JPH09271731A - Removing method of objective material - Google Patents
Removing method of objective materialInfo
- Publication number
- JPH09271731A JPH09271731A JP8110619A JP11061996A JPH09271731A JP H09271731 A JPH09271731 A JP H09271731A JP 8110619 A JP8110619 A JP 8110619A JP 11061996 A JP11061996 A JP 11061996A JP H09271731 A JPH09271731 A JP H09271731A
- Authority
- JP
- Japan
- Prior art keywords
- target substance
- titanium oxide
- water
- substance
- contact angle
- 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
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 239000011941 photocatalyst Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 24
- 239000013076 target substance Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- -1 polyhydroxysiloxane Polymers 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 239000000809 air pollutant Substances 0.000 claims description 3
- 231100001243 air pollutant Toxicity 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000004687 hexahydrates Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007539 photo-oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- GLDPGGLLQUPPPH-UHFFFAOYSA-N C(C)O[Si](OCC)(OCC)OCC.CO[Si](OC)(OC)OC.Br[Si](Br)(Br)Br.Cl[Si](Cl)(Cl)Cl.C1(=CC=CC=C1)[Si](OCC)(OCC)OCC.C1(=CC=CC=C1)[Si](OC)(OC)OC.C1(=CC=CC=C1)[Si](Br)(Br)Br.C1(=CC=CC=C1)[Si](Cl)(Cl)Cl.C(CCCCCCCCCCCCCCCCC)[Si](OCC)(OCC)OCC Chemical compound C(C)O[Si](OCC)(OCC)OCC.CO[Si](OC)(OC)OC.Br[Si](Br)(Br)Br.Cl[Si](Cl)(Cl)Cl.C1(=CC=CC=C1)[Si](OCC)(OCC)OCC.C1(=CC=CC=C1)[Si](OC)(OC)OC.C1(=CC=CC=C1)[Si](Br)(Br)Br.C1(=CC=CC=C1)[Si](Cl)(Cl)Cl.C(CCCCCCCCCCCCCCCCC)[Si](OCC)(OCC)OCC GLDPGGLLQUPPPH-UHFFFAOYSA-N 0.000 description 1
- JSJVPYUECUEVET-UHFFFAOYSA-N C(CCCCC)[Si](Cl)(Cl)Cl.C(CC)[Si](OC(C)C)(OC(C)C)OC(C)C.C(CC)[Si](OCC)(OCC)OCC.C(CC)[Si](OC)(OC)OC.C(CC)[Si](Br)(Br)Br.C(CC)[Si](Cl)(Cl)Cl.C(C)[Si](OC(C)C)(OC(C)C)OC(C)C.C(C)O[SiH](OCC)OCC Chemical compound C(CCCCC)[Si](Cl)(Cl)Cl.C(CC)[Si](OC(C)C)(OC(C)C)OC(C)C.C(CC)[Si](OCC)(OCC)OCC.C(CC)[Si](OC)(OC)OC.C(CC)[Si](Br)(Br)Br.C(CC)[Si](Cl)(Cl)Cl.C(C)[Si](OC(C)C)(OC(C)C)OC(C)C.C(C)O[SiH](OCC)OCC JSJVPYUECUEVET-UHFFFAOYSA-N 0.000 description 1
- WIJQGKRFCKTZMC-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OCC)(OCC)OCC.C(CCCCCCCCC)[Si](OC)(OC)OC.C(CCCCC)[Si](OCC)(OCC)OCC.C(CCCCC)[Si](OC)(OC)OC.C(CCCCC)[Si](Br)(Br)Br Chemical compound C(CCCCCCCCC)[Si](OCC)(OCC)OCC.C(CCCCCCCCC)[Si](OC)(OC)OC.C(CCCCC)[Si](OCC)(OCC)OCC.C(CCCCC)[Si](OC)(OC)OC.C(CCCCC)[Si](Br)(Br)Br WIJQGKRFCKTZMC-UHFFFAOYSA-N 0.000 description 1
- KVRZJLOGPINXKQ-UHFFFAOYSA-N C1(=CC=CC=C1)C[SiH](OCC)OCC.C1(=CC=CC=C1)C[SiH](OC)OC.C1(=CC=CC=C1)C[SiH](Br)Br.C1(=CC=CC=C1)C[SiH](Cl)Cl.C1(=CC=CC=C1)[Si](OCC)(OCC)C1=CC=CC=C1.C1(=CC=CC=C1)[Si](OC)(OC)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C[SiH](OCC)OCC.C1(=CC=CC=C1)C[SiH](OC)OC.C1(=CC=CC=C1)C[SiH](Br)Br.C1(=CC=CC=C1)C[SiH](Cl)Cl.C1(=CC=CC=C1)[Si](OCC)(OCC)C1=CC=CC=C1.C1(=CC=CC=C1)[Si](OC)(OC)C1=CC=CC=C1 KVRZJLOGPINXKQ-UHFFFAOYSA-N 0.000 description 1
- VYOQTQNGUXNZLD-UHFFFAOYSA-N C1(=CC=CC=C1)[Si](Br)(Br)C1=CC=CC=C1.C1(=CC=CC=C1)[Si](Cl)(Cl)C1=CC=CC=C1.C[Si](OCC)(OCC)C.C[Si](OC)(OC)C.C[Si](Br)(Br)C.C[Si](Cl)(Cl)C.CO[Si](OCC)(OCC)OC.CO[Si](OCC)(OCC)OC Chemical compound C1(=CC=CC=C1)[Si](Br)(Br)C1=CC=CC=C1.C1(=CC=CC=C1)[Si](Cl)(Cl)C1=CC=CC=C1.C[Si](OCC)(OCC)C.C[Si](OC)(OC)C.C[Si](Br)(Br)C.C[Si](Cl)(Cl)C.CO[Si](OCC)(OCC)OC.CO[Si](OCC)(OCC)OC VYOQTQNGUXNZLD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- RXFVSVHLVGNIRI-UHFFFAOYSA-N FC(CC[Si](Br)(Br)Br)(F)F.FC(CC[Si](Cl)(Cl)Cl)(F)F.C(=C)[Si](OCC)(OCC)OCC.C(=C)[Si](OC)(OC)OC.C(=C)[Si](Br)(Br)Br.[SiH4].C(=C)[Si](Cl)(Cl)Cl.SCCC[Si](OCC)(OCC)OCC Chemical compound FC(CC[Si](Br)(Br)Br)(F)F.FC(CC[Si](Cl)(Cl)Cl)(F)F.C(=C)[Si](OCC)(OCC)OCC.C(=C)[Si](OC)(OC)OC.C(=C)[Si](Br)(Br)Br.[SiH4].C(=C)[Si](Cl)(Cl)Cl.SCCC[Si](OCC)(OCC)OCC RXFVSVHLVGNIRI-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- PTHGSOGQNNUSME-UHFFFAOYSA-N [H+].[SiH4].[Br-].Br.Br Chemical compound [H+].[SiH4].[Br-].Br.Br PTHGSOGQNNUSME-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- AHQDZKRRVNGIQL-UHFFFAOYSA-N methyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(OC(C)(C)C)OC(C)(C)C AHQDZKRRVNGIQL-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- KVENDAGPVNAYLY-UHFFFAOYSA-N tribromo(ethyl)silane Chemical compound CC[Si](Br)(Br)Br KVENDAGPVNAYLY-UHFFFAOYSA-N 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、悪臭、有害物質、
有機物付着汚れ、微生物等の被対象物質を、光触媒作用
により化学変化させて捕捉し、これを水洗除去する方法
に関する。特には、水洗による化学変化生成物の除去性
に優れ、被対象物質を長期にわたって有効に除去しうる
方法に関する。TECHNICAL FIELD The present invention relates to a foul odor, a harmful substance,
The present invention relates to a method in which target substances such as organic substance-attached stains and microorganisms are chemically changed by a photocatalytic action to be captured, and the resulting substances are washed and removed with water. In particular, the present invention relates to a method capable of effectively removing a target substance over a long period of time, which has excellent removability of chemical change products by washing with water.
【０００２】[0002]
【従来の技術】特開平６−３１５６１４には、光触媒作
用を有する酸化チタンを用いて大気汚染物質（窒素酸化
物、イオウ酸化物、ハイドロカーボン類等）を除去する
方法が提案されている。その方法は、大気汚染物質をま
ず酸化チタンの光触媒（光酸化）作用により反応生成物
（硝酸、硫酸、カーボン等）に変換して酸化チタン上に
付着させて捕捉し、次いで付着した生成物を降水により
洗浄して、酸化チタンの光触媒機能を維持・回復するこ
とを要旨とする。2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 6-315614 proposes a method of removing atmospheric pollutants (nitrogen oxides, sulfur oxides, hydrocarbons, etc.) by using titanium oxide having a photocatalytic action. The method is to convert air pollutants into reaction products (nitric acid, sulfuric acid, carbon, etc.) by the photocatalytic (photooxidation) action of titanium oxide, attach them on titanium oxide and capture them, and then remove the attached products. The main point is to maintain and restore the photocatalytic function of titanium oxide by washing with precipitation.
【０００３】[0003]
【発明が解決しようとする課題】しかし、酸化チタンか
らなる層の表面と水との接触角は２０°程度のため、付
着した反応生成物の性質によっては、降水による洗浄作
用程度では充分に除去されない。このため、酸化チタン
表面に付着物が堆積し光触媒機能が低下することによ
り、長期の使用に耐えないという問題点があった。そこ
で、本発明は、付着物の性質に依らず、付着した反応生
成物を効果的に除去しうる被対象物質除去方法を提供す
ることを目的とする。However, since the contact angle between water and the surface of the layer made of titanium oxide is about 20 °, depending on the nature of the attached reaction product, it can be removed sufficiently by the washing action by precipitation. Not done. For this reason, there is a problem that the titanium oxide surface cannot be used for a long period of time due to the deposition of deposits on the surface of the titanium oxide and the deterioration of the photocatalytic function. Therefore, an object of the present invention is to provide a method for removing a target substance that can effectively remove the attached reaction product regardless of the property of the attached material.
【０００４】[0004]
【課題を解決するための手段】第一に、本発明者は、部
材表面に付着する物質の性質と、該部材表面の水との接
触角との間に図１に示す関係があることを見出した。図
１の横軸は、部材表面と水との接触角を示し、縦軸は、
水洗→乾燥の繰り返し後における部材表面の付着汚れの
程度を示す。親水性の汚れについては、接触角が０°近
辺と８０°以上が汚れが少ない。両性物質汚れについて
は、接触角２０°以下と１４０°以上が汚れが少ない。
疎水性の汚れについては、接触角６０°以下と１８０°
近辺が汚れが少ない。図１より、結局全ての性質の付着
物をきれいに水洗しうる表面を得るには、水との接触角
が５°未満（後述実施例６参照）の超親水性表面にする
か、同角が１８０°に近い超撥水性表面にする必要があ
ることが分る。すなわち、水との接触角を５°未満の超
親水性表面にすれば、付着物の性質に依らず、付着した
分解生成物を効果的に除去しうる。First, the present inventor has found that there is a relationship shown in FIG. 1 between the property of a substance adhering to the surface of a member and the contact angle of the surface of the member with water. I found it. The horizontal axis of FIG. 1 represents the contact angle between the surface of the member and water, and the vertical axis represents
Indicates the degree of stains on the surface of the member after repeated washing and drying. With respect to hydrophilic stains, there is little stain when the contact angle is around 0 ° and 80 ° or more. Regarding amphoteric substance stains, there is little stain at contact angles of 20 ° or less and 140 ° or more.
Contact angle 60 ° or less and 180 ° for hydrophobic stains
There is little dirt in the vicinity. From FIG. 1, after all, in order to obtain a surface on which deposits of all properties can be washed thoroughly with water, a superhydrophilic surface having a contact angle with water of less than 5 ° (see Example 6 described later) is used, or the same angle is used. It turns out that it is necessary to have a superhydrophobic surface close to 180 °. That is, when the superhydrophilic surface has a contact angle with water of less than 5 °, the attached decomposition products can be effectively removed regardless of the nature of the attached material.
【０００５】第二に本発明者は、部材の表面に酸化チタ
ン等の光半導体が存在すると、該表面に励起波長以下の
フォトンが照射されることにより、伝導電子と正孔が生
成し、それによりおそらく表面の極性が生じることによ
り、表面の親水性が維持・回復されることを見出した。
したがって、酸化チタン等の光半導体が存在し、かつ発
明の実施の形態において例示するようなある条件を満足
する場合には、部材表面に上記光を照射すれば、表面を
水との接触角が５°未満の超親水性状態に維持・回復し
うる。Secondly, the present inventor has found that when an optical semiconductor such as titanium oxide is present on the surface of a member, conduction electrons and holes are generated by irradiating the surface with photons having an excitation wavelength or less, It was found that the surface hydrophilicity is maintained / restored, probably due to the surface polarity.
Therefore, when an optical semiconductor such as titanium oxide is present and a certain condition as exemplified in the embodiment of the invention is satisfied, when the surface of the member is irradiated with the above light, the contact angle with water on the surface becomes It is possible to maintain and recover the superhydrophilic state of less than 5 °.
【０００６】その理由は、現在次のように考えている。
すなわち、酸化チタンは元来親水性の表面を形成しうる
が、コンタミによりその性質が弱まりやすく、実測値と
しては２０°程度の報告があるにすぎない（「日本化学
会誌」（１９８６）８〜１１頁）。また後述する比較例
３でも１５°程度に止まった。それに対し、酸化ケイ素
（シリカ）や、表面がヒドロキシ化されたシロキサン樹
脂では、元来親水性の表面であり、なおかつ酸化チタン
と比較してコンタミによる親水性質の影響を受けにくい
（但し、両者は光半導体ではないため、単独では光照射
による親水化現象は生じない）。したがってこれらのシ
リカや、ヒドロキシ化されたシロキサン樹脂を光半導体
と混合して表面層を形成すれば、表面層中に存する不純
物成分に左右されず、工業的見地よりみて確実に高度の
親水性を実現できるようになるのである。なお、酸化ス
ズを添加して高度に親水化される理由は現在明らかでは
ない。結局、上記二つの知見を活用すれば半永久的に付
着物の性質に依らず、効果的に付着した分解生成物を除
去しうる方法が得られることとなる。The reason for this is currently considered as follows.
That is, titanium oxide can form a hydrophilic surface by nature, but its properties are apt to be weakened by contamination, and there is only a reported value of about 20 ° ("Journal of the Chemical Society of Japan" (1986) 8- (P. 11). Further, in Comparative Example 3 described later, it stopped at about 15 °. On the other hand, silicon oxide (silica) and siloxane resin whose surface has been hydroxylated have a hydrophilic surface by nature and are less susceptible to hydrophilic properties due to contamination compared to titanium oxide (however, both are Since it is not an optical semiconductor, the phenomenon of hydrophilicity does not occur by irradiation alone.) Therefore, if these silica and hydroxylated siloxane resin are mixed with the photo-semiconductor to form the surface layer, they are not affected by the impurity components present in the surface layer, and ensure a high degree of hydrophilicity from an industrial viewpoint. It will be possible. The reason why tin oxide is added to make it highly hydrophilic is not clear at present. After all, if the above two findings are utilized, a method capable of effectively removing the attached decomposition products semipermanently without depending on the properties of the attached substances can be obtained.
【０００７】すなわち、本発明の被対象物質除去方法
は、光触媒作用を発揮する物質を含む表面層を有する部
材の表面に、該光触媒の励起波長よりも短い波長の光の
照射下において、被対象物質を接近させ、該被対象物質
を光触媒作用により化学変化させて生成物としてこれを
該表面上に捕捉し、該生成物を水で洗浄して除去する被
対象物質除去方法であって； 上記部材表面を、水との
接触角５°未満の親水性とすることを特徴とする。That is, the method of removing a target substance according to the present invention is such that the surface of a member having a surface layer containing a substance exhibiting a photocatalytic action is irradiated with light having a wavelength shorter than the excitation wavelength of the photocatalyst. A method for removing a target substance, which comprises bringing a substance into close proximity, chemically changing the target substance by photocatalysis, capturing the product as a product on the surface, and washing the product with water to remove the product; It is characterized in that the surface of the member is made hydrophilic with a contact angle with water of less than 5 °.
【０００８】[0008]
（１）部材表面と水との接触角が５°未満の超親水性表
面にする方法としては以下を挙げることができる。 部材表面に、酸化チタンと酸化スズからなる層を形
成する方法である。このような層の形成方法としては、
例えば、酸化チタンゾルと酸化スズゾルを混合し、基材
に塗布し、焼成する。 部材表面に、酸化チタンと酸化ケイ素からなる層を
形成する方法である。このような層の形成方法として
は、例えば、酸化チタンゾルとコロイダルシリカを混合
し、基材に塗布し、焼成する。(1) The following may be mentioned as a method of forming a superhydrophilic surface in which the contact angle between the member surface and water is less than 5 °. This is a method of forming a layer composed of titanium oxide and tin oxide on the surface of a member. As a method of forming such a layer,
For example, titanium oxide sol and tin oxide sol are mixed, applied to a base material, and baked. This is a method of forming a layer composed of titanium oxide and silicon oxide on the surface of a member. As a method of forming such a layer, for example, titanium oxide sol and colloidal silica are mixed, coated on a base material, and baked.
【０００９】 部材表面に、酸化チタンとシリコーン
樹脂からなる混合層を形成後、励起波長以下のフォトン
を照射して混合層の少なくとも最表面に存するシリコー
ン樹脂を、ヒドロキシシロキサンに変化させる方法であ
る。このような層の形成方法としては、例えば、まず、
オルガノアルコキシシランと酸化チタンを混合し、基材
に塗布し、オルガノアルコキシシランを加水分解、脱水
縮重合させて、ポリオルガノシロキサンと酸化チタンか
らなる混合層を形成する。その後、励起波長以下のフォ
トンを照射して混合層の少なくとも最表面に存するオル
ガノ基を水酸基に置換させる。This is a method of forming a mixed layer of titanium oxide and a silicone resin on the surface of a member, and then irradiating a photon having an excitation wavelength or less to change the silicone resin present on at least the outermost surface of the mixed layer to hydroxysiloxane. As a method for forming such a layer, for example, first,
Organoalkoxysilane and titanium oxide are mixed and coated on a substrate, and the organoalkoxysilane is hydrolyzed and dehydrated and polycondensed to form a mixed layer of polyorganosiloxane and titanium oxide. Then, photons having an excitation wavelength or less are irradiated to replace at least the outermost organo group of the mixed layer with a hydroxyl group.
【００１０】ここで、使用できるシリコーン樹脂は、加
水分解性基を２〜４個有するシランの加水分解縮合物を
含むものである。その原料となる加水分解性シランの例
としては、 メチルトリクロルシラン メチルトリブロムシラン メチルトリメトキシシラン メチルトリエトキシシラン メチルトリイソプロポキシシラン メチルトリｔ−ブトキシシラン エチルトリクロルシラン エチルトリブロムシラン エチルトリメトキシシラン エチルトリエトキシシラン エチルトリイソプロポキシシラン ｎ−プロピルトリクロルシラン ｎ−プロピルトリブロムシラン ｎ−プロピルトリメトキシシラン ｎ−プロピルトリエトキシシラン ｎ−プロピルトリイソプロポキシシラン ｎ−ヘキシルトリクロルシラン ｎ−ヘキシルトリブロムシラン ｎ−ヘキシルトリメトキシシラン ｎ−ヘキシルトリエトキシシラン ｎ−デシルトリメトキシシラン ｎ−デシルトリエトキシシラン ｎ−オクタデシルトリメトキシシラン ｎ−オクタデシルトリエトキシシラン フェニルトリクロルシラン フェニルトリブロムシラン 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 テトラクロルシラン テトラブロムシラン テトラメトキシシラン テトラエトキシシラン テトラブトキシシラン ジメトキシジエトキシシラン ジメトキシジエトキシシラン ジメチルジクロルシラン ジメチルジブロムシラン ジメチルジメトキシシラン ジメチルジエトキシシラン ジフェニルジクロルシラン ジフェニルジブロムシラン ジフェニルジメトキシシラン ジフェニルジエトキシシラン フェニルメチルジクロルシラン フェニルメチルジブロムシラン フェニルメチルジメトキシシラン フェニルメチルジエトキシシラン トリクロルヒドロシラン トリブロムヒドロシラン トリメトキシヒドロシラン トリエトキシヒドロシラン γ−グリシドキシプロピルトリメトキシシラン γ−グリシドキシプロピルトリエトキシシラン γ−グリシドキシプロピルメチルジメトキシシラン γ−グリシドキシプロピルメチルジエトキシシラン β−（3,4-エポキシシクロヘキシル）エチルトリメトキ
シシラン β−（3,4-エポキシシクロヘキシル）エチルトリエトキ
シシラン γ−（メタ）アクリロキシプロピルトリメトキシシラン γ−（メタ）アクリロキシプロピルトリエトキシシラン γ−（メタ）アクリロキシプロピルメチルジメトキシシ
ラン γ−（メタ）アクリロキシプロピルメチルジエトキシシ
ラン γ−アミノプロピルトリメトキシシラン γ−アミノプロピルトリエトキシシラン γ−アミノプロピルメチルジメトキシシラン γ−アミノプロピルメチルジエトキシシラン γ−メルカプトプロピルトリメトキシシラン γ−メルカプトプロピルトリエトキシシラン ビニルトリクロルシシラン ビニルトリブロムシラン ビニルトリメトキシシラン ビニルトリエトキシシラン トリフルオロプロピルトリクロルシラン トリフルオロプロピルトリブロムシシラン トリフルオロプロピルトリメトキシシラン トリフルオロプロピルトリエトキシシラン およびこれらの部分加水分解物などが挙げられる。原料
の入手のしやすさ、扱いやすさから考えてジアルコキシ
シラン、トリアルコキシシラン、テトラアルコキシシラ
ンを用いるのが好ましい。The silicone resin which can be used here contains a hydrolyzed condensate of silane having 2 to 4 hydrolyzable groups. Examples of the hydrolyzable silane as the raw material are methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, and ethyl. Triethoxysilane ethyltriisopropoxysilane n-propyltrichlorosilane n-propyltribromosilane n-propyltrimethoxysilane n-propyltriethoxysilane n-propyltriisopropoxysilane n-hexyltrichlorosilane n-hexyltribromosilane n -Hexyltrimethoxysilane n-hexyltriethoxysilane n-decyltrimethoxysilane n-decyltriethoxysilane n-octa Syltrimethoxysilane n-octadecyltriethoxysilane Phenyltrichlorosilane Phenyltribromosilane Phenyltrimethoxysilane Phenyltriethoxysilane Tetrachlorosilane Tetrabromosilane Tetramethoxysilane Tetraethoxysilane Tetrabutoxysilane Dimethoxydiethoxysilane Dimethoxydiethoxysilane Dimethyldi Chlorosilane Dimethyldibromosilane Dimethyldimethoxysilane Dimethyldiethoxysilane Diphenyldichlorosilane Diphenyldibromosilane Diphenyldimethoxysilane Diphenyldiethoxysilane Phenylmethyldichlorosilane Phenylmethyldibromsilane Phenylmethyldimethoxysilane Phenylmethyldiethoxysilane Trichlorohydrosilane Tribromide Silane Trimethoxyhydrosilane Triethoxyhydrosilane γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropyltriethoxysilane γ-glycidoxypropylmethyldimethoxysilane γ-glycidoxypropylmethyldiethoxysilane β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane β- (3,4-epoxycyclohexyl) ethyltriethoxysilane γ- (meth) acryloxypropyltrimethoxysilane γ- (meth) acryloxypropyltriethoxysilane γ- (meth) acry Roxypropylmethyldimethoxysilane γ- (meth) acryloxypropylmethyldiethoxysilane γ-aminopropyltrimethoxysilane γ-aminopropyltriethoxysilane γ-aminopropylmethyldimethoxysilane γ-Aminopropylmethyldiethoxysilane γ-mercaptopropyltrimethoxysilane γ-mercaptopropyltriethoxysilane Vinyltrichlorosilane Silane Vinyltribromosilane Vinyltrimethoxysilane Vinyltriethoxysilane Trifluoropropyltrichlorosilane Trifluoropropyltribromosilane Tri Fluoropropyltrimethoxysilane Examples include trifluoropropyltriethoxysilane and partial hydrolysates thereof. It is preferable to use dialkoxysilane, trialkoxysilane, or tetraalkoxysilane from the viewpoint of easy availability and handling of the raw materials.
【００１１】（２）上記親水性を維持しつつ、光触媒
（光酸化）反応をより強める方法としては以下を挙げる
ことができる。白金、パラジウム、ルテニウム、金、銀
を部材表面層に添加し、固定する方法である。これらの
添加によって上記の効果がある理由は、光酸化反応を促
進するには、電子と正孔の再結合を防止しつつ、正孔と
水酸イオンとの反応により生成する水酸ラジカル等の活
性酸素を生成させる必要がある（これら活性酸素が酸化
反応に直接寄与するため）が、上記金属は電子を有効に
捕捉し再結合を生じさせない働きをするのである。これ
らの働きをする金属には他に銅、鉄、ニッケル、コバル
トがあるが、これら金属はおそらく（ガス等の）吸着性
が大きすぎるため親水性を悪化させるものと思われる。(2) The following can be mentioned as a method of further enhancing the photocatalytic (photooxidation) reaction while maintaining the hydrophilicity. In this method, platinum, palladium, ruthenium, gold and silver are added to the surface layer of the member and fixed. The reason why the addition of these has the above-mentioned effect is that in order to promote the photo-oxidation reaction, while preventing recombination of electrons and holes, hydroxyl radicals and the like generated by the reaction between holes and hydroxyl ions are generated. Although it is necessary to generate active oxygen (because these active oxygen directly contribute to the oxidation reaction), the metal functions to effectively trap electrons and prevent recombination. Other metals that perform these functions include copper, iron, nickel, and cobalt, but these metals probably have too large an adsorptive property (gas, etc.) and thus deteriorate hydrophilicity.
【００１２】本発明における光触媒作用を有する部材の
基材としては、タイル、レンガ、ガラス、プラスチッ
ク、紙、金属、フィルム、コーティング層を有する建材
（積層鋼板、塩ビ鋼板、ホーロー鋼板、アルマイト処理
アルミニウム、クロメート処理金属等）、コンクリー
ト、ＡＬＣ、陶磁器、石、石膏、ＦＲＣ、ＧＲＣ、木
材、モルタル、石綿、けい酸カルシウム板、化粧無機建
材（軽量気泡コンクリート板や石綿セメントけい酸カル
シウム板などの無機基材の表層にアクリル、ウレタン、
ポリエステルなどの樹脂塗料で塗装したもの）、サッ
シ、カーテンウォール等様々なものを限定なく使用でき
る。The base material of the member having a photocatalytic action in the present invention is tile, brick, glass, plastic, paper, metal, film, or building material having a coating layer (laminated steel plate, PVC steel plate, enamel steel plate, alumite treated aluminum, Chromate treated metal, etc.), concrete, ALC, ceramics, stone, gypsum, FRC, GRC, wood, mortar, asbestos, calcium silicate board, inorganic inorganic building materials (lightweight aerated concrete board, asbestos cement calcium silicate board, etc.) Acrylic, urethane,
Various things such as sash, curtain wall, etc. can be used without limitation.
【００１３】[0013]
【実施例】以下、本発明の実施例を説明する。以下の実
施例１〜５に係る試料及び比較例１〜４に係る試料を準
備した。実施例１ 酸化チタンゾル（石原産業製ＳＴＳ１１）と酸化スズゾ
ル（多木化学製、平均結晶子径３．５nm）を溶質重量比
８５：１５で混合した。この混合したものを１５cm角の
施釉タイル（東陶機器製ＡＢ０２Ｅ１１）に固形分重量
で３０mg塗布し、８００℃で１０分焼成した。その後、
塩化パラジウム水溶液を塗布し、紫外線照射（条件０．
５mW/cm2で１分）でパラジウムを試料表面に光還元固定
した。Embodiments of the present invention will be described below. Samples according to Examples 1 to 5 and Comparative Examples 1 to 4 below were prepared. Example 1 Titanium oxide sol (STS11 manufactured by Ishihara Sangyo) and tin oxide sol (manufactured by Taki Chemical Co., Ltd., average crystallite diameter 3.5 nm) were mixed at a solute weight ratio of 85:15. This mixture was applied to a 15 cm square glazed tile (AB02E11 manufactured by Toto Kikai Co., Ltd.) in a solid content of 30 mg and baked at 800 ° C. for 10 minutes. afterwards,
An aqueous palladium chloride solution was applied, and ultraviolet irradiation (condition 0.
Palladium was photoreduced and immobilized on the sample surface at 5 mW / cm 2 for 1 minute).
【００１４】実施例２ 酸化チタンゾル（石原産業製ＳＴＳ１１）とシリカゾル
（日産化学製、スノーテックス２０）を溶質重量比８
０：２０で混合した。この混合したものを１５cm角の施
釉タイル（東陶機器製ＡＢ０２Ｅ１１）に固形分重量で
３０mg塗布し、８００℃で１０分焼成した。その後、ヘ
キサクロロ白金酸（IV）六水和物水溶液を塗布し、紫外
線照射（条件０．５mW/cm2で１分）で白金を試料表面に
光還元固定した。 Example 2 A solute weight ratio of titanium oxide sol (STS11 manufactured by Ishihara Sangyo) and silica sol (Snowtex 20 manufactured by Nissan Kagaku) was set to 8
Mixed at 0:20. This mixture was applied to a 15 cm square glazed tile (AB02E11 manufactured by Toto Kikai Co., Ltd.) in a solid content of 30 mg and baked at 800 ° C. for 10 minutes. Then, an aqueous solution of hexachloroplatinic acid (IV) hexahydrate was applied, and platinum was photoreduced and immobilized on the surface of the sample by ultraviolet irradiation (condition: 0.5 mW / cm 2 for 1 minute).
【００１５】実施例３ テトラエトキシシランと酸化チタンゾル（日産化学製Ｔ
Ａ１５）を、溶質重量比５０：５０で混合し、さらにヘ
キサクロロ白金酸（IV）六水和物水溶液を、酸化チタン
固形分に対する白金の量が２mol%となるように添加し
た。この液状物をソーダライムガラスに塗布し、１５０
℃で１０分焼成した。 Example 3 Tetraethoxysilane and titanium oxide sol (Nissan Chemical T
A15) was mixed at a solute weight ratio of 50:50, and hexachloroplatinic acid (IV) hexahydrate aqueous solution was further added so that the amount of platinum was 2 mol% with respect to the titanium oxide solid content. Apply this liquid to soda lime glass and
It was baked at 0 ° C for 10 minutes.
【００１６】実施例４ アルミニウム表面をアルマイト処理（陽極酸化後、アク
リル電着塗装）した基材上に、メチルトリメトキシシラ
ンを塗布し、１５０℃で焼成して膜厚５μm のベースコ
ート層を形成した。次に、メチルトリメトキシシランと
酸化チタンゾル（日産化学製ＴＡ１５）を溶質重量比５
０：５０で混合し、さらにヘキサクロロ白金酸（IV）六
水和物水溶液を、酸化チタン固形分に対する白金の量が
２mol%となるように添加した液状物を上記ベースコート
層上に塗布し、１５０℃で１０分焼成した。 Example 4 Methyltrimethoxysilane was coated on a base material whose aluminum surface was anodized (after anodization and then acrylic electrodeposition coating), and baked at 150 ° C. to form a base coat layer having a thickness of 5 μm. . Next, methyltrimethoxysilane and titanium oxide sol (TA15 manufactured by Nissan Kagaku) were added in a solute weight ratio of 5
The mixture was mixed at 0:50, and an aqueous solution of hexachloroplatinic acid (IV) hexahydrate was added so that the amount of platinum was 2 mol% with respect to the solid content of titanium oxide. It was baked at 0 ° C for 10 minutes.
【００１７】実施例５ アルミニウム表面をクロメート処理（クロムメッキによ
る化成処理後、塗装を施さない状態のもの）した基材上
に、メチルトリメトキシシランを塗布し、１５０℃で焼
成して膜厚５μm のベースコート層を形成した。次に、
メチルトリメトキシシランと酸化チタンゾル（日産化学
製ＴＡ１５）を溶質重量比５０：５０で混合し、さらに
ヘキサクロロ白金酸（IV）六水和物水溶液を、酸化チタ
ン固形分に対する白金の量が２mol%となるように添加し
た液状物を上記ベースコート層上に塗布し、１５０℃で
１０分焼成した。 EXAMPLE 5 Methyltrimethoxysilane was coated on a substrate whose aluminum surface had been chromate-treated (chemical conversion treatment by chrome plating and then not coated), and baked at 150 ° C. to a film thickness of 5 μm. To form a base coat layer. next,
Methyltrimethoxysilane and titanium oxide sol (TA15 manufactured by Nissan Kagaku Co., Ltd.) were mixed at a solute weight ratio of 50:50, and an aqueous solution of hexachloroplatinic acid (IV) hexahydrate was added so that the amount of platinum was 2 mol% based on the solid content of titanium oxide. The liquid substance added as described above was coated on the base coat layer and baked at 150 ° C. for 10 minutes.
【００１８】比較例１ 施釉タイル（東陶機器製ＡＢ０２Ｅ１１）。比較例２ アルミニウム表面をクロメート処理（クロムメッキによ
る化成処理後、フッ素樹脂をコーティング）したもの。 Comparative Example 1 A glazed tile (AB02E11 manufactured by Toto Kikai). Comparative Example 2 A surface of aluminum that was chromate-treated (chemical conversion treatment by chrome plating, and then coated with fluororesin).
【００１９】比較例３ 施釉タイル（東陶機器製ＡＢ０２Ｅ１１）に、酸化チタ
ンゾル（石原産業製ＳＴＳ１１）を固形分重量で３０mg
塗布し、８００℃で１０分焼成した。その後、塩化パラ
ジウム水溶液を塗布し、紫外線照射（条件０．５mW/cm2
で１分）でパラジウムを試料表面に光還元固定したもの
を準備した。 Comparative Example 3 Titanium oxide sol (STS11 manufactured by Ishihara Sangyo Co., Ltd.) was added to a glazed tile (AB02E11 manufactured by Totoki Kikai Co., Ltd.) in a solid content of 30 mg.
It was applied and baked at 800 ° C. for 10 minutes. Then, apply palladium chloride aqueous solution and irradiate with ultraviolet rays (condition 0.5mW / cm 2
1 minute) was used to prepare palladium on the surface of which the photoreduction was fixed.
【００２０】比較例４ アルミニウム表面をアルマイト処理（陽極酸化後、アク
リル電着塗装）した基材上に、メチルトリメトキシシラ
ンを塗布し、１５０℃で焼成して膜厚５μm のベースコ
ート層を形成した。次にテトラフルオロエチレンと酸化
チタンゾル（日産化学製ＴＡ１５）を溶質重量比５０：
５０で混合し、さらにヘキサクロロ白金酸（IV）六水和
物水溶液を、酸化チタン固形分に対する白金の量が２mo
l%となるように添加した液状物を上記ベースコート層上
に塗布し、１５０℃で１０分焼成した。 Comparative Example 4 Methyltrimethoxysilane was coated on a base material whose aluminum surface was anodized (after anodization and then acrylic electrodeposition coating) and baked at 150 ° C. to form a base coat layer having a thickness of 5 μm. . Next, tetrafluoroethylene and titanium oxide sol (TA15 manufactured by Nissan Kagaku) were used in a solute weight ratio of 50:
The mixture was mixed at 50, and an aqueous solution of hexachloroplatinic acid (IV) hexahydrate was added to the titanium oxide solid content in an amount of 2 mo.
The liquid substance added so as to be 1% was applied onto the above base coat layer and baked at 150 ° C. for 10 minutes.
【００２１】これらの試料に対して以下の項目を測定し
た。 水との接触角：接触角測定器（協和界面科学社製）によ
り水を約５μm 滴下後、３０秒後に測定した。 水との接触角の維持性：１週間０．６mW/cm2のＢＬＢラ
ンプ（紫外線照度は太陽光並）を照射し続けた後の水と
の接触角を測定した。The following items were measured for these samples. Contact angle with water: Measured with a contact angle measuring instrument (manufactured by Kyowa Interface Science Co., Ltd.) after dropping water by about 5 μm for 30 seconds. Maintainability of contact angle with water: The contact angle with water was measured after continuously irradiating a BLB lamp of 0.6 mW / cm 2 (ultraviolet illuminance was almost the same as sunlight) for one week.
【００２２】気体分解率（Ｓ系ガス）：メチルメルカプ
タンを１１リットル容器に３ppm 入れ、０．６mW/cm2の
ＢＬＢランプを３０分照射後の分解率を測定した。○は
７０％以上、△は３０〜７０％、×は３０％未満を示
す。 気体分解率（Ｎ系ガス）：ＮＯ、ＮＯ2 混合ガス（Ｎ
Ｏ：ＮＯ2 ＝９：１）を１１リットル容器に３ppm 入
れ、Ｓ系ガスの場合と同様に測定、評価した。Gas decomposition rate (S type gas): 3 ppm of methyl mercaptan was placed in an 11 liter container and the decomposition rate was measured after irradiation with a 0.6 mW / cm 2 BLB lamp for 30 minutes. ◯ indicates 70% or more, Δ indicates 30 to 70%, and x indicates less than 30%. Gas decomposition rate (N-based gas): NO, NO 2 mixed gas (N
3 ppm of O: NO 2 = 9: 1) was placed in an 11-liter container, and the same measurement and evaluation as in the case of S-based gas were carried out.
【００２３】疎水物質除去性：燃焼生成物の除去性を測
定した。具体的には、疎水性カーボンブラックを試料面
に噴射させ、水洗し、放置するサイクルを繰返したとき
の試料面の汚れ具合を観察した。○は汚れが目立たない
ことを示し、×は汚れが目立つことを示す。Hydrophobic substance removability: Removability of combustion products was measured. Specifically, the degree of soiling of the sample surface was observed when the cycle of spraying hydrophobic carbon black on the sample surface, washing with water, and leaving it was repeated. ○ indicates that the stain is not noticeable, and × indicates that the stain is noticeable.
【００２４】親水物質除去性：無機質汚れの除去性を測
定した。具体的には、イエローオーカー含有物を分散し
た懸濁液を４５°に傾斜させた試料面に流し、乾燥し、
水洗し、乾燥するサイクルを繰返したときの試料面の汚
れ具合を観察した。○は汚れが目立たないことを示し、
×は汚れが目立つことを示す。Removability of hydrophilic substances: Removability of inorganic stains was measured. Specifically, a suspension in which the yellow ocher-containing material is dispersed is poured onto a sample surface inclined at 45 °, dried,
When the cycle of washing with water and drying was repeated, the degree of contamination on the sample surface was observed. ○ indicates that dirt is not noticeable,
X indicates that the stain is conspicuous.
【００２５】測定結果をまとめて表１に示す。The measurement results are summarized in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１から分るように、各実施例とも、水と
の接触角は０°できわめて高い親水性を示した。さら
に、この親水性は１週間の紫外線照射後も高いまま維持
された。一方、各比較例は、水との接触角が５°以上で
あった。As can be seen from Table 1, in each of the examples, the contact angle with water was 0 °, which showed extremely high hydrophilicity. Furthermore, this hydrophilicity remained high even after 1 week of UV irradiation. On the other hand, in each comparative example, the contact angle with water was 5 ° or more.
【００２８】気体（メチルメルカプタン）及びＮＯ、Ｎ
Ｏ2 混合ガスの分解率については、実施例及び酸化チタ
ンを含む比較例３、４はいずれも良好であった。しか
し、光触媒物質を含まない比較例１、２は、当然のこと
ながら分解率が低かった。Gas (methyl mercaptan) and NO, N
Regarding the decomposition rate of the O 2 mixed gas, the examples and Comparative examples 3 and 4 containing titanium oxide were good. However, the decomposition rates of Comparative Examples 1 and 2 containing no photocatalytic substance were naturally low.
【００２９】疎水物質除去性は、各実施例及び比較的親
水性の比較例１及び３は良好であった。しかし、比較的
疎水性の比較例２及び４は不良であった。親水物質除去
性は、各実施例及び比較的疎水性の比較例２及び４は良
好であった。しかし、比較的親水性の比較例１及び３は
不良であった。The hydrophobic substance-removing property was good in each of the examples and in the comparative examples 1 and 3 which were relatively hydrophilic. However, Comparative Examples 2 and 4, which were relatively hydrophobic, were poor. The hydrophilic substance removability was good in each Example and Comparative Examples 2 and 4 which were relatively hydrophobic. However, Comparative Examples 1 and 3, which are relatively hydrophilic, were poor.
【００３０】「水と接触角５°未満」が本発明の被対象
物質除去方法の条件であるが、この根拠となる実験例
（実施例６）を以下に説明する。実施例６ アナターゼ型チタニアゾル（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（ＡＢ０２Ｅ０
１）に塗布し、８８０℃の温度で１０分焼成した。その
後、銅濃度５０μmol/g の酢酸銅１水塩の水溶液を０．
３ｇスプレーコーティング法により塗布した後乾燥さ
せ、ＢＬＢ蛍光灯により０．４mW/cm2の紫外線照度で紫
外線を１０分間照射して酢酸銅１水塩を光還元析出させ
ることにより試料を得た。"The contact angle with water is less than 5 °" is a condition of the method for removing a target substance according to the present invention, and an experimental example (Example 6) which is the basis for this is described below. Example 6 A mixture of anatase-type titania sol (STS-11) and colloidal silica sol (Snowtex 20) (ratio of silica in the solid content is 10% by weight) is 4.5 mg in terms of solid content, and is 15 cm square glazed tile (AB02E0).
It was applied to 1) and baked at a temperature of 880 ° C. for 10 minutes. After that, an aqueous solution of copper acetate monohydrate having a copper concentration of 50 μmol / g was added to 0.2%.
A sample was obtained by applying 3 g of spray coating method and then drying, and irradiating with ultraviolet light of 0.4 mW / cm 2 of UV light by a BLB fluorescent lamp for 10 minutes to cause photoreductive precipitation of copper acetate monohydrate.
【００３１】この試料の水との接触角は４．０°であっ
た。次に、この試料について以下に示す汚泥試験（親水
性汚れ試験）を行った。まず、イエローオーカー６４．
３重量％、焼成関東ローム粘土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１．０５ｇ
／リットルの濃度で水に懸濁させたスラリーを調整し
た。つぎに、４５度に傾斜させた試料及び施釉タイル
（ＡＢ０２Ｅ０１）（比較例）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と光沢度変化を調べた。
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光沢度を試験前
の光沢度で割ることにより求めた。The contact angle of this sample with water was 4.0 °. Next, the sludge test (hydrophilic stain test) shown below was performed on this sample. First, yellow ocher 64.
1.05 g of 3% by weight, calcined Kanto loam clay 21.4% by weight, hydrophobic carbon black 4.8% by weight, silica powder 4.8% by weight, hydrophilic carbon black 4.7% by weight
A slurry suspended in water at a concentration of 1 / liter was prepared. Next, 150 ml of the above slurry was applied to a sample tilted at 45 degrees and a glazed tile (AB02E01) (comparative example).
To dry for 15 minutes, then 150 ml of distilled water
And allowed to dry for 15 minutes and this cycle was repeated 25 times. The change in color difference and the change in gloss before and after the test were examined.
The glossiness was measured according to Japanese Industrial Standard (JIS) Z8741 and the change in glossiness was obtained by dividing the glossiness after the test by the glossiness before the test.
【００３２】汚泥試験の結果は、本実施例の試料は色差
変化２．０、光沢度変化８１．５％と、良好であった。
一方、比較例の施釉タイルについては、水との接触角１
９．４°、色差変化４．６、光沢度変化６８．３％と不
良であった。したがって、水との接触角５°未満で、親
水性汚れを効果的に除去できる超親水性表面が得られる
との結論を得た。As a result of the sludge test, the sample of this example showed a good change in color difference of 2.0 and a change in glossiness of 81.5%.
On the other hand, for the glazed tile of the comparative example, the contact angle with water is 1
9.4 °, change in color difference 4.6, change in gloss 68.3%. Therefore, it was concluded that a contact angle with water of less than 5 ° provides a superhydrophilic surface that can effectively remove hydrophilic stains.
【００３３】[0033]
【発明の効果】以上の説明から明らかなように、本発明
は、水洗による化学変化生成物の除去性に優れ、被対象
物質を長期にわたって有効に除去しうる被対象物質除去
方法を提供することができる。したがって、大気汚染物
質の除去等、住環境の改善に資することきわめて大であ
る。As is apparent from the above description, the present invention provides a method for removing a target substance which is excellent in removing chemical change products by washing with water and which can effectively remove the target substance for a long period of time. You can Therefore, it greatly contributes to the improvement of the living environment such as the removal of air pollutants.
【図１】部材表面付着物質の性質と、部材表面の水との
接触角との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the property of a substance adhering to a member surface and the contact angle of water on the member surface.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 35/02 Ｂ０１Ｄ 53/36 ＺＡＢＪ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location B01J 35/02 B01D 53/36 ZABJ
Claims (7)
を有する部材の表面に、該光触媒の励起波長よりも短い
波長の光の照射下において、被対象物質を接近させ、該
被対象物質を光触媒作用により化学変化させて生成物と
してこれを該表面上に捕捉し、該生成物を水で洗浄して
除去する被対象物質除去方法であって；上記部材表面
を、水との接触角５°未満の親水性とすることを特徴と
する被対象物質除去方法。1. A target substance is brought close to the surface of a member having a surface layer containing a substance exhibiting a photocatalytic action under irradiation with light having a wavelength shorter than the excitation wavelength of the photocatalyst, and the target substance is A method of removing a target substance, which comprises chemically converting by photocatalysis to capture the product as a product on the surface, and washing the product with water to remove the target substance; A method for removing a target substance, which has hydrophilicity of less than °.
の親水性とする請求項１記載の被対象物質除去方法。2. A contact angle of water on the surface of the member is approximately 0 °.
The method for removing a target substance according to claim 1, wherein the target substance is made hydrophilic.
ズを主成分とする物質からなる請求項１又は２記載の被
対象物質除去方法。3. The method for removing a target substance according to claim 1, wherein the outermost surface of the member is made of a substance containing titanium oxide and tin oxide as main components.
イ素を主成分とする物質からなる請求項１又は２記載の
被対象物質除去方法。4. The method for removing a target substance according to claim 1, wherein the outermost surface of the member is made of a substance containing titanium oxide and silicon oxide as main components.
コーン樹脂を主成分とする物質からなり、かつその最表
面は酸化チタンとポリヒドロキシシロキサンを主成分と
する物質からなる請求項１又は２記載の被対象物質除去
方法。5. The surface layer of the member is made of a material containing titanium oxide and silicone resin as main components, and the outermost surface thereof is made of a material containing titanium oxide and polyhydroxysiloxane as main components. The method for removing a target substance described.
金、パラジウム、ルテニウム、金及び銀の内の少なくと
も１種が添加されている請求項１〜５いずれか１項記載
の被対象物質除去方法。6. The target substance according to claim 1, wherein at least one of platinum, palladium, ruthenium, gold and silver is added to the substance forming the surface layer of the member. Removal method.
求項１〜６いずれか１項記載の被対象物質除去方法。7. The method of removing a target substance according to claim 1, wherein the target substance is an air pollutant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8110619A JPH09271731A (en) | 1996-04-08 | 1996-04-08 | Removing method of objective material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8110619A JPH09271731A (en) | 1996-04-08 | 1996-04-08 | Removing method of objective material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000247608A Division JP2001087629A (en) | 2000-08-17 | 2000-08-17 | N-based or s-based gas removing member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09271731A true JPH09271731A (en) | 1997-10-21 |
Family
ID=14540398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8110619A Pending JPH09271731A (en) | 1996-04-08 | 1996-04-08 | Removing method of objective material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09271731A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021716A1 (en) * | 1999-09-17 | 2001-03-29 | Nihon Parkerizing Co., Ltd. | PHOTOCATALYST COATING MATERIAL FOR NOx REMOVAL AND METHOD OF FORMING COATING FILM OF THE SAME |
| US6582839B1 (en) | 1999-09-02 | 2003-06-24 | Central Glass Company, Limited | Article with photocatalytic film |
| JP2003206601A (en) * | 2002-01-15 | 2003-07-25 | Taisei Laminator Co Ltd | Roofing material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60139756A (en) * | 1983-12-06 | 1985-07-24 | ミネソタ マイニング アンド マニユフアクチユアリング コンパニー | Polysiloxane composition |
| JPS60187322A (en) * | 1984-03-06 | 1985-09-24 | Toyota Central Res & Dev Lab Inc | Purifying method of waste |
| JPH01288321A (en) * | 1988-05-13 | 1989-11-20 | Matsushita Electric Ind Co Ltd | Deodorization by photocatalyst |
| JPH0431740A (en) * | 1990-05-28 | 1992-02-03 | Fujitsu Ltd | Method for inspecting presence or absence of contaminant in atmosphere |
| JPH0490763A (en) * | 1990-08-03 | 1992-03-24 | Okitsumo Kk | Deodorizing material and product using the same |
| JPH06315614A (en) * | 1993-03-11 | 1994-11-15 | Agency Of Ind Science & Technol | Method for removing contaminants and cleaning material |
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH07259448A (en) * | 1994-03-23 | 1995-10-09 | Shin Etsu Chem Co Ltd | Mold glass for glass louver provided with silicone foaming layer |
-
1996
- 1996-04-08 JP JP8110619A patent/JPH09271731A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60139756A (en) * | 1983-12-06 | 1985-07-24 | ミネソタ マイニング アンド マニユフアクチユアリング コンパニー | Polysiloxane composition |
| JPS60187322A (en) * | 1984-03-06 | 1985-09-24 | Toyota Central Res & Dev Lab Inc | Purifying method of waste |
| JPH01288321A (en) * | 1988-05-13 | 1989-11-20 | Matsushita Electric Ind Co Ltd | Deodorization by photocatalyst |
| JPH0431740A (en) * | 1990-05-28 | 1992-02-03 | Fujitsu Ltd | Method for inspecting presence or absence of contaminant in atmosphere |
| JPH0490763A (en) * | 1990-08-03 | 1992-03-24 | Okitsumo Kk | Deodorizing material and product using the same |
| JPH06315614A (en) * | 1993-03-11 | 1994-11-15 | Agency Of Ind Science & Technol | Method for removing contaminants and cleaning material |
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH07259448A (en) * | 1994-03-23 | 1995-10-09 | Shin Etsu Chem Co Ltd | Mold glass for glass louver provided with silicone foaming layer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6582839B1 (en) | 1999-09-02 | 2003-06-24 | Central Glass Company, Limited | Article with photocatalytic film |
| WO2001021716A1 (en) * | 1999-09-17 | 2001-03-29 | Nihon Parkerizing Co., Ltd. | PHOTOCATALYST COATING MATERIAL FOR NOx REMOVAL AND METHOD OF FORMING COATING FILM OF THE SAME |
| JP2003206601A (en) * | 2002-01-15 | 2003-07-25 | Taisei Laminator Co Ltd | Roofing material |
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