended the sample surface. On the other hand, in the # 5 sample, the oleic acid became round, and lightly rubbed off the surface.
【0028】次に、疎水性カーボンブラック1重量部、
親水性カーボンブラック1重量部からなる粉体混合物を
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#5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150ml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を、色差
計(東京電色)を用いて計測した。色差は日本工業規格
(JIS)H0201に従い、ΔE*表示を用いて評価
した。その結果、#5試料の試験前後の色差変化は0.
4とほとんど変化しなかった。Next, 1 part by weight of hydrophobic carbon black,
A slurry was prepared by suspending a powder mixture consisting of 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. 150 ml of the above slurry was made to flow down on a # 5 sample inclined at 45 degrees and dried for 15 minutes, then 150 ml of distilled water was made to flow down and dried for 15 minutes, and this cycle was repeated 25 times. The change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standards (JIS) H0201 using ΔE * notation. As a result, the color difference change of the # 5 sample before and after the test was 0.
There was almost no change from 4.
【0029】[0029]
【発明の効果】本発明では、ガラス食器の表面に、実質
的に透明な光触媒性酸化物粒子を含有する表面層を備え
ることにより、光触媒の光励起に応じて、表面層の表面
は親水性を呈する。それにより、水で濯ぐ又は水に浸漬
する程度の簡単な洗浄で前記表面層の表面は清浄化され
るようになる。According to the present invention, the surface of glass tableware is provided with a surface layer containing substantially transparent photocatalytic oxide particles, so that the surface of the surface layer becomes hydrophilic in response to photoexcitation of the photocatalyst. Present. As a result, the surface of the surface layer can be cleaned by simple washing such as rinsing with water or immersion in water.
【図1】本発明に係るガラス食器の表面構造を示す図。FIG. 1 is a diagram showing a surface structure of glass tableware according to the present invention.
【図2】本発明に係るガラス食器の他の表面構造を示す
図。FIG. 2 is a diagram showing another surface structure of the glass tableware according to the present invention.
Claims (8)
含有する表面層を備え、前記光触媒の光励起に応じて、
前記層の表面は親水性を呈し、以てガラス食器の前記層
表面を水で洗浄するのが容易になる易洗浄性ガラス食
器。1. A surface layer containing photocatalyst particles is provided on the surface of a glass tableware substrate, and in response to photoexcitation of the photocatalyst,
The easily washable glass tableware in which the surface of the layer exhibits hydrophilicity and thus the surface of the layer of the glass tableware can be easily washed with water.
れていることを特徴とする請求項1に記載のガラス食
器。2. The glass tableware according to claim 1, wherein the surface layer further contains silica.
れていることを特徴とする請求項1に記載のガラス食
器。3. The glass tableware according to claim 1, wherein the surface layer further contains a solid acid.
有されていることを特徴とする請求項1に記載のガラス
食器。4. The glass tableware according to claim 1, wherein the surface layer further contains silicone.
起に応じて、水との接触角に換算して10゜以下の親水
性を呈することを特徴とする請求項1〜4に記載のガラ
ス食器。5. The surface of the surface layer exhibits hydrophilicity of 10 ° or less in terms of contact angle with water in response to photoexcitation of the photocatalyst. Glass tableware.
起に応じて、水との接触角に換算して5゜以下の親水性
を呈することを特徴とする請求項1〜4に記載のガラス
食器。6. The surface of the surface layer exhibits hydrophilicity of 5 ° or less in terms of contact angle with water in response to photoexcitation of the photocatalyst. Glass tableware.
な保護層が設けられていることを特徴とする請求項1〜
6に記載のガラス食器。7. The method according to claim 1, wherein a protective layer capable of being made hydrophilic is further provided on the surface of the surface layer.
The glass tableware according to 6.
する工程と;前記ガラス食器の表面層に含有される光触
媒を光励起することにより、前記層の表面を親水性にす
る工程と;前記ガラス食器を水で濯ぐ又は水に浸漬する
ことにより、前記層の表面に付着する堆積物及び/又は
汚染物を表面から釈放させて水により洗い流す工程;か
らなるガラス食器の洗浄方法。8. A step of preparing the glass tableware according to claim 1; and a step of making the surface of the layer hydrophilic by photoexciting a photocatalyst contained in a surface layer of the glass tableware. A method of washing glass tableware, comprising the steps of rinsing the glass tableware with water or immersing it in water to release deposits and / or contaminants adhering to the surface of the layer from the surface and wash away with water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8307000A JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35464995 | 1995-12-22 | ||
JP7-354649 | 1995-12-22 | ||
JP8307000A JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH09224800A true JPH09224800A (en) | 1997-09-02 |
Family
ID=18438979
Family Applications (71)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
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 |
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 |
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 |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
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 |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield 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 |
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 |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging 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 |
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 |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
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 |
JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
JP28895596A Expired - Lifetime JP3774955B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning handrail and handrail cleaning method |
JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
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 |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
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 |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
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 |
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 |
Family Applications Before (51)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
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 |
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 |
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 |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
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 |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield 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 |
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 |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging 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 |
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 |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
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 |
JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
JP28895596A Expired - Lifetime JP3774955B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning handrail and handrail cleaning method |
JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
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JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
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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 |
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JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
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 |
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CN102923836A (en) * | 2012-11-15 | 2013-02-13 | 常州大学 | Method for treating washing wastewater by using composite-film modified sintered gangue ceramsite |
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