JPH1085610A - Photocatalytic hydrophilic member and its production - Google Patents
Photocatalytic hydrophilic member and its productionInfo
- Publication number
- JPH1085610A JPH1085610A JP8281226A JP28122696A JPH1085610A JP H1085610 A JPH1085610 A JP H1085610A JP 8281226 A JP8281226 A JP 8281226A JP 28122696 A JP28122696 A JP 28122696A JP H1085610 A JPH1085610 A JP H1085610A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- photocatalytic
- oxide
- water
- coating
- 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
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002344 surface layer Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000010304 firing Methods 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910008332 Si-Ti Inorganic materials 0.000 abstract 3
- 229910006749 Si—Ti Inorganic materials 0.000 abstract 3
- 230000000694 effects Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000003981 vehicle Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 9
- 239000000428 dust Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 230000001443 photoexcitation Effects 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000002772 conduction electron Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 239000002243 precursor Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000006059 cover glass Substances 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
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 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
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001074085 Scophthalmus aquosus Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004888 barrier function 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
- 238000011109 contamination Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 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
- 238000012643 polycondensation polymerization Methods 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
- 239000004575 stone Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 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
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MZZINWWGSYUHGU-UHFFFAOYSA-J ToTo-1 Chemical compound [I-].[I-].[I-].[I-].C12=CC=CC=C2C(C=C2N(C3=CC=CC=C3S2)C)=CC=[N+]1CCC[N+](C)(C)CCC[N+](C)(C)CCC[N+](C1=CC=CC=C11)=CC=C1C=C1N(C)C2=CC=CC=C2S1 MZZINWWGSYUHGU-UHFFFAOYSA-J 0.000 description 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
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 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
- 238000010276 construction Methods 0.000 description 1
- 238000010411 cooking Methods 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 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
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 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
- 239000011241 protective layer Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000004044 response Effects 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for making a member surface highly hydrophilic and maintaining it. More specifically, the present invention relates to an anti-fog technology for preventing the fogging and water droplets from forming on a mirror, lens, glass, prism or other transparent member by making the surface of the member highly hydrophilic. The present invention also prevents the surface from being stained by highly hydrophilizing the surface of a building, a window glass, a mechanical device or an article,
Alternatively, the present invention relates to a technique for self-cleaning (self-cleaning) or easily cleaning a surface.
【０００２】[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。2. Description of the Related Art It is often experienced that in cold weather, windshields and windows of automobiles and other vehicles, window glasses of buildings, lenses of glasses, and cover glasses of various instrument panels are fogged by condensed moisture. In addition, mirrors and eyeglass lenses in bathrooms and washrooms are often fogged by steam. Furthermore,
Vehicle windshields and windows, building windows, vehicle rearview mirrors, eyeglass lenses, masks and helmet shields are subjected to rainfall and splashes, and when a large number of discrete droplets of water adhere to the surface, their surfaces become shaded. , Blurred, mottled, or cloudy, again losing visibility. Needless to say, the above "clouding" has a profound effect on safety and efficiency of various operations. For example, if the windshield or window glass of the vehicle or the rearview mirror of the vehicle is overcast or cloudy in cold weather or rainy weather, it becomes difficult to secure a view, and traffic safety is impaired. Fogging of the endoscope lens and the dental dentoscope hinders accurate diagnosis, surgery, and treatment. When the cover glass of the instrument panel becomes cloudy, it becomes difficult to read the data.
【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３−１
２９３５７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。It has been proposed to make the surface hydrophilic in order to eliminate the "clouding". For example, 3-1
No. 29357 discloses a method in which 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, thereby making the surface of the polymer layer hydrophilic. An anti-fogging method for a mirror is disclosed. However, with such acidic groups, the surface polarity is not sufficient and the surface loses hydrophilicity over time due to contaminants adhering to the surface,
It is considered that the anti-fog performance is gradually lost.
【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．１
５−２４）。[0004] On the other hand, in the fields of construction and paints, stains on building exterior materials, outdoor buildings and their coatings have become a problem with environmental pollution. Dust and particles suspended in the air accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater as it rains and flows down the building's outer walls. Furthermore, in the rain, the floating dust is carried by the rain and flows down on the outer wall of the building or the surface of the outdoor building. As a result, pollutants adhere to the surface along the path of rainwater. When the surface dries, striped stains appear on the surface. Dirt on building exterior materials and coatings consists of combustion products such as carbon black, and inorganic pollutants such as urban dust and clay particles. It is thought that such a variety of contaminants complicates antifouling measures (Yoshinori Tachibana, "Method for Accelerated Testing of Contamination of Exterior Wall Finishing Materials", Proc. No., October 1989, p.
5-24).
【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（ＰＴ
ＦＥ）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。According to conventional wisdom, in order to prevent dirt on the building exterior and the like, polytetrafluoroethylene (PT) is used.
Although water-repellent paints such as FE) were considered preferable, recently it has been considered that it is desirable to make the surface of the paint film as hydrophilic as possible for urban dust containing a large amount of hydrophobic components. (Polymer, Vol. 44, May 1995, p. 307). Therefore, it has been proposed to paint a building with a hydrophilic graft polymer (newspaper "Chemical Industry Daily", January 30, 1995). According to reports, this coating exhibits a hydrophilicity of 30 to 40 ° in contact angle with water. However, the contact angle of inorganic dust represented by clay minerals with water is from 20 ° to 50 °, and has an affinity for the graft polymer having 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】[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。As described above, by making the surface of the member hydrophilic, it is possible to prevent clouding and water droplet formation of the member, and to prevent the surfaces of buildings, window glasses, mechanical devices and articles from becoming dirty. Although there are proposals to prevent or to self-clean (self-clean) or easily clean the surface, the effect was not satisfactory because the surface could not 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 capable of maintaining a surface with a high degree of hydrophilicity for a long period of time.
【０００７】[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。SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst, the surface of the member is highly hydrophilized when the photocatalyst is photoexcited. This phenomenon is considered to proceed by the following mechanism. That is, when light having energy equal to or greater than the energy gap between the upper end of the valence band of the photocatalyst and the lower end of the conduction electron band is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. However, one or both of these actions probably imparts polarity to the surface and collects polar components such as water and hydroxyl groups. Then, one or both of the conduction electrons and holes and the above-mentioned polar components cooperate to cut the chemical bond between the adsorption surface and the contaminant chemically adsorbed on the surface, and the chemically adsorbed water on the surface. It adsorbs and a physisorbed water layer is formed on it.
【０００８】本発明では、光触媒性酸化チタンと、ケイ
素とチタンの複合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
らにその上にケイ素とチタンの複合酸化物を含有する表
面層が形成されている、光触媒性親水性部材を提供す
る。表面層にケイ素とチタンの複合酸化物が含有される
と、前記複合酸化物表面はハメットの酸度関数Ｈｏ＝−
５．６程度の酸性を呈するため、表面の極性が光の有無
にかかわらず極端に大きな状態になる。そのために、疎
水性分子よりも極性分子である水分子を選択的に吸着さ
せやすい。そのため安定な物理吸着水層が形成されやす
く、暗所に保持しても、表面の親水性をかなり長期にわ
たり高度に維持できる。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。In the present invention, a surface layer containing a photocatalytic titanium oxide and a complex oxide of silicon and titanium is formed, or a layer containing a photocatalytic titanium oxide is formed, and further a silicon and titanium oxide layer is formed thereon. Provided is a photocatalytic hydrophilic member, on which a surface layer containing a composite oxide is formed. When the composite oxide of silicon and titanium is contained in the surface layer, the surface of the composite oxide has a Hammett acidity function Ho = −.
Since it has an acidity of about 5.6, the polarity of the surface becomes extremely large regardless of the presence or absence of light. Therefore, it is easier to selectively adsorb a water molecule which is a polar molecule than a hydrophobic molecule. Therefore, a stable physically adsorbed water layer is easily formed, and even if the layer is kept in a dark place, the hydrophilicity of the surface can be maintained at a high level for a considerably long period. Furthermore, since the photocatalytic oxide is contained in the surface layer, even when the hydrophilicity of the surface has been lost due to long-term storage in a dark place, etc., the superhydrophilicity is increased according to the photoexcitation of the photocatalytic oxide. Will be presented.
【０００９】[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、ケイ素とチタンの複合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、さらにその上にケイ素とチタ
ンの複合酸化物を含有する表面層が形成されているよう
にする。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the first embodiment of the present invention, as shown in FIG. 1, a surface layer containing a photocatalytic titanium oxide and a composite oxide of silicon and titanium is formed on a substrate surface. To be. In the second embodiment of the present invention, as shown in FIG. 2, a photocatalytic titanium oxide-containing layer is formed on a substrate surface, and a surface layer containing a composite oxide of silicon and titanium is further formed thereon. To have been.
【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／ＪＰ９６／００７
３３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。The term “highly hydrophilic” in the present invention means a state exhibiting water wettability of 10 ° or less, preferably 5 ° or less in terms of a contact angle with water. PCT / JP96 / 007
As shown in No. 33, if the surface of the member is less than 10 ° in terms of the contact angle with water, condensed water forms individual water droplets even if moisture or steam in the air is dewed. Without this, the tendency to form a uniform water film becomes remarkable. Therefore, the tendency that light scattering fogging does not occur on the surface becomes remarkable. Similarly, when windowpanes, vehicle rearview mirrors, vehicle windshields, spectacle lenses, or helmet shields are exposed to rain or splashes, a high degree of visibility and visibility is achieved without discrete and unsightly water droplets. As a result, the effects of ensuring the safety of vehicles and traffic, and improving the efficiency of various tasks and activities are dramatically improved. Also, as shown in PCT / JP96 / 00733, if the surface of the member is in a state of 10 ° or less, preferably 5 ° or less in terms of a contact angle with water, urban dust,
Combustion products such as carbon black contained in exhaust gas from automobiles, hydrophobic contaminants such as oils and fats, and sealant eluting components, and inorganic clay contaminants are unlikely to adhere to each other. Can be dropped.
【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。If the surface of the member can maintain the above-mentioned high degree of hydrophilicity, in addition to the above-mentioned anti-fogging effect and surface cleaning effect, it also has an anti-static effect (dust-preventing effect), a heat-insulating effect, an effect of preventing bubbles from adhering in water, heat exchange. The effect of improving the efficiency of the vessel, the effect of biocompatibility, and the like are exhibited.
【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。The substrate to which the present invention can be applied is a transparent member in the case where the above antifogging effect is expected, and glass, plastic, or the like can be suitably used as the material. Speaking of applicable base materials, mirrors such as rearview mirrors for vehicles, mirrors for bathrooms, mirrors for toilets, dental mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, Lenses such as illumination lenses, semiconductor lenses, and copier lenses; prisms; windows of buildings and towers; automobiles, rail vehicles, aircraft, ships, submersibles, snowmobiles, ropeway gondolas, and amusement park gondolas. , Windowpanes for vehicles such as spacecraft; cars, railcars, aircraft, ships, submarines,
Windshields for vehicles such as snowmobiles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, spaceships; protective goggles, sports goggles, shields for protective masks, shields for sports masks, shields for helmets , A frozen food display case; a cover glass of a measuring instrument; and a film to be attached to the surface of the article. As a substrate to which the present invention can be applied, when the above surface cleaning effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth, and the like. Combinations and their laminates can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, window glasses, structural members, vehicle exteriors and coatings,
Exterior of machinery and equipment, dust cover and paint, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guard rail exterior and paint, tunnel interior and paint, insulators, solar cell covers , Solar water heater heat collecting cover, greenhouse, vehicle lighting cover, housing equipment, toilet bowl, bathtub, wash basin, lighting equipment, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking It includes a range, a kitchen hood, a ventilation fan, and a film to be attached to the surface of the article. As a substrate to which the present invention can be applied, when the above antistatic effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, cloth,
Combinations thereof and laminates thereof can be suitably used.
Speaking of applicable base materials, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housing and parts for household electrical appliances, exterior and coating, OA equipment Product housing, parts, exterior and painting, building materials, building exterior, building interior, window frames, window glass, structural members, vehicle exterior and painting, machinery and articles exterior, dustproof cover and painting, and on the above article surface Includes film to be applied.
【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、０．００１ｍ
Ｗ／ｃｍ２以上あればよいが、０．０１ｍＷ／ｃｍ２以
上だと好ましく、０．１ｍＷ／ｃｍ２以上だとより好ま
しい。A photocatalytic oxide is a material that emits light (excitation light) having an energy (ie, shorter wavelength) larger than the energy gap between the conduction electron band and the valence band of an oxide crystal. An oxide that can generate conduction electrons and holes by the excitation of electrons (photoexcitation) in the band. Anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, bismuth trioxide, tungsten trioxide, Ferric oxide, strontium titanate and the like can be suitably used. Here, as a light source used for photoexcitation of the photocatalytic oxide, indoor lighting such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, and a mercury lamp, the sun, and a light source in which light from those light sources is guided by a low-loss fiber are used. It can be suitably used. In order for the substrate surface to be highly hydrophilized by photoexcitation of the photocatalytic oxide, the illuminance of the excitation light is 0.001 m
W suffices / cm 2 or more, but preferably that it 0.01 mW / cm 2 or more, and more preferably it 0.1 mW / cm 2 or more.
【００１４】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ｐ
ｔ、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。また、上
記白金族金属の添加により、ケイ素とチタンとの複合酸
化物の酸度が向上するので、親水維持性も向上する。上
記表面層にＭｏを添加してもよい。この場合もケイ素と
チタンとの複合酸化物の酸度が向上するので、親水維持
性は向上する。It is preferable that the thickness of the surface layer be 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the more transparent the member can be. Further, when the film thickness is reduced, the wear resistance of the surface layer is improved. The surface of the surface layer may be further provided with a wear-resistant or corrosion-resistant protective layer capable of being made hydrophilic and other functional films. Preferably, the surface layer does not have a very high refractive index as compared to the substrate. Preferably, the refractive index of the surface layer is 2 or less. Then, light reflection at the interface between the base material and the surface layer can be suppressed. When the substrate is a glass or glazed tile containing an alkali network modifying ion such as sodium, an intermediate layer such as silica may be formed between the substrate and the surface layer. Then, the diffusion of the alkali network modifying ions from the base material to the surface layer during the firing is prevented, and the photocatalytic function is more effectively exhibited. Metals such as Ag, Cu, and Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria adhering to the surface. Furthermore, this surface layer inhibits the growth of microorganisms such as molds, algae and moss. Therefore, adhesion of dirt on the member surface due to microorganisms can be more effectively suppressed. The surface layer has p
Platinum group metals such as t, Pd, Rh, Ru, Os, Ir can be added. The surface layer to which the metal is added can enhance the oxidizing activity of the photocatalyst, and promote the decomposition of contaminants attached to the member surface. Further, the addition of the platinum group metal improves the acidity of the composite oxide of silicon and titanium, so that the hydrophilicity is also improved. Mo may be added to the surface layer. Also in this case, the acidity of the composite oxide of silicon and titanium is improved, so that the hydrophilicity retention is improved.
【００１５】図１の親水性部材の形成方法は、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；
又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、ケイ素とチ
タンとの複合酸化物が光触媒性酸化チタン粒子間の粒界
に形成されうる４５０〜９００℃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）以上であり、ケイ素とチタンとの複合
酸化物が光触媒性酸化チタン粒子間の粒界に形成されう
る４５０〜９００℃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。The method for forming the hydrophilic member shown in FIG. 1 is, for example, a mixture of a photocatalytic titanium oxide sol and a tetraalkoxysilane such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
Or a mixture of a photocatalytic titanium oxide sol and a silica sol;
Is applied onto the surface of the base material by a method such as spray coating, flow coating, spin coating, dip coating, roll coating, and the like, and a composite oxide of silicon and titanium is formed at a grain boundary between the photocatalytic titanium oxide particles. It is obtained by firing at a temperature of 450 to 900 ° C. and fixing the surface layer to the substrate. In another method for forming the hydrophilic member of FIG. 1, for example, tetraalkoxytitanium such as tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium; 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 tin oxide and silica sol, on a substrate surface, spray coating, flow coating, spin coating, dip coating, roll coating, electron After coating by a method such as beam evaporation, the temperature is higher than the temperature at which the precursor of the photocatalytic titanium oxide changes to a photocatalytic oxide (the crystallization temperature of anatase-type titanium oxide), and the composite oxide of silicon and titanium forms a photocatalyst. 4 that can be formed at the grain boundaries between crystalline titanium oxide particles And calcined at a temperature of 0 to 900 ° C., it is obtained by fixing the surface layer to the substrate.
【００１６】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
布し、ケイ素とチタンとの複合酸化物が形成されうる４
５０〜９００℃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）以上であり、かつケイ素とチ
タンとの複合酸化物が形成される５００〜８００℃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。In the method of forming the hydrophilic member shown in FIG. 2, for example, a sol in which photocatalytic titanium oxide particles are
After coating and drying by a method such as spray coating, flow coating, spin coating, dip coating, roll coating, and the like, further, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetraalkoxysilane such as tetrabutoxysilane; A silica sol; applied by any of the above methods to form a composite oxide of silicon and titanium.
It is obtained by firing at a temperature of 50 to 900 ° C. and fixing the surface layer to the substrate. In another method of forming the hydrophilic member of FIG. 2, for example, tetraalkoxytitanium such as tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium; titanium chelate, acetate titanium; titanium sulfate, titanium tetrachloride Spray coating, flow coating, spin coating, dip coating, roll coating, electron beam evaporation of a photocatalytic titanium oxide precursor such as a soluble inorganic titanium compound such as titanium hydroxide; amorphous titanium oxide And then dried, and then a tetraalkoxysilane such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; or a silica sol; Oxidation Baking at a temperature of 500 to 800 ° C., which is equal to or higher than the temperature at which the precursor of tan converts to a photocatalytic oxide (the crystallization temperature of anatase-type titanium oxide), and at which a composite oxide of silicon and titanium is formed. And by fixing the surface layer to a substrate. In the hydrophilic member shown in FIG. 2, it is preferable that the photocatalytic oxide layer has a thickness of 10 nm or more, because the photocatalytic oxide is particularly excellent in hydrophilicity by photoexcitation.
【００１７】[0017]
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固形分３５重量％）とコロイダルシリ
カ（日産化学、スノーテックスＯ、固形分２０重量％）
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、その粒界に生成するケイ素とチタン
との複合酸化物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。Embodiment 1 FIG. (Figure 1 type, titanium oxide sol + silica sol) Ammonia peptized anatase type titanium oxide sol (Ishihara Sangyo, STS-11 solid content 35% by weight) and colloidal silica (Nissan Chemical, Snowtex O, solid content 20% by weight)
Are mixed at a molar ratio of solids of 88:12, and 10 ×
It is applied to the surface of a 5 cm square glazed tile (TOTO Kiki, AB02E11) by the flow coating method,
For 1 hour to obtain a sample coated with a film composed of anatase-type titanium oxide particles, silica particles, and a composite oxide of silicon and titanium formed at the grain boundaries.
The thickness of the coating was 0.3 μm. The contact angle with water of the sample immediately after firing was 5 °. Here, the contact angle with water is determined by a contact angle measuring device (Kyowa Interface Science, CA-X150).
After dropping a water drop from the micro syringe on the sample surface, 30
Measured after seconds. After leaving the sample in the dark for one week, the contact angle with water was still 5 °. Thereafter, the sample surface was irradiated with ultraviolet light having an illuminance of 0.03 mW / cm 2 for about one day using an ultraviolet light source (Sankyo Electric, black light blue (BLB) fluorescent lamp), and the contact angle with water became 0 °. Was.
【００１８】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、８
０℃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、その粒界に生成するケイ素とチタ
ンとの複合酸化物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３
０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。Embodiment 2 FIG. (Figure 1 type, titanium alkoxide + silica sol) On a 10 cm square soda lime glass plate surface, 6 parts by weight of tetraethoxysilane (Wako Pure Chemical), 86 parts by weight of ethanol, 6 parts by weight of pure water, 2 parts by weight of 36% hydrochloric acid Is applied by a flow coating method,
Dry at a temperature of 0 ° C. In the process so far, tetraethoxysilane was converted into silanol by hydrolysis, and subsequently, a thin film of amorphous silica was formed on the surface of the glass plate by dehydration-condensation polymerization. Next, a coating obtained by mixing 1 g of a liquid containing 5 parts by weight of silica sol and 95 parts by weight of ethanol, and 5 g of a liquid containing 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 composed of amorphous titanium oxide and silica sol was formed on the surface of the glass plate. Then 500
By baking at ℃, the amorphous titanium oxide phase changes to anatase type titanium oxide, anatase type titanium oxide particles, silica particles, and a coating composed of a composite oxide of silicon and titanium generated at the grain boundaries A coated sample was obtained. Next, oleic acid was applied to the surface of the sample and stretched sufficiently. The surface was rubbed with a sponge impregnated with bath magic phosphorus, rinsed with running water, and then dried at 50 ° C. with a dryer.
The surface was intentionally contaminated by drying for 0 minutes.
As a result, the contact angle of the sample surface with water was 70 °.
Then, using a BLB fluorescent lamp, the UV illuminance was 0.2 mW /
Irradiation in cm 2 for 2 days. As a result, the contact angle of the sample surface with water was increased to 3 °. Next, the sample was allowed to stand in a dark place for one day, and the change in the contact angle of the sample surface with water was measured. As a result, the contact angle with water was maintained at a low value of about 5 °.
【００１９】[0019]
【発明の効果】本発明では、光触媒性酸化チタンと、ケ
イ素とチタンとの複合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
らにその上にケイ素とチタンとの複合酸化物を含有する
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、ケイ素とチタンとの複合酸化物が酸性を示すことに
基づく極性付与効果により、遮光時の親水性も長期にわ
たり維持されるようになる。According to the present invention, a layer containing a photocatalytic titanium oxide and a composite oxide of silicon and titanium is formed, or a layer containing a photocatalytic titanium oxide is formed. By forming a layer containing a composite oxide with titanium, 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 At the same time, the polarity imparting effect based on the fact that the composite oxide of silicon and titanium exhibits acidity allows the hydrophilicity during light shielding to be maintained for a long time.
【図１】 本発明の一実施態様を示す図。FIG. 1 is a diagram showing one embodiment of the present invention.
【図２】 本発明の他の実施態様を示す図。FIG. 2 is a diagram showing another embodiment of the present invention.
Claims (7)
イ素とチタンからなる複合酸化物を含有する表面層が形
成されていることを特徴とする光触媒性親水性部材。1. A photocatalytic hydrophilic member, wherein a surface layer containing a photocatalytic titanium oxide and a composite oxide composed of silicon and titanium is formed on a surface of a base material.
が形成され、さらにその上にケイ素とチタンからなる複
合酸化物を含有する表面層が形成されていることを特徴
とする光触媒性親水性部材。2. A photocatalytic hydrophilic material, wherein a photocatalytic titanium oxide-containing layer is formed on the surface of a substrate, and a surface layer containing a composite oxide composed of silicon and titanium is further formed thereon. Sex members.
ｎｍ以上であることを特徴とする請求項２に記載の光触
媒性親水性部材。3. The photocatalytic oxide-containing layer has a thickness of 10
The photocatalytic hydrophilic member according to claim 2, wherein the thickness is not less than nm.
と、シリカ粒子又はテトラアルコキシシランを含有層で
被覆する工程、４５０〜９００℃の温度で焼成してケイ
素とチタンからなる複合酸化物を形成する工程、を含む
光触媒性親水性部材の製造方法。4. A step of coating the surface of a base material with a layer containing photocatalytic titanium oxide particles and silica particles or tetraalkoxysilane, and baking at a temperature of 450 to 900 ° C. to obtain a composite oxide comprising silicon and titanium. Forming a photocatalytic hydrophilic member.
で被覆する工程、さらにその上にテトラアルコキシシラ
ンを含む液状物で被覆する工程、４５０〜９００℃の温
度で焼成してケイ素とチタンからなる複合酸化物を形成
する工程、を含む光触媒性親水性部材の製造方法。5. A step of coating the surface of the substrate with a layer containing a photocatalytic titanium oxide, a step of coating it further with a liquid containing tetraalkoxysilane, and baking at a temperature of 450 to 900 ° C. to form silicon and titanium. Forming a composite oxide comprising: a photocatalytic hydrophilic member.
粒子を含有層で被覆する工程、４５０〜９００℃の温度
で焼成して無定型酸化チタンを結晶化させるとともに、
ケイ素とチタンからなる複合酸化物を形成する工程、を
含む光触媒性親水性部材の製造方法。6. A step of coating the surface of a base material with a layer containing amorphous titanium oxide and silica particles, baking at a temperature of 450 to 900 ° C. to crystallize the amorphous titanium oxide,
Forming a composite oxide composed of silicon and titanium.
被覆する工程、さらにその上にテトラアルコキシシラン
を含む液状物で被覆する工程、４５０〜９００℃の温度
で焼成して無定型酸化チタンを結晶化させるとともに、
ケイ素とチタンからなる複合酸化物を形成する工程、を
含む光触媒性親水性部材の製造方法。7. A step of coating the surface of the base material with an amorphous titanium oxide-containing layer, a step of coating the substrate surface with a liquid containing tetraalkoxysilane, and a step of firing at a temperature of 450 to 900 ° C. to form an amorphous oxide. While crystallizing titanium,
Forming a composite oxide composed of silicon and titanium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8281226A JPH1085610A (en) | 1996-09-17 | 1996-09-17 | Photocatalytic hydrophilic member and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8281226A JPH1085610A (en) | 1996-09-17 | 1996-09-17 | Photocatalytic hydrophilic member and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1085610A true JPH1085610A (en) | 1998-04-07 |
Family
ID=17636131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8281226A Pending JPH1085610A (en) | 1996-09-17 | 1996-09-17 | Photocatalytic hydrophilic member and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1085610A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001245778A (en) * | 2000-03-03 | 2001-09-11 | Toray Ind Inc | Carpet or the like |
| EP1153658A1 (en) * | 2000-05-11 | 2001-11-14 | Ichikoh Industries Limited | Visible light response type photocatalyst |
| US6938546B2 (en) | 2002-04-26 | 2005-09-06 | Mitsubishi Heavy Industries, Ltd. | Printing press, layered formation and making method thereof, and printing plate and making method thereof |
| US7695774B2 (en) | 2002-01-31 | 2010-04-13 | Fuji Xerox Co., Ltd. | Titanium oxide photocatalyst thin film and production method of titanium oxide photocatalyst thin film |
| US7929225B2 (en) * | 2008-03-28 | 2011-04-19 | Fujinon Corporation | Lens assembly and imaging device |
-
1996
- 1996-09-17 JP JP8281226A patent/JPH1085610A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001245778A (en) * | 2000-03-03 | 2001-09-11 | Toray Ind Inc | Carpet or the like |
| EP1153658A1 (en) * | 2000-05-11 | 2001-11-14 | Ichikoh Industries Limited | Visible light response type photocatalyst |
| US7695774B2 (en) | 2002-01-31 | 2010-04-13 | Fuji Xerox Co., Ltd. | Titanium oxide photocatalyst thin film and production method of titanium oxide photocatalyst thin film |
| US6938546B2 (en) | 2002-04-26 | 2005-09-06 | Mitsubishi Heavy Industries, Ltd. | Printing press, layered formation and making method thereof, and printing plate and making method thereof |
| US7929225B2 (en) * | 2008-03-28 | 2011-04-19 | Fujinon Corporation | Lens assembly and imaging device |
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