JPH10235204A - Photocatalytic hydrophilic member - Google Patents
Photocatalytic hydrophilic memberInfo
- Publication number
- JPH10235204A JPH10235204A JP9059827A JP5982797A JPH10235204A JP H10235204 A JPH10235204 A JP H10235204A JP 9059827 A JP9059827 A JP 9059827A JP 5982797 A JP5982797 A JP 5982797A JP H10235204 A JPH10235204 A JP H10235204A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- surface layer
- photocatalytic
- oxide
- acid compound
- 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 26
- 239000002344 surface layer Substances 0.000 claims abstract description 29
- -1 boric acid compound Chemical class 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000004327 boric acid Substances 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000576 coating method Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000003981 vehicle Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000000428 dust Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 230000001443 photoexcitation Effects 0.000 description 5
- 239000002772 conduction electron Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 238000003618 dip coating 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
- 239000011259 mixed solution Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000006229 carbon black Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic 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
- 238000010586 diagram Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 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
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002734 clay mineral 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 238000001035 drying 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
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm 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
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 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 1
- 238000011282 treatment Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- Specific Sealing Or Ventilating Devices For Doors And Windows (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Surface Treatment Of Glass (AREA)
- 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−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 of 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−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−、眼鏡のレンズ、マスクやヘルメットのシ
−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−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−ガラス
が曇るとデ−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 glazings of automobiles and other vehicles, glazings 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 back mirrors, eyeglass lenses, masks and helmet shields are subjected to rainfall and splashes, and when a large number of discrete water droplets adhere to the surface, the Can be dark, 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 back mirror of the vehicle is overcast or cloudy in cold weather or rainy weather, it is 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. If the cover glass of the instrument panel becomes fogged, 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−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−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, whereby the surface of the polymer layer becomes hydrophilic. A mirror anti-fogging method 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−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−
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−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−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, a hydrophilic graft polymer
It has been proposed to paint a building at (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 typified by clay minerals with water is from 20 ° to 50 °, and has an affinity for a graft polymer having a contact angle of 30 to 40 ° with water. It is thought that the coating of the graft polymer cannot prevent contamination by inorganic dust because it easily adheres.
【０００６】[0006]
【発明が解決しようとする課題】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−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 the member from fogging or forming water droplets, and also to prevent the surfaces of buildings, window glasses, mechanical devices and articles from becoming dirty. Although there are proposals that can prevent blemishes or clean the surface by self-cleaning or can be easily cleaned, the effect was not sufficient 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−ギャップ以上のエネルギ
−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、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 and the lower end of the conduction electron band of the photocatalyst is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited to cause conduction electrons and holes. Are produced, and one or both of them may possibly impart a polarity to the surface and collect polar components such as water and hydroxyl groups. Then, due to the coordinated action of one or both of the conduction electrons and holes and the above-mentioned polar component, the chemically adsorbed water is adsorbed on the surface, and a physically adsorbed water layer is formed thereon.
【０００８】本発明では、基材表面に、光触媒性酸化物
とホウ酸化合物又はホウケイ酸化合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物含有層が形成
され、さらにその上にホウ酸化合物又はホウケイ酸化合
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を提供する。表面層にホウ酸化合
物、ホウケイ酸化合物、アルミノホウ酸化合物、ケイ酸
化合物のいずれかが含有されると、これらの物質は蓄水
性を有するので、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。[0008] In the present invention, a surface layer containing a photocatalytic oxide and a boric acid compound or a borosilicate compound is formed on the surface of a substrate, or a photocatalytic oxide-containing layer is formed, and further thereon. Provided is a photocatalytic hydrophilic member, wherein a surface layer containing a boric acid compound or a borosilicate compound is formed. If the surface layer contains any of a boric acid compound, a borosilicate compound, an aluminoboric acid compound, and a silicate compound, these substances have a water storage property, so that a stable physical adsorption water layer is easily formed, and Even if held in place, the hydrophilicity of the surface can be maintained at a high level for a considerably long time. Furthermore, because 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, the photocatalytic oxide exhibits superhydrophilicity in response to photoexcitation of the photocatalytic oxide. Become like
【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、それ以外にホウ酸化合物、ホウケイ酸化合物、ア
ルミノホウ酸化合物、ケイ酸化合物のいずれかを含有す
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、さらにその上にホ
ウ酸化合物、ホウケイ酸化合物、アルミノホウ酸化合
物、ケイ酸化合物のいずれか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 a first embodiment of the present invention, as shown in FIG. 1, a photocatalytic titanium oxide and a boric acid compound, a borosilicate compound, an alumino borate compound, A surface layer containing any of the silicate compounds is formed. 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 boric acid compound, a borosilicate compound, an aluminoborate compound, and a silicic acid A surface layer containing any of the compounds is formed.
【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−や車両用風防ガラスや眼鏡レンズや
ヘルメットのシ−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−ボンブラック等の燃
焼生成物、油脂、シ−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 a window glass, a vehicle back mirror, a vehicle windshield, an eyeglass lens, or a shield of a helmet is exposed to rainfall or splashing, discrete unsightly water droplets are not formed, and high visibility and visibility are achieved. As a result, the effects of ensuring vehicle safety, ensuring the safety of vehicles and traffic, and improving the efficiency of various tasks and activities are dramatically improved. Similarly, as shown in PCT / JP96 / 00733, when 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, exhaust gas from city dust, automobiles, etc. Combustion products such as carbon black contained in water, hydrophobic contaminants such as oils and fats, sealant eluting components, and inorganic clay contaminants are unlikely to adhere to each other. You can drop it.
【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−、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−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−モ−ビル、オ−トバイ、ロ−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−グル、スポ−ツ用ゴ−グル、防護
用マスクのシ−ルド、スポ−ツ用マスクのシ−ルド、ヘ
ルメットのシ−ルド、冷凍食品陳列ケ−スのガラス；計
測機器のカバ−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−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−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−ドレ−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−、太陽熱温水器集熱カ
バ−、ビニ−ルハウス、車両用照明灯のカバ−、住宅設
備、便器、浴槽、洗面台、照明器具、照明カバ−、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−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−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−
ディオテ−プ、ビデオテ−プ、アナログレコ−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−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 vehicle back mirrors, bathroom mirrors, toilet mirrors, 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, railway vehicles, aircraft, ships, submersibles, snowmobiles, lowway gondolas, and amusement parks. Windowpanes for vehicles such as gondola and spacecraft; cars, railcars, aircraft, ships, submarines,
Windshields for vehicles such as snowmobiles, snowmobiles, motorcycles, lowway gondola, amusement park gondola, spaceships; protective goggles, sports goggles, protective Includes mask shield, sports mask shield, helmet shield, frozen food display case glass; measuring instrument cover glass; and film for attaching to the surface of the article. . When the surface cleaning effect is expected as a substrate to which the present invention can be applied, 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, 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 sound barriers, railway sound barriers, bridges, exterior and paint of garlands, tunnel interior and paint, Insulators, solar cell covers, solar water heater heat collection covers, vinyl houses, vehicular lighting covers, housing equipment, toilets, bathtubs, washbasins, lighting fixtures, lighting covers, kitchenware, tableware, tableware Includes washer, dish dryer, sink, cooking range, kitchen hood, ventilator, and film for application to the surface of the article. When the antistatic effect is expected as a substrate to which the present invention can be applied, 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,
Diode tapes, video tapes, analog records, housing and parts and exteriors and paintings for household electrical appliances, housings and parts and exteriors and paintings for OA equipment products, building materials, building exteriors, building interiors, window frames, windows It includes glass, structural members, vehicle exteriors and coatings, exteriors of machinery and articles, dustproof covers and paintings, and films to be attached to the article surfaces.
【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−ギャップよりも大き
なエネルギ−（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−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−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／ｃｍ 2 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 conductive oxide of an oxide crystal.
Greater than the energy gap between the valence band and the valence band
Light (excitation light) of high energy (ie, short wavelength)
When irradiated, the excitation (photoexcitation) of electrons in the valence band
Is an oxide that can generate conduction electrons and holes.
Tase type titanium oxide, rutile type titanium oxide, tin oxide, acid
Zinc oxide, bismuth trioxide, tungsten trioxide, oxide
Ferric iron, strontium titanate, etc. can be suitably used.
You. Here, as a light source used for photoexcitation of photocatalytic oxide
Are fluorescent, incandescent, metal halide, mercury
Lamps, the sun, and the light from those light sources.
Light sources guided by low-loss fibers can be used favorably
You. Due to photoexcitation of photocatalytic oxide, substrate surface is highly enhanced
To be made hydrophilic, the illuminance of the excitation light is 0.001 m
W / cmTwo Or more, but 0.01 mW / cm TwoLess than
Preferably above, 0.1 mW / cmTwo More than that
New
【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。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.
【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、ホウ酸化合物、ホウケイ酸化
合物、アルミノホウ酸化合物、ケイ酸化合物のいずれか
を含有する混合液を基材表面上に、スプレ−コ−ティン
グ、フロ−コ−ティング、スピンコ−ティング、ディッ
プコ−ティング、ロ−ルコ−ティング等の方法で塗布
後、室温放置又は熱処理により、表面層を基材に固定す
る。The method for forming the hydrophilic member shown in FIG. 1 is, for example, a method in which a mixed solution containing a photocatalytic titanium oxide sol and a boric acid compound, a borosilicate compound, an aluminoboric acid compound, or a silicate compound is coated on a substrate surface. After coating by a method such as spray coating, flow coating, spin coating, dip coating, roll coating, etc., the surface layer is fixed to the substrate by standing at room temperature or by heat treatment.
【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−コ−ティング、フロ−コ−ティング、スピンコ
−ティング、ディップコ−ティング、ロ−ルコ−ティン
グ等の方法で塗布、乾燥後、ホウ酸化合物、ホウケイ酸
化合物、アルミノホウ酸化合物、ケイ酸化合物のいずれ
かを含有する混合液を、さらにその上に上記いずれかの
方法で塗布し、室温放置又は熱処理により、表面層を固
定する。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−ト、アセテ
−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−
コ−ティング、フロ−コ−ティング、スピンコ−ティン
グ、ディップコ−ティング、ロ−ルコ−ティング、電子
ビ−ム蒸着等の方法で塗布、乾燥後、ホウ酸化合物、ホ
ウケイ酸化合物、アルミノホウ酸化合物、ケイ酸化合物
のいずれかを含有する混合液を、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−ゼ型酸化
チタンの結晶化温度）以上の温度で焼成し、表面層を基
材に固定する。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, etc. The mixed solution containing any of them is further applied thereon by any one of the above methods, and the surface layer is fixed by standing at room temperature or by heat treatment. In another method for forming the hydrophilic member shown in FIG. 2, for example, tetraalkoxytitanium such as tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium; titanium chelate, acetate titanium; A precursor of a photocatalytic titanium oxide such as a soluble inorganic titanium compound such as titanium chloride; titanium hydroxide; and amorphous titanium oxide is sprayed on a substrate surface.
Coating, flow-coating, spin-coating, dip-coating, roll-coating, electron beam evaporation and the like are applied and dried, and then a boric acid compound, a borosilicate compound, an alumino-boric acid compound, A mixed solution containing any of the silicate compounds is further applied thereon by any of the methods described above, and the temperature at which the precursor of the photocatalytic titanium oxide changes to a photocatalytic oxide (anatase type titanium oxide) Crystallization temperature) or more, and the surface layer is fixed to the 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]
【発明の効果】本発明によれば、基材表面を長期にわた
り高度の親水性に維持できるようになる。According to the present invention, the substrate surface can be maintained at a high degree of hydrophilicity for a long period of 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 (2)
外にホウ酸化合物、ホウケイ酸化合物、アルミノホウ酸
化合物、ケイ酸化合物のいずれか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 surface layer containing a photocatalytic oxide and any one of a boric acid compound, a borosilicate compound, an aluminoboric acid compound, and a silicate compound formed on a surface of a substrate. A photocatalytic hydrophilic member.
成され、さらにその上にホウ酸化合物、ホウケイ酸化合
物、アルミノホウ酸化合物、ケイ酸化合物のいずれかを
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 oxide-containing layer is formed on the surface of a substrate, and a surface layer containing any of a boric acid compound, a borosilicate compound, an aluminoboric acid compound, and a silicate compound is further formed thereon. A photocatalytic hydrophilic member, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9059827A JPH10235204A (en) | 1997-02-27 | 1997-02-27 | Photocatalytic hydrophilic member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9059827A JPH10235204A (en) | 1997-02-27 | 1997-02-27 | Photocatalytic hydrophilic member |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000268210A Division JP2001146491A (en) | 2000-09-05 | 2000-09-05 | Photo-catalytic hydrophilic tile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10235204A true JPH10235204A (en) | 1998-09-08 |
Family
ID=13124460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9059827A Pending JPH10235204A (en) | 1997-02-27 | 1997-02-27 | Photocatalytic hydrophilic member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10235204A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001171127A (en) * | 1999-10-05 | 2001-06-26 | Canon Inc | Base for ink-jet recording head, ink-jet recording head, ink-jet recording unit and ink-jet recording apparatus |
| JP2002115463A (en) * | 2000-10-05 | 2002-04-19 | Takenaka Komuten Co Ltd | Opening construction and exterior wall panel of building under conditions in which rain water constantly hits glass surface |
| WO2002042517A1 (en) * | 2000-11-24 | 2002-05-30 | Murakami Corporation | Composite element and method for preparation thereof |
| KR20030012537A (en) * | 2001-08-01 | 2003-02-12 | 현대자동차주식회사 | Compositions of Photo-Catalyst for Automotive |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH0940872A (en) * | 1995-07-28 | 1997-02-10 | Nippon Kayaku Co Ltd | Composition containing photocatalyst |
| JPH10113563A (en) * | 1996-10-11 | 1998-05-06 | Asahi Glass Co Ltd | Photocatalyst and production thereof |
| JPH10176140A (en) * | 1996-12-18 | 1998-06-30 | Sumitomo Chem Co Ltd | Photocatalyst coating composition and photocatalyst |
| JPH10237354A (en) * | 1997-02-25 | 1998-09-08 | Matsushita Electric Works Ltd | Coating agent and building material |
-
1997
- 1997-02-27 JP JP9059827A patent/JPH10235204A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH0940872A (en) * | 1995-07-28 | 1997-02-10 | Nippon Kayaku Co Ltd | Composition containing photocatalyst |
| JPH10113563A (en) * | 1996-10-11 | 1998-05-06 | Asahi Glass Co Ltd | Photocatalyst and production thereof |
| JPH10176140A (en) * | 1996-12-18 | 1998-06-30 | Sumitomo Chem Co Ltd | Photocatalyst coating composition and photocatalyst |
| JPH10237354A (en) * | 1997-02-25 | 1998-09-08 | Matsushita Electric Works Ltd | Coating agent and building material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001171127A (en) * | 1999-10-05 | 2001-06-26 | Canon Inc | Base for ink-jet recording head, ink-jet recording head, ink-jet recording unit and ink-jet recording apparatus |
| JP4666739B2 (en) * | 1999-10-05 | 2011-04-06 | キヤノン株式会社 | Inkjet recording head substrate, inkjet recording head, inkjet recording unit, inkjet recording apparatus, inkjet recording head substrate manufacturing method, and inkjet recording head manufacturing method |
| JP2002115463A (en) * | 2000-10-05 | 2002-04-19 | Takenaka Komuten Co Ltd | Opening construction and exterior wall panel of building under conditions in which rain water constantly hits glass surface |
| JP4518227B2 (en) * | 2000-10-05 | 2010-08-04 | 株式会社竹中工務店 | Opening structure of building and outer wall panel under the condition that rainwater hits glass surface constantly |
| WO2002042517A1 (en) * | 2000-11-24 | 2002-05-30 | Murakami Corporation | Composite element and method for preparation thereof |
| US6878450B2 (en) | 2000-11-24 | 2005-04-12 | Murakami Corporation | Composite element and method for preparation thereof |
| KR20030012537A (en) * | 2001-08-01 | 2003-02-12 | 현대자동차주식회사 | Compositions of Photo-Catalyst for Automotive |
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