JP3613085B2 - Photocatalytic hydrophilic member - Google Patents
Photocatalytic hydrophilic member Download PDFInfo
- Publication number
- JP3613085B2 JP3613085B2 JP23956899A JP23956899A JP3613085B2 JP 3613085 B2 JP3613085 B2 JP 3613085B2 JP 23956899 A JP23956899 A JP 23956899A JP 23956899 A JP23956899 A JP 23956899A JP 3613085 B2 JP3613085 B2 JP 3613085B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- amorphous
- photocatalytic
- water
- hydrophilicity
- 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.)
- Expired - Lifetime
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- 230000001699 photocatalysis Effects 0.000 title claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 36
- 239000002344 surface layer Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 14
- 239000011941 photocatalyst Substances 0.000 claims description 10
- 230000001443 photoexcitation Effects 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 7
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 3
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000005357 flat glass Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000000428 dust Substances 0.000 description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000002772 conduction electron Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000012643 polycondensation polymerization Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material 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
- 239000006229 carbon black Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 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
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 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
- 230000001681 protective effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- GPMKKHIGAJLBMZ-UHFFFAOYSA-J titanium(4+);tetraacetate Chemical compound [Ti+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O GPMKKHIGAJLBMZ-UHFFFAOYSA-J 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta 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
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000002079 cooperative effect Effects 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
Description
【０００１】
【発明の属する技術分野】
本発明は、部材表面を高度の親水性になし、かつ維持する技術に関する。より詳しくは、本発明は、鏡、レンズ、ガラス、プリズムその他の透明部材の表面を高度に親水化することにより、部材の曇りや水滴形成を防止する防曇技術に関する。本発明は、また、建物や窓ガラスや機械装置や物品の表面を高度に親水化することにより、表面が汚れるのを防止し、又は表面を自己浄化（セルフクリーニング）し若しくは容易に清掃する技術に関する。
【０００２】
【従来の技術】
寒冷時に自動車その他の乗物の風防ガラスや窓ガラス、建物の窓ガラス、眼鏡のレンズ、および各種計器盤のカバーガラスが凝縮湿分で曇るのはしばしば経験されることである。また、浴室や洗面所の鏡や眼鏡のレンズが湯気で曇ることも良く遭遇される。更に、車両の風防ガラスや窓ガラス、建物の窓ガラス、車両のバックミラー、眼鏡のレンズ、マスクやヘルメットのシールドが降雨や水しぶきを受け、離散した多数の水滴が表面に付着すると、それらの表面は翳り、ぼやけ、斑模様になり、或いは曇り、やはり可視性が失われる。言うまでもなく、上記“曇り”は安全性や種々の作業の能率に深い影響を与える。例えば、車両の風防ガラスや窓ガラス、車両のバックミラーが、寒冷時や雨天に翳り或いは曇ると、視界の確保が困難となり、交通の安全性が損なわれる。内視鏡レンズや歯科用歯鏡が曇ると、的確な診断、手術、処置の障害となる。計器盤のカバーガラスが曇るとデータの読みが困難となる。
【０００３】
上記“曇り”の解消のために、表面を親水性にすることが提案されている。例えば、実開平３−１２９３５７号には、基材の表面にポリマー層を設け、この層に紫外線を照射した後アルカリ水溶液により処理することにより高密度の酸性基を生成し、これによりポリマー層の表面を親水性にすることからなる鏡の防曇方法が開示されている。しかし、この方法で得られる程度の酸性基では、表面極性が充分でなく、表面に付着する汚染物質により時間が経つにつれて表面は親水性を失い、防曇性能が次第に失われるものと考えられる。
【０００４】
他方、建築及び塗料の分野においては、環境汚染に伴い、建築外装材料や屋外建造物やその塗膜の汚れが問題となっている。大気中に浮遊する煤塵や粒子は晴天には建物の屋根や外壁に堆積する。堆積物は降雨に伴い雨水により流され、建物の外壁を流下する。更に、雨天には浮遊煤塵は雨によって持ち運ばれ、建物の外壁や屋外建造物の表面を流下する。その結果、表面には、雨水の道筋に沿って汚染物質が付着する。表面が乾燥すると、表面には縞状の汚れが現れる。建築外装材料や塗膜の汚れは、カーボンブラックのような燃焼生成物や、都市煤塵や、粘土粒子のような無機質物質の汚染物質からなる。このような汚染物質の多様性が防汚対策を複雑にしているものと考えられている（橘高義典著“外壁仕上材料の汚染の促進試験方法”、日本建築学会構造系論文報告集、第４０４号、１９８９年１０月、ｐ．１５−２４）。
【０００５】
従来の通念では、上記建築外装などの汚れを防止するためにはポリテトラフルオロエチレン（ＰＴＦＥ）のような撥水性の塗料が好ましいと考えられていたが、最近では、疎水性成分を多く含む都市煤塵に対しては、塗膜の表面を出来るだけ親水性にするのが望ましいと考えられている（高分子、４４巻、１９９５年５月号、ｐ．３０７）。そこで、親水性のグラフトポリマーで建物を塗装することが提案されている（新聞“化学工業日報”、１９９５年１月３０日）。報告によれば、この塗膜は水との接触角に換算して３０〜４０゜の親水性を呈する。しかしながら、粘土鉱物で代表される無機質塵埃の水との接触角は２０゜から５０゜であり、水との接触角が３０〜４０゜のグラフトポリマーに対して親和性を有しその表面に付着しやすいので、このグラフトポリマーの塗膜は無機質塵埃による汚れを防止することができないと考えられる。
【０００６】
【発明の解決すべき課題】
上記の如く、部材表面を親水性にすることにより、部材の曇りや水滴形成を防止したり、また、建物や窓ガラスや機械装置や物品の表面が汚れるのを防止し、又は表面を自己浄化（セルフクリーニング）し若しくは容易に清掃することができる提案は存在するものの、表面を高度の親水性に長期にわたり維持できないため、その効果は充分でなかった。そこで、本発明では、上記事情に鑑み、表面を長期にわたり高度の親水性に維持できる部材を提供することを目的とする。
【０００７】
【課題を解決するための手段、及び作用】
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電子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、上記極性成分の協調的な作用により、吸着表面と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。
【０００８】
本発明では、光触媒性酸化チタンと、アモルファス酸化物を含有する表面層が形成されている、或いは光触媒性酸化チタン含有層が形成され、さらにその上にアモルファス酸化物を含有する表面層が形成されている、部材を提供する。表面層にアモルファス酸化物が含有されると、前記アモルファス酸化物は、開いた構造であるため、優れた蓄水性を有し、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。さらに、表面層に光触媒性酸化物が含有されていることにより、長期の暗所放置などで表面の親水性が失われてきた場合においても、光触媒性酸化物の光励起に応じて超親水性を呈するようになる。
【０００９】
【発明の実施の形態】
本発明の第一実施態様においては、図１に示すように、基材表面に、光触媒性酸化チタンと、アモルファス酸化物を含有する表面層が形成されているようにする。本発明の第二実施態様においては、図２に示すように、基材表面に、光触媒性酸化チタン含有層が形成され、さらにその上にアモルファス酸化物を含有する表面層が形成されているようにする。
【００１０】
本発明における高度の親水性とは、水との接触角に換算して１０゜以下、好ましくは５゜以下の水濡れ性を呈する状態をいう。ＰＣＴ／ＪＰ９６／００７３３号に示したように、部材表面が水との接触角に換算して１０゜以下の状態であれば、空気中の湿分や湯気が結露しても、凝縮水が個々の水滴を形成せずに一様な水膜になる傾向が顕著になる。従って、表面に光散乱性の曇りを生じない傾向が顕著になる。同様に、窓ガラスや車両用バックミラーや車両用風防ガラスや眼鏡レンズやヘルメットのシールドが降雨や水しぶきを浴びた場合に、離散した目障りな水滴が形成されずに、高度の視界と可視性を確保し、車両や交通の安全性を保証し、種々の作業や活動の能率を向上させる効果が飛躍的に向上する。また、同様にＰＣＴ／ＪＰ９６／００７３３号に示したように、部材表面が水との接触角に換算して１０゜以下、好ましくは５゜以下の状態であれば、都市煤塵、自動車等の排気ガスに含有されるカーボンブラック等の燃焼生成物、油脂、シーラント溶出成分等の疎水性汚染物質、及び無機粘土質汚染物質双方が付着しにくく、付着しても降雨や水洗により簡単に落せる状態になる。
【００１１】
部材表面が上記高度の親水性を維持できれば、上記防曇効果、表面清浄化効果の他、帯電防止効果（ほこり付着防止効果）、断熱効果、水中での気泡付着防止効果、熱交換器における効率向上効果、生体親和性効果等が発揮されるようになる。
【００１２】
本発明が適用可能な基材としては、上記防曇効果を期待する場合には透明な部材であり、その材質はガラス、プラスチック等が好適に利用できる。適用可能な基材を用途でいえば、車両用バックミラー、浴室用鏡、洗面所用鏡、歯科用鏡、道路鏡のような鏡；眼鏡レンズ、光学レンズ、写真機レンズ、内視鏡レンズ、照明用レンズ、半導体用レンズ、複写機用レンズのようなレンズ；プリズム；建物や監視塔の窓ガラス；自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、ロープウエイのゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の窓ガラス；自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、スノーモービル、オートバイ、ロープウエイのゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の風防ガラス；防護用ゴーグル、スポーツ用ゴーグル、防護用マスクのシールド、スポーツ用マスクのシールド、ヘルメットのシールド、冷凍食品陳列ケースのガラス；計測機器のカバーガラス、及び上記物品表面に貼付させるためのフィルムを含む。本発明が適用可能な基材としては、上記表面清浄化効果を期待する場合にはその材質は、例えば、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、それらの組合せ、それらの積層体が好適に利用できる。適用可能な基材を用途でいえば、建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装、交通標識、各種表示装置、広告塔、道路用防音壁、鉄道用防音壁、橋梁、ガードレールの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー、ビニールハウス、車両用照明灯のカバー、住宅設備、便器、浴槽、洗面台、照明器具、照明カバー、台所用品、食器、食器洗浄器、食器乾燥器、流し、調理レンジ、キッチンフード、換気扇、及び上記物品表面に貼付させるためのフィルムを含む。本発明が適用可能な基材としては、上記帯電防止効果を期待する場合にはその材質は、例えば、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、それらの組合せ、それらの積層体が好適に利用できる。適用可能な基材を用途でいえば、ブラウン管、磁気記録メディア、光記録メディア、光磁気記録メディア、オーディオテープ、ビデオテープ、アナログレコード、家庭用電気製品のハウジングや部品や外装及び塗装、ＯＡ機器製品のハウジングや部品や外装及び塗装、建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装、及び上記物品表面に貼付させるためのフィルムを含む。
【００１３】
光触媒性酸化物とは、酸化物結晶の伝導電子帯と価電子帯との間のエネルギーギャップよりも大きなエネルギー（すなわち短い波長）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）によって、伝導電子と正孔を生成しうる酸化物をいい、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。ここで光触媒性酸化物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、水銀ランプのような室内照明、太陽、それらの光源からの光を低損失のファイバーで誘導した光源等が好適に利用できる。光触媒性酸化物の光励起により、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。
【００１４】
ここでアモルファス酸化物には、無定型シリカ、水ガラス、無定型酸化チタン、水酸化チタン、無定型アルミナ、水酸化アルミニウム等が好適に利用できる。
【００１５】
上記表面層の膜厚は０．２μｍ以下にするのが好ましい。そうすれば、光の干渉による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部材の透明度を確保することができる。更に、膜厚を薄くすれば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よい。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における光の反射を抑制できる。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や施釉タイルの場合には、基材と上記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。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を死滅させることができる。更に、この表面層は、黴、藻、苔のような微生物の成長を抑制する。従って、微生物起因の部材表面の汚れ付着がより有効に抑制されるようになる。上記表面層にはｐｔ、Ｐｄ、Ｒｈ、Ｒｕ、Ｏｓ、Ｉｒ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、光触媒による酸化活性を増強させることができ、部材表面に付着した汚染物質の分解を促進する。
【００１６】
図１の親水性部材の形成方法について、アモルファス酸化物が無定型シリカである場合を例にとり説明する。この場合、例えば光触媒性酸化チタンゾルと、テトラエトキシシラン、テトラメトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシランとの混合物を、基材表面上に、スプレーコーティング、フローコーティング、スピンコーティング、ディップコーティング、ロールコーティング等の方法で塗布後、乾燥させて、テトラアルコキシシランを加水分解、脱水縮重合させることにより無定型シリカを生成させるとともに、表面層を基材に固定することにより得られる。図１の親水性部材を形成する他の方法においては、光触媒性酸化チタンゾルとシリカゾルとの混合物を、基材表面上に、スプレーコーティング、フローコーティング、スピンコーティング、ディップコーティング、ロールコーティング等の方法で塗布後、表面層を基材に固定することにより得られる。図１の親水性部材を形成する他の方法においては、例えば、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のテトラアルコキシチタン；チタンキレート、アセテートチタン；硫酸チタン、四塩化チタン等の溶解性無機チタン化合物；水酸化チタン；無定型酸化チタンなどの光触媒性酸化チタンの前駆体とシリカゾルを基材表面上に、スプレーコーティング、フローコーティング、スピンコーティング、ディップコーティング、ロールコーティング、電子ビーム蒸着等の方法で塗布後、光触媒性酸化チタンの上記前駆体が光触媒性酸化物に変化する温度（アナターゼ型酸化チタンの結晶化温度）以上である４００℃以上の温度で焼成し、表面層を基材に固定することにより得られる。
【００１７】
図２の親水性部材の形成方法は、例えば光触媒性酸化チタン粒子を懸濁したゾルを基材表面上に、スプレーコーティング、フローコーティング、スピンコーティング、ディップコーティング、ロールコーティング等の方法で塗布、乾燥後、をさらにその上にテトラエトキシシラン、テトラメトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン；又はシリカゾル；を、上記いずれかの方法で塗布後、乾燥させて、テトラアルコキシシランを加水分解、脱水縮重合させることにより無定型シリカを生成させるとともに、表面層を基材に固定することにより得られる。図２の親水性部材を形成する他の方法においては、例えば、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のテトラアルコキシチタン；チタンキレート、アセテートチタン；硫酸チタン、四塩化チタン等の溶解性無機チタン化合物；水酸化チタン；無定型酸化チタンなどの光触媒性酸化チタンの前駆体を基材表面上に、スプレーコーティング、フローコーティング、スピンコーティング、ディップコーティング、ロールコーティング、電子ビーム蒸着等の方法で塗布、乾燥後、テトラエトキシシラン、テトラメトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン；又はシリカゾル；を、さらにその上に上記いずれかの方法で塗布し、光触媒性酸化チタンの上記前駆体が光触媒性酸化物に変化する温度（アナターゼ型酸化チタンの結晶化温度）以上である４００℃以上の温度で焼成し、表面層を基材に固定することにより得られる。図２の親水性部材においては、光触媒性酸化物層の膜厚が１０ｎｍ以上だと特に光触媒の光励起による親水化性能に優れ、好ましい。
【００１８】
【実施例】
実施例１．（図１型、酸化チタンゾル＋シリカゾル）
アンモニア解膠アナターゼ型酸化チタンゾル（石原産業、ＳＴＳ−１１）とコロイダルシリカ（日産化学、スノーテックスＯ）を固形分のモル比で８８：１２の割合で混合し、１０×５ｃｍ角の施釉タイル（東陶機器、ＡＢ０２Ｅ１１）の表面に、フローコーティング法により塗布し、８００℃の温度で１時間焼成し、アナターゼ型酸化チタン粒子と、シリカ粒子とからなる被膜で被覆された試料を得た。被膜の膜厚は０．３μｍであった。焼成直後の試料の水との接触角は５゜であった。ここで水との接触角は、接触角測定器（協和界面科学、ＣＡ−Ｘ１５０）により、マイクロシリンジから試料表面に水滴を滴下した後３０秒後に測定した。試料を１週間暗所に放置した後の水との接触角は依然５゜であった。その後、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、照度０．０３ｍＷ／ｃｍ２の紫外線を約１日間試料表面に照射したところ、水との接触角は０゜になった。
【００１９】
実施例２．（図１型、チタンアルコキシド＋シリカゾル）
１０ｃｍ角のソーダライムガラス板表面に、テトラエトキシシラン（和光純薬）６重量部、エタノール８６重量部、純水６重量部、３６％塩酸２重量部からなるコーティング溶液を、フローコーティング法により塗布し、８０℃の温度で乾燥させた。ここまでの過程で、テトラエトキシシランは加水分解によりシラノールになり、続いて脱水縮重合により無定型シリカの薄膜がガラス板表面に形成された。次に、シリカゾル５重量部とエタノール９５重量部からなる液状物１ｇと、テトラエトキシチタン１０重量部、エタノール９０重量部、３６％塩酸１重量部からなる液状物５ｇとを混合して得たコーティング溶液を、フローコーティング法により塗布し、８０℃の温度で乾燥させた。ここまでの過程で、テトラエトキシチタンは加水分解により水酸化チタンになり、続いて脱水縮重合により無定型酸化チタンに変化した。すなわちここまでの過程で、ガラス板表面には無定型酸化チタンとシリカゾルからなる薄膜が形成された。次いで５００℃で焼成することにより、無定型酸化チタンをアナターゼ型酸化チタンに相変化し、アナターゼ型酸化チタン粒子と、シリカ粒子とからなる被膜で被覆された試料を得た。次いで、試料表面にオレイン酸を塗布し、充分に伸した後、バスマジックリンを染み込ませたスポンジで表面をこすり、流水で濯いだ後、乾燥器により５０℃で３０分乾燥させることにより、表面を故意に汚染させた。その結果、試料表面の水との接触角は７０゜となった。その後、ＢＬＢ蛍光灯を用い、紫外線照度０．２ｍＷ／ｃｍ２で２日間照射した。その結果、試料表面の水との接触角は３゜まで親水化された。次に、暗所で１日間放置し、試料表面の水との接触角の変化を測定した。その結果、水との接触角は５゜程度と低い値に維持された。
【００２０】
【発明の効果】
本発明では、光触媒性酸化チタンと、アモルファス酸化物を含有する層が形成されている、或いは光触媒性酸化チタン含有層が形成され、さらにその上にアモルファス酸化物を含有する層が形成されているようにすることにより、光触媒の光励起に応じて表面が親水化されるようになるので、表面を恒久的に高度の親水性に維持できるようになるとともに、アモルファス酸化物の示す蓄水効果により、遮光時の親水性も長期にわたり維持されるようになる。
【図面の簡単な説明】
【図１】本発明の一実施態様を示す図。
【図２】本発明の他の実施態様を示す図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a technique for making and maintaining a highly hydrophilic surface of a member. More specifically, the present invention relates to an anti-fogging technique for preventing fogging or water droplet formation of a member by highly hydrophilizing the surface of a mirror, lens, glass, prism or other transparent member. The present invention also prevents the surface from becoming dirty by highly hydrophilizing the surface of a building, window glass, mechanical device or article, or self-cleans the surface or easily cleans the surface. About.
[0002]
[Prior art]
It is often experienced that windshields and window glass of automobiles and other vehicles, building window glass, eyeglass lenses, and cover glass of various instrument panels become cloudy with condensed moisture during cold weather. In addition, it is often encountered that the mirrors in bathrooms and bathrooms and the lenses of spectacles become cloudy with steam. In addition, when windshields and window glass of vehicles, window glass of buildings, rear mirrors of vehicles, lens of glasses, shields of masks and helmets are subjected to rain and splashes, and many discrete water droplets adhere to the surface, those surfaces It is swaying, blurred, mottled, or cloudy and still loses visibility. Needless to say, the above “cloudiness” has a profound effect on safety and efficiency of various operations. For example, when the windshield glass, window glass, and vehicle rearview mirror of a vehicle are struck or clouded in cold weather or rainy weather, it becomes difficult to secure a field of view and traffic safety is impaired. When the endoscope lens or dental dental mirror becomes clouded, it becomes an obstacle to accurate diagnosis, surgery, and treatment. If the cover glass of the instrument panel is fogged, it will be difficult to read the data.
[0003]
In order to eliminate the “cloudiness”, it has been proposed to make the surface hydrophilic. For example, in Japanese Utility Model Laid-Open No. 3-129357, a polymer layer is provided on the surface of a base material, and this layer is irradiated with ultraviolet rays and then treated with an aqueous alkali solution to generate high-density acidic groups. A mirror anti-fogging method comprising making the surface hydrophilic is disclosed. However, it is considered that the acidic group to the extent obtained by this method has insufficient surface polarity, and the surface loses hydrophilicity over time due to contaminants adhering to the surface, and the antifogging performance is gradually lost.
[0004]
On the other hand, in the field of architecture and paint, contamination of building exterior materials, outdoor buildings and coating films has become a problem with environmental pollution. Dust and particles floating in the atmosphere accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater along with the rain and flows down the outer wall of the building. Furthermore, in the rainy weather, suspended dust is carried by the rain and flows down the outer wall of the building and the surface of the outdoor building. As a result, contaminants adhere to the surface along the rainwater path. As the surface dries, striped stains appear on the surface. The dirt on building exterior materials and coatings consists of combustion products such as carbon black, urban dust, and inorganic contaminants such as clay particles. It is considered that such a variety of pollutants complicates antifouling measures (Yoshinori Tachibana, “Testing method for promoting the contamination of exterior wall finishing materials”, Architectural Institute of Japan Structured Papers, No. 404 No., October 1989, p.15-24).
[0005]
Conventional wisdom has been that water-repellent paints such as polytetrafluoroethylene (PTFE) have been considered preferable to prevent dirt on the exterior of the building, but recently, cities that contain a large amount of hydrophobic components. For dust, it is considered desirable to make the surface of the coating as hydrophilic as possible (Polymer, Vol. 44, May 1995, p. 307). Therefore, it has been proposed to paint buildings with hydrophilic graft polymers (newspaper "Chemical Industry Daily", January 30, 1995). According to reports, this coating film exhibits a hydrophilicity of 30 to 40 ° in terms of a contact angle with water. However, the contact angle with water of inorganic dust typified by clay minerals is 20 ° to 50 °, and it has an affinity for graft polymers with a contact angle with water of 30 to 40 ° and adheres to the surface. Therefore, it is considered that this graft polymer coating film cannot prevent contamination by inorganic dust.
[0006]
Problems to be Solved by the Invention
As mentioned above, by making the surface of the member hydrophilic, it is possible to prevent the member from being fogged and forming water droplets, to prevent the surface of buildings, window glass, mechanical devices and articles from becoming dirty, or to self-clean the surface. Although there are proposals that can be (self-cleaning) or easily cleaned, the effect is not sufficient because the surface cannot be maintained at a high degree of hydrophilicity for a long time. In view of the above circumstances, an object of the present invention is to provide a member that can maintain a highly hydrophilic surface over a long period of time.
[0007]
[Means for solving the problems and actions]
The present invention is based on the discovery that in a member in which a surface layer containing a photocatalyst is formed, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the mechanism shown below. That is, when the photocatalyst is irradiated with light having an energy greater than the energy gap between the upper end of the valence band and the lower end of the conduction electron band of the photocatalyst, electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. However, due to the action of either or both of them, polarity is probably imparted to the surface, and polar components such as water and hydroxyl groups are collected. And by the cooperative action of either or both of the conduction electrons and holes and the polar component, the chemical bond between the adsorbing surface and the contaminant chemically adsorbed on the surface is broken, and chemically adsorbed water It is adsorbed and a physical adsorption water layer is formed on it.
[0008]
In the present invention, a photocatalytic titanium oxide and a surface layer containing an amorphous oxide are formed, or a photocatalytic titanium oxide containing layer is formed, and a surface layer containing an amorphous oxide is further formed thereon. and which provides a section member. When amorphous oxide is contained in the surface layer, the amorphous oxide has an open structure, so it has excellent water storage, so a stable physical adsorption water layer is easily formed and kept in a dark place. Even so, the hydrophilicity of the surface can be maintained at a high level for a fairly long time. Furthermore, since the surface layer contains a photocatalytic oxide, even when the hydrophilicity of the surface has been lost due to standing in the dark for a long period of time, it becomes superhydrophilic according to the photoexcitation of the photocatalytic oxide. Present.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the first embodiment of the present invention, as shown in FIG. 1, a surface layer containing photocatalytic titanium oxide and amorphous oxide is formed on the surface of the substrate. In the second embodiment of the present invention, as shown in FIG. 2, a photocatalytic titanium oxide-containing layer is formed on the substrate surface, and a surface layer containing an amorphous oxide is further formed thereon. To.
[0010]
High hydrophilicity in the present invention refers to a state exhibiting water wettability of 10 ° or less, preferably 5 ° or less in terms of contact angle with water. As shown in PCT / JP96 / 00733, if the surface of the member is in a state of 10 ° or less in terms of contact angle with water, the condensed water is not separated even if moisture or steam in the air is condensed. The tendency to form a uniform water film without forming water droplets becomes remarkable. Therefore, the tendency not to cause light scattering haze on the surface becomes remarkable. Similarly, when window glass, vehicle rearview mirrors, vehicle windshields, eyeglass lenses, and helmet shields are exposed to rain or splashing water, high visibility and visibility are achieved without the formation of discrete and annoying water droplets. Securing, guaranteeing the safety of vehicles and traffic, and improving the efficiency of various operations and activities are dramatically improved. Similarly, as shown in PCT / JP96 / 00733, if the surface of the member is 10 ° or less, preferably 5 ° or less in terms of the contact angle with water, exhaust from urban dust, automobiles, etc. Combustion products such as carbon black contained in the gas, hydrophobic contaminants such as oil and fat, sealant elution components, and inorganic clay contaminants are difficult to adhere, and even if they adhere, they can be easily removed by rainfall or water washing become.
[0011]
If the surface of the member can maintain the above-mentioned high hydrophilicity, in addition to the antifogging effect and surface cleaning effect, antistatic effect (dust adhesion preventing effect), heat insulation effect, bubble adhesion preventing effect in water, efficiency in heat exchanger An improvement effect, a biocompatibility effect, etc. come to be exhibited.
[0012]
The base material to which the present invention can be applied is a transparent member when the antifogging effect is expected, and glass, plastic or the like can be suitably used as the material. Applicable base materials include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, Lenses such as illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola Windshields of vehicles such as automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, gondola of amusement parks, and spacecraft; Protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case glass; -Glass, and films to be attached to the article surface. As the base material to which the present invention can be applied, when the above-mentioned surface cleaning effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, those Combinations and laminates thereof can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, window glass, structural members, exterior and painting of vehicles, exteriors of machinery and equipment, dust covers and paintings, traffic signs, various Display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar cell covers, solar water heater heat collection covers, plastic houses, vehicle lighting Covers, housing equipment, toilets, bathtubs, washstands, lighting fixtures, lighting covers, kitchenware, dishes, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, and for attaching to the surface of the article Includes film. As the base material to which the present invention is applicable, when the antistatic effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, and combinations thereof These laminates can be suitably used. Speaking of applicable base materials, cathode ray tube, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, household electrical appliance housings and parts, exterior and coating, OA equipment Product housing and parts, exterior and coating, building materials, building exterior, building interior, window frame, window glass, structural members, exterior and painting of vehicles, exterior of machinery and equipment, dust cover and painting, and on the surface of the article Includes film for application.
[0013]
A photocatalytic oxide is a substance in the valence band when irradiated with light (excitation light) having an energy (ie short wavelength) larger than the energy gap between the conduction electron band and the valence band of the oxide crystal. An oxide that can generate conduction electrons and holes by electron excitation (photoexcitation). Anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, second oxide Iron, strontium titanate and the like can be suitably used. Here, the light source used for photoexcitation of the photocatalytic oxide includes indoor lighting such as fluorescent lamps, incandescent lamps, metal halide lamps, mercury lamps, the sun, and light sources in which light from these light sources is guided by low-loss fibers. It can be suitably used. By photoexcitation of photocatalytic oxide, because the substrate surface is highly hydrophilized, illuminance of the excitation light, may if 0.001 mW / cm 2 or more, preferably that it 0.01 mW / cm 2 or more More preferably, it is 0.1 mW / cm 2 or more.
[0014]
Here, amorphous silica, water glass, amorphous titanium oxide, titanium hydroxide, amorphous alumina, aluminum hydroxide, and the like can be suitably used as the amorphous oxide.
[0015]
The film thickness of the surface layer is preferably 0.2 μm or less. By doing so, coloration of the surface layer due to light interference can be prevented. Further, the thinner the surface layer, the more transparent the member can be secured. Furthermore, if the film thickness is reduced, the wear resistance of the surface layer is improved. Further, a wear-resistant or corrosion-resistant protective layer that can be hydrophilized or other functional film may be provided on the surface of the surface layer. The surface layer preferably has a refractive index that is not so high as compared with the base material. Preferably, the refractive index of the surface layer is 2 or less. If it does so, reflection of the light in the interface of a base material and a surface layer can be suppressed. In the case where the substrate is glass or a glazed tile containing alkali network modifying ions such as sodium, an intermediate layer such as silica may be formed between the substrate and the surface layer. If it does so, it will prevent that an alkali network modification ion diffuses from a base material to a surface layer during baking, and a photocatalytic function will be exhibited better. 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 attached to the surface. Furthermore, this surface layer suppresses the growth of microorganisms such as straw, algae and moss. Therefore, the adhesion of dirt on the surface of the member caused by microorganisms is more effectively suppressed. A platinum group metal such as pt, Pd, Rh, Ru, Os, and Ir can be added to the surface layer. The surface layer to which the metal is added can enhance the oxidation activity by the photocatalyst and promote the decomposition of the contaminants attached to the member surface.
[0016]
The method for forming the hydrophilic member in FIG. 1 will be described by taking the case where the amorphous oxide is amorphous silica as an example. In this case, for example, a mixture of a photocatalytic titanium oxide sol and a tetraalkoxysilane such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is spray coated, flow coated, spin coated, After applying by a method such as dip coating or roll coating, it is dried to obtain amorphous silica by hydrolysis and dehydration condensation polymerization of tetraalkoxysilane, and the surface layer is fixed to a substrate. In another method of forming the hydrophilic member of FIG. 1, a mixture of photocatalytic titanium oxide sol and silica sol is sprayed, flow coated, spin coated, dip coated, roll coated, etc. on the substrate surface. It is obtained by fixing the surface layer to the substrate after application. In another method of forming the hydrophilic member of FIG. 1, for example, tetraalkoxy titanium such as tetraethoxy titanium, tetramethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium; titanium chelate, acetate titanium; titanium sulfate, titanium tetrachloride. Soluble inorganic titanium compounds such as: Titanium hydroxide; A precursor of photocatalytic titanium oxide such as amorphous titanium oxide and silica sol on the surface of the substrate, spray coating, flow coating, spin coating, dip coating, roll coating, electronic After coating by a method such as beam evaporation, the surface layer is baked at a temperature of 400 ° C. or higher, which is equal to or higher than the temperature at which the precursor of photocatalytic titanium oxide changes to photocatalytic oxide (crystallization temperature of anatase type titanium oxide). Can be obtained by fixing to a substrate.
[0017]
The hydrophilic member shown in FIG. 2 is formed by, for example, applying a sol in which photocatalytic titanium oxide particles are suspended onto a substrate surface by a method such as spray coating, flow coating, spin coating, dip coating, roll coating, and drying. Thereafter, a tetraalkoxysilane such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane; or silica sol; is applied by any of the above methods and then dried to obtain a tetraalkoxysilane. Amorphous silica is produced by hydrolysis and dehydration condensation polymerization, and the surface layer is fixed to a substrate. In another method of forming the hydrophilic member of FIG. 2, for example, tetraalkoxy titanium such as tetraethoxy titanium, tetramethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium; titanium chelate, acetate titanium; titanium sulfate, titanium tetrachloride. Soluble inorganic titanium compounds such as: Titanium hydroxide; A precursor of photocatalytic titanium oxide such as amorphous titanium oxide, spray coating, flow coating, spin coating, dip coating, roll coating, electron beam evaporation on the substrate surface After coating and drying by a method such as, tetraalkoxysilane such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane; or silica sol; Oxidation Calcined at Tan of the temperature at which the precursor is changed to photocatalytic oxide (anatase crystallization temperature of the titanium oxide) or more 400 ° C. or higher, obtained by fixing the surface layer to the substrate. In the hydrophilic member of FIG. 2, it is particularly preferable that the photocatalytic oxide layer has a thickness of 10 nm or more because the hydrophilicity of the photocatalyst by photoexcitation is excellent.
[0018]
【Example】
Example 1. (Figure 1 type, titanium oxide sol + silica sol)
Ammonia peptization anatase-type titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) and colloidal silica (Nissan Chemical Co., Snowtex O) were mixed at a molar ratio of solids of 88:12, and a 10 × 5 cm square glazed tile ( A sample coated with a film made of anatase-type titanium oxide particles and silica particles was obtained by applying to the surface of Totoki Equipment, AB02E11) by a flow coating method and firing at 800 ° C. for 1 hour. The film thickness was 0.3 μm. The contact angle with water of the sample immediately after baking was 5 °. Here, the contact angle with water was measured 30 seconds after a water droplet was dropped from the microsyringe onto the sample surface with a contact angle measuring device (Kyowa Interface Science, CA-X150). The contact angle with water after leaving the sample in the dark for one week was still 5 °. After that, when an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp) was used to irradiate the sample surface with ultraviolet light having an illuminance of 0.03 mW / cm 2 for about one day, the contact angle with water became 0 °. It was.
[0019]
Example 2 (Figure 1 type, titanium alkoxide + silica sol)
A coating solution consisting of 6 parts by weight of tetraethoxysilane (Wako Pure Chemical), 86 parts by weight of ethanol, 6 parts by weight of pure water and 2 parts by weight of 36% hydrochloric acid is applied to the surface of a 10 cm square soda lime glass plate by the flow coating method. And dried at a temperature of 80 ° C. In the process so far, tetraethoxysilane was converted to silanol by hydrolysis, and then an amorphous silica thin film was formed on the glass plate surface by dehydration condensation polymerization. Next, a coating obtained by mixing 5 g of silica sol and 1 g of a liquid consisting of 95 parts of ethanol and 5 g of a liquid consisting of 10 parts by weight of tetraethoxytitanium, 90 parts by weight of ethanol and 1 part by weight of 36% hydrochloric acid. The solution was applied by a flow coating method and dried at a temperature of 80 ° C. In the process so far, tetraethoxytitanium was converted to titanium hydroxide by hydrolysis, and subsequently changed to amorphous titanium oxide by dehydration condensation polymerization. That is, in the process so far, a thin film made of amorphous titanium oxide and silica sol was formed on the glass plate surface. Next, by firing at 500 ° C., amorphous titanium oxide was phase-changed to anatase-type titanium oxide, and a sample coated with a film composed of anatase-type titanium oxide particles and silica particles was obtained. Next, after applying oleic acid to the sample surface and stretching it sufficiently, the surface was rubbed with a sponge soaked in bath magicrin, rinsed with running water, and then dried at 50 ° C. for 30 minutes by a drier. The surface was deliberately contaminated. As a result, the contact angle of the sample surface with water was 70 °. Then, it irradiated for 2 days with the illumination intensity of ultraviolet rays 0.2mW / cm < 2 > using the BLB fluorescent lamp. As a result, the contact angle of the sample surface with water was made hydrophilic to 3 °. Next, the sample was left in a dark place for 1 day, and the change in contact angle with water on the sample surface was measured. As a result, the contact angle with water was maintained at a low value of about 5 °.
[0020]
【The invention's effect】
In the present invention, a layer containing a photocatalytic titanium oxide and an amorphous oxide is formed, or a layer containing a photocatalytic titanium oxide is formed, and a layer containing an amorphous oxide is further formed thereon. By doing so, the surface becomes hydrophilic in response to photoexcitation of the photocatalyst, so that the surface can be permanently maintained at a high degree of hydrophilicity, and by the water storage effect exhibited by the amorphous oxide, The hydrophilicity at the time of light shielding is also maintained over a long period of time.
[Brief description of the drawings]
FIG. 1 shows an embodiment of the present invention.
FIG. 2 is a diagram showing another embodiment of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23956899A JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35464995 | 1995-12-22 | ||
| JP7-354649 | 1995-12-22 | ||
| JP23956899A JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8281220A Division JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000227056A Division JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
| JP2004214860A Division JP2004306036A (en) | 1995-12-22 | 2004-07-22 | Photocatalytic hydrophilic member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000127289A JP2000127289A (en) | 2000-05-09 |
| JP3613085B2 true JP3613085B2 (en) | 2005-01-26 |
Family
ID=18438979
Family Applications (71)
| Application Number | Title | Priority Date | Filing Date |
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| JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
| JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
| JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
| JP15017196A Expired - Lifetime JP3760509B2 (en) | 1995-12-22 | 1996-05-22 | Greenhouse ceiling and its condensation prevention method |
| JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
| JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
| JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
| JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
| JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
| JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
| JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
| JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
| JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
| JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
| 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 |
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| 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 (58)
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| JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
| JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
| JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
| JP15017196A Expired - Lifetime JP3760509B2 (en) | 1995-12-22 | 1996-05-22 | Greenhouse ceiling and its condensation prevention method |
| JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
| JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
| JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
| JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
| JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
| JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
| JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
| JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
| JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
| JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
| 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 |
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| 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 |
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| JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
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| 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 |
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| 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 |
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| 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 |
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| 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 |
Family Applications After (12)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| JP (71) | JPH09231821A (en) |
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| JP3488496B2 (en) * | 1993-12-21 | 2004-01-19 | 日揮ユニバーサル株式会社 | Poison-resistant deodorizing photocatalyst |
| JP3391543B2 (en) * | 1993-12-27 | 2003-03-31 | 花王株式会社 | Hydrophilizing agent and hydrophilizing method |
| JP2883000B2 (en) * | 1994-03-29 | 1999-04-19 | 三菱重工業株式会社 | Automobile sound insulation wall cleaning device |
| JP3693363B2 (en) * | 1994-03-30 | 2005-09-07 | 松下エコシステムズ株式会社 | Supporting method for forming a photocatalyst layer |
| JPH07331120A (en) * | 1994-06-10 | 1995-12-19 | Hitachi Ltd | Coating for removing nitrogen oxide and its use |
| JP2832239B2 (en) * | 1994-06-21 | 1998-12-09 | 三井金属鉱業株式会社 | Lighting equipment with photocatalytic function |
| JPH0810576A (en) * | 1994-07-05 | 1996-01-16 | Ebara Res Co Ltd | Removing method of harmful gas and device therefor |
| JPH08119673A (en) * | 1994-10-21 | 1996-05-14 | Kansai Paint Co Ltd | Hydrophilization treatment of glass |
| JPH09129012A (en) * | 1995-03-31 | 1997-05-16 | Toshiba Lighting & Technol Corp | Photocatalyst, fluorescent lamp and luminaire |
| JPH08277147A (en) * | 1995-03-31 | 1996-10-22 | Nippon Muki Co Ltd | Plate glass |
| JP3101537B2 (en) * | 1995-05-10 | 2000-10-23 | ワイケイケイ株式会社 | Antifouling building material and exterior building material unit |
| JPH0929103A (en) * | 1995-05-17 | 1997-02-04 | Toshiba Lighting & Technol Corp | Photocatalytic body, photocatalytic device, light source and lightening equipment |
| JPH08313705A (en) * | 1995-05-22 | 1996-11-29 | Seiko Epson Corp | Anti-clouding article and its production |
| JP3127827B2 (en) * | 1995-06-14 | 2001-01-29 | 東陶機器株式会社 | Anti-fog seal |
| ATE391553T1 (en) * | 1995-06-19 | 2008-04-15 | Nippon Soda Co | SUPPORT STRUCTURE WITH PHOTOCATALYST AND PHOTOCATALYTIC COATING MATERIAL |
| JPH0990889A (en) * | 1995-09-27 | 1997-04-04 | Toshiba Lighting & Technol Corp | Sign body and externally illuminated sign device |
| JPH09173783A (en) * | 1995-10-27 | 1997-07-08 | Matsushita Electric Ind Co Ltd | Sheet glass and resin plate and their production and method for removing contaminant |
| JP4237830B2 (en) * | 1995-12-20 | 2009-03-11 | 日本曹達株式会社 | Photocatalyst-carrying lighting fixture |
| JPH09231821A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
-
1996
- 1996-04-05 JP JP8083499A patent/JPH09231821A/en active Pending
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2001
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