JPH09227805A - Photocatalytic hydrophilic coating composition - Google Patents
Photocatalytic hydrophilic coating compositionInfo
- Publication number
- JPH09227805A JPH09227805A JP8284532A JP28453296A JPH09227805A JP H09227805 A JPH09227805 A JP H09227805A JP 8284532 A JP8284532 A JP 8284532A JP 28453296 A JP28453296 A JP 28453296A JP H09227805 A JPH09227805 A JP H09227805A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- water
- photocatalytic
- base material
- oxide
- 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 25
- 239000008199 coating composition Substances 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000356 contaminant Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 2
- -1 aluminum alkoxide Chemical class 0.000 abstract description 6
- 239000002772 conduction electron Substances 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052753 mercury Inorganic materials 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 17
- 239000003981 vehicle Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000000428 dust Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001443 photoexcitation Effects 0.000 description 4
- 239000006059 cover glass Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 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
- 230000003405 preventing effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 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
- 239000004744 fabric Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000004575 stone 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000000470 constituent 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 230000005660 hydrophilic surface Effects 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
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000004071 soot 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
- 238000011282 treatment Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
- F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
- F24F8/22—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Finishing Walls (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Prevention Of Fouling (AREA)
- Optical Elements Other Than Lenses (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Building Environments (AREA)
- Refuge Islands, Traffic Blockers, Or Guard Fence (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Rear-View Mirror Devices That Are Mounted On The Exterior Of The Vehicle (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Road Signs Or Road Markings (AREA)
- Greenhouses (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Joining Of Glass To Other Materials (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
- Bridges Or Land Bridges (AREA)
- Panels For Use In Building Construction (AREA)
- Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
- Accessories Of Cameras (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 surface of a member highly hydrophilic. More specifically, the present invention relates to an antifogging technique for preventing fogging and formation of water droplets on a member such as a mirror, a lens, a glass, a prism and the like by making the surface of the transparent 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-mentioned "cloudiness" 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. If the cover glass of the instrument panel becomes cloudy, it will be 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. Soot and particles floating in the atmosphere 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 the conventional wisdom, polytetrafluoroethylene (PT) is used to prevent stains on the building exterior and the like.
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、基材表面に塗布し固着させ
るだけで、部材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. Therefore, in view of the above circumstances, an object of the present invention is to provide a member that can maintain the surface of the member to have a high degree of hydrophilicity for a long period of time only by coating and fixing the surface of the substrate.
【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、無定
型アルミナ又はその前駆体からなり、基材表面に塗布し
固着させた後に、紫外線を照射して光触媒性酸化チタン
を光励起させると、それに応じて表面が親水性を呈する
ようになることを特徴とする光触媒性親水性塗料組成物
を提供する。表面層に酸化チタンの他に無定型アルミナ
が含有されると、前記無定型アルミナは優れた蓄水性を
有するため、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。表面が
高度に親水性を呈するようになると、付着した湿分の凝
縮水及び／又は水滴によって曇り又は翳るのが防止され
るようになる。また、表面が高度に親水性を呈するよう
になると、降雨に晒されたときに、付着堆積物及び／又
は汚染物が雨滴により洗い流されるようになる。さら
に、表面が高度に親水性を呈するようになると、水で洗
浄するのが容易になり、水で濯ぐ或いは簡単な水拭き程
度で付着堆積物及び／又は汚染物が雨滴により洗い流さ
れるようになる。In the present invention, the photocatalytic titanium oxide and amorphous alumina or its precursor are coated on the surface of the base material and fixed, and then the photocatalytic titanium oxide is photoexcited by irradiation with ultraviolet rays. The photocatalytic hydrophilic coating composition is characterized in that the surface thereof becomes hydrophilic. When the surface layer contains amorphous alumina in addition to titanium oxide, the amorphous alumina has excellent water storage, so that a stable physically adsorbed water layer is easily formed, and even if kept in a dark place, The hydrophilicity of the surface can be maintained highly for a fairly long time. Furthermore, because the surface layer contains a photocatalytic oxide, even when the surface loses its hydrophilicity after being left in the dark for a long period of time, it becomes superhydrophilic depending on the photoexcitation of the photocatalytic oxide. Come to present. When the surface becomes highly hydrophilic, it will prevent clouding or overhanging due to condensed water and / or water droplets of the attached moisture. Also, when the surface becomes highly hydrophilic, deposited deposits and / or contaminants will be washed away by raindrops when exposed to rainfall. In addition, the highly hydrophilic surface makes it easier to wash with water, so that deposited deposits and / or contaminants can be washed away by raindrops with just a water rinse or a simple water wipe. Become.
【０００９】[0009]
【発明の実施の形態】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／ＪＰ９
６／００７３３号に示したように、部材表面が水との接
触角に換算して１０゜以下の状態であれば、空気中の湿
分や湯気が結露しても、凝縮水が個々の水滴を形成せず
に一様な水膜になる傾向が顕著になる。従って、表面に
光散乱性の曇りを生じない傾向が顕著になる。同様に、
窓ガラスや車両用バックミラーや車両用風防ガラスや眼
鏡レンズやヘルメットのシールドが降雨や水しぶきを浴
びた場合に、離散した目障りな水滴が形成されずに、高
度の視界と可視性を確保し、車両や交通の安全性を保証
し、種々の作業や活動の能率を向上させる効果が飛躍的
に向上する。また、同様にＰＣＴ／ＪＰ９６／００７３
３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。BEST MODE FOR CARRYING OUT THE INVENTION The term "high hydrophilicity" in the present invention means that the contact angle with water is 10 ° or less, preferably 5 ° or less.
い う Refers to the state exhibiting the following water wettability. PCT / JP9
As shown in No. 6/00733, if the surface of the member is in a state where the contact angle with water is 10 ° or less, even if moisture or steam in the air is condensed, the condensed water will be an individual water droplet. The tendency that a uniform water film is formed without forming a film becomes remarkable. Therefore, the tendency that light scattering fogging does not occur on the surface becomes remarkable. Similarly,
When the window glass, vehicle rearview mirror, vehicle windshield, spectacle lens or helmet shield is exposed to rain or splashes, discrete and annoying water droplets are not formed, ensuring high visibility and visibility. The effect of guaranteeing the safety of vehicles and traffic and improving the efficiency of various work and activities is dramatically improved. Also, similarly, PCT / JP96 / 0073
As shown in No. 3, when the surface of the member is in a state of being 10 ° or less, preferably 5 ° or less in terms of a contact angle with water, carbon dust contained in exhaust gas of city dust, automobiles, etc. Both of the hydrophobic contaminants such as combustion products, oils and fats, sealant eluting components, and inorganic clay contaminants hardly adhere, and even if they adhere, they can be easily dropped by rainfall or washing.
【００１０】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 hydrophilicity, in addition to the above-mentioned antifogging effect and surface cleaning effect, it also has an antistatic effect (dust preventing effect), a heat insulating effect, a bubble preventing effect in water, heat exchange. The effect of improving the efficiency of the vessel, the effect of biocompatibility, and the like are exhibited.
【００１１】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 when the above anti-fogging effect is expected, and glass, plastic, and 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.
【００１２】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.
【００１３】上記表面層の膜厚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。本発明の塗料組成物
において溶媒の重量比率を多くすれば表面層の膜厚が薄
くなる。その意味で溶媒の重量は、塗膜形成要素（酸化
チタンと、アルミナ又はその前駆体）の１０倍以上、よ
り好ましくは１００倍以上あるのがよい。ここで溶媒に
は水、エタノール、プロパノール等が好適に利用でき
る。The thinner the surface layer, the more the transparency of the member can be secured. Further, when the film thickness is reduced, the wear resistance of the surface layer is improved. In the coating composition of the present invention, if the weight ratio of the solvent is increased, the film thickness of the surface layer becomes thin. In that sense, the weight of the solvent is preferably 10 times or more, more preferably 100 times or more that of the coating film forming element (titanium oxide and alumina or a precursor thereof). Here, water, ethanol, propanol or the like can be preferably used as the solvent.
【００１４】無定型アルミナの前駆体としては、アルミ
ニウムアルコキシド、アルミニウムキレート等が好適に
利用できる。Aluminum alkoxide, aluminum chelate and the like can be preferably used as the precursor of the amorphous alumina.
【００１５】本発明の塗料中には、さらにＡｇ、Ｃｕ、
Ｚｎ等の抗菌性金属を添加してもよい。そうすれば、塗
膜を形成したときに、表面に付着した細菌を死滅させる
ことができる。更に、黴、藻、苔のような微生物の成長
を抑制することができる。In the coating material of the present invention, Ag, Cu,
An antibacterial metal such as Zn may be added. Then, when the coating film is formed, the bacteria attached to the surface can be killed. Furthermore, the growth of microorganisms such as mold, algae and moss can be suppressed.
【００１６】本発明の塗料中には、さらにＰｔ、Ｐｄ、
Ｒｈ、Ｒｕ、Ｏｓ、Ｉｒのような白金族金属を添加する
ことができる。そうすれば、塗膜を形成したときに、塗
膜の光触媒による酸化活性を増強させることができ、塗
膜表面に付着した汚染物質の分解を促進する。In the paint of the present invention, Pt, Pd,
Platinum group metals such as Rh, Ru, Os, Ir can be added. Then, when the coating film is formed, the photocatalytic oxidation activity of the coating film can be enhanced, and the decomposition of contaminants attached to the surface of the coating film is promoted.
【００１７】[0017]
【実施例】塩酸解膠アナターゼ型酸化チタンゾル（石原
産業、ＣＳ−Ｃ、固形分濃度３０重量％）と、無定型酸
化アルミニウムゾル（日産化学、アルミナゾル−１０
０、固形分濃度１０重量％）を固形分のモル比で８８：
１２になるように混合して塗料組成物を得た。この塗料
組成物を、１０ｃｍ角のソーダライムガラスに、フロー
コーティング法により塗布し、５００℃で１時間焼成し
て、塗膜試料を作製した。焼成直後の水との接触角は１
゜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。得られた試料を２週間放置した後、紫外線光源（三
共電気、ブラックライトブルー（ＢＬＢ）蛍光灯）を用
い、照度０．３ｍＷ／ｃｍ２の紫外線を約１０日間＃２
試料表面に照射した。その結果、水との接触角は１゜に
回復した。その後、暗所に１日放置したが、水との接触
角は３゜程度に維持された。次に＃２試料表面に息を吹
きかけて曇りの有無を観察した。その結果、曇りは生じ
なかった。EXAMPLE An anatase hydrochloride anatase type titanium oxide sol (Ishihara Sangyo, CS-C, solid concentration 30% by weight) and an amorphous aluminum oxide sol (Nissan Chemical, alumina sol-10)
0, solid content concentration 10% by weight) in a molar ratio of solid content of 88:
The mixture was mixed so as to have a coating composition of 12. This coating composition was applied to 10 cm square soda lime glass by a flow coating method and baked at 500 ° C. for 1 hour to prepare a coating film sample. The contact angle with water immediately after firing is 1
Was ゜. Here, the contact angle with water was measured by a contact angle measuring device (Kyowa Interface Science, CA-X150) 30 seconds after a water droplet was dropped on the sample surface from the micro syringe. After leaving the obtained sample for 2 weeks, an ultraviolet light source (Sankyo Denki, Black Light Blue (BLB) fluorescent lamp) was used to expose the sample to ultraviolet light having an illuminance of 0.3 mW / cm 2 for about 10 days # 2.
The sample surface was irradiated. As a result, the contact angle with water recovered to 1 °. After that, it was left in the dark for one day, but the contact angle with water was maintained at about 3 °. Next, the surface of # 2 sample was blown to observe the presence or absence of cloudiness. As a result, no clouding occurred.
【００１８】[0018]
【発明の効果】本発明では、塗料組成物の構成要素を、
光触媒性酸化チタンと、無定型アルミナ又はその前駆体
からなるようにしたので、基材表面に塗布し固着させた
後に、塗膜に紫外線を照射して光触媒性酸化チタンを光
励起させるだけで、それに応じて表面が親水性を呈する
ようになり、かつ無定型アルミナの蓄水効果により、遮
光時の親水性も長期にわたり維持されるようになる。In the present invention, the constituents of the coating composition are
Since it is made of photocatalytic titanium oxide and amorphous alumina or its precursor, after coating and fixing it on the surface of the base material, it is possible to irradiate the coating film with ultraviolet rays to photoexcite the photocatalytic titanium oxide. Accordingly, the surface becomes hydrophilic, and due to the water storage effect of the amorphous alumina, the hydrophilicity at the time of shading is also maintained for a long time.
Claims (4)
又はその前駆体からなり、基材表面に塗布し固着させた
後に、紫外線を照射して光触媒性酸化チタンを光励起さ
せると、それに応じて表面が親水性を呈するようになる
ことを特徴とする光触媒性親水性塗料組成物。1. A photocatalytic titanium oxide and amorphous alumina or a precursor thereof, which is applied to the surface of a base material and fixed thereto, and then is irradiated with ultraviolet rays to photoexcite the photocatalytic titanium oxide. A photocatalytic hydrophilic coating composition, wherein the composition exhibits hydrophilicity.
又はその前駆体からなり、基材表面に塗布し固着させた
後に、紫外線を照射して光触媒性酸化チタンを光励起さ
せると、それに応じて表面が親水性を呈し、以て付着し
た湿分の凝縮水及び／又は水滴によって曇り又は翳るの
が防止されるようになることを特徴とする光触媒性親水
性塗料組成物。2. A photocatalytic titanium oxide and amorphous alumina or a precursor thereof, which is applied to the surface of a base material and fixed thereto, and then irradiated with ultraviolet rays to photoexcite the photocatalytic titanium oxide. Shows a hydrophilic property, whereby clouding or overhanging due to condensed water and / or water droplets of attached moisture is prevented, and a photocatalytic hydrophilic coating composition is characterized.
又はその前駆体からなり、基材表面に塗布し固着させた
後に、紫外線を照射して光触媒性酸化チタンを光励起さ
せると、それに応じて表面が親水性を呈し、以て降雨に
晒されたときに、付着堆積物及び／又は汚染物が雨滴に
より洗い流されるを可能にすることを特徴とする光触媒
性親水性塗料組成物。3. A photocatalytic titanium oxide and amorphous alumina or a precursor thereof, which is applied to the surface of a base material and fixed thereto, and then irradiated with ultraviolet rays to photoexcite the photocatalytic titanium oxide. Exhibits a hydrophilic property, thereby enabling the adhered deposits and / or contaminants to be washed away by raindrops when exposed to rainfall.
又はその前駆体からなり、基材表面に塗布し固着させた
後に、紫外線を照射して光触媒性酸化チタンを光励起さ
せると、それに応じて表面が親水性を呈し、以て水で洗
浄するのが容易になることを特徴とする光触媒性親水性
塗料組成物。4. A photocatalytic titanium oxide and amorphous alumina or a precursor thereof, which is applied to the surface of a base material and fixed thereto, and then irradiated with ultraviolet rays to photoexcite the photocatalytic titanium oxide, whereby the surface is correspondingly exposed. Shows a hydrophilic property and is easily washed with water, and therefore, a photocatalytic hydrophilic coating composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8284532A JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35464995 | 1995-12-22 | ||
| JP7-354649 | 1995-12-22 | ||
| JP8284532A JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09227805A true JPH09227805A (en) | 1997-09-02 |
Family
ID=18438979
Family Applications (71)
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|---|---|---|---|
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| JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
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| JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
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| JP8272815A Pending JPH09224957A (en) | 1995-12-22 | 1996-09-06 | Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop |
| JP8272814A Pending JPH09226041A (en) | 1995-12-22 | 1996-09-06 | Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member |
| JP8272808A Pending JPH09229724A (en) | 1995-12-22 | 1996-09-07 | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
| JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
| JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
| JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
| JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
| JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
| JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
| JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
| JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
| JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
| JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
| JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
| JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
| JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
| JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
| JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
| JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
| JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
| JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
| JP08282811A Expired - Fee Related JP3075195B2 (en) | 1995-12-22 | 1996-09-18 | Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror |
| JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
| JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
| JP28453496A Expired - Lifetime JP3173391B2 (en) | 1995-12-22 | 1996-09-19 | Hydrophilic film, and method for producing and using the same |
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| JP28895596A Expired - Lifetime JP3774955B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning handrail and handrail cleaning method |
| JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
| JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
| JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
| JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
| JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
| JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
| JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
| JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
| JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
| JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
| JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
| JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
| JP8323516A Pending JPH09241038A (en) | 1995-12-22 | 1996-11-19 | Photocatalytic hydrophilic member and its production |
| JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
| JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
| JP23956799A Expired - Lifetime JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
| JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
| JP34300999A Expired - Fee Related JP3844182B2 (en) | 1995-12-22 | 1999-12-02 | Hydrophilic film and method for producing and using the same |
| JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
| JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
| JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
| JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
| JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
| JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
| JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
| JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
| JP2002020533A Expired - Fee Related JP3882625B2 (en) | 1995-12-22 | 2002-01-29 | Sound insulation wall and cleaning method for sound insulation wall |
| JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Family Applications Before (36)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
| JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
| JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
| JP15017196A Expired - Lifetime JP3760509B2 (en) | 1995-12-22 | 1996-05-22 | Greenhouse ceiling and its condensation prevention method |
| JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
| JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
| JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
| JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
| JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
| JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
| JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
| JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
| JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
| JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
| JP8272815A Pending JPH09224957A (en) | 1995-12-22 | 1996-09-06 | Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop |
| JP8272814A Pending JPH09226041A (en) | 1995-12-22 | 1996-09-06 | Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member |
| JP8272808A Pending JPH09229724A (en) | 1995-12-22 | 1996-09-07 | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
| JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
| JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
| JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
| JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
| JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
| JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
| JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
| JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
| JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
| JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
| JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
| JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
| JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
| JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
| JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
| JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
| JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
| JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
| JP08282811A Expired - Fee Related JP3075195B2 (en) | 1995-12-22 | 1996-09-18 | Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror |
Family Applications After (34)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
| JP28453496A Expired - Lifetime JP3173391B2 (en) | 1995-12-22 | 1996-09-19 | Hydrophilic film, and method for producing and using the same |
| JP28579796A Expired - Lifetime JP3697795B2 (en) | 1995-12-22 | 1996-09-20 | Display and cleaning method thereof |
| JP28895596A Expired - Lifetime JP3774955B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning handrail and handrail cleaning method |
| JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
| JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
| JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
| JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
| JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
| JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
| JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
| JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
| JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
| JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
| JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
| JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
| JP8323516A Pending JPH09241038A (en) | 1995-12-22 | 1996-11-19 | Photocatalytic hydrophilic member and its production |
| JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
| JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
| JP23956799A Expired - Lifetime JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
| JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
| JP34300999A Expired - Fee Related JP3844182B2 (en) | 1995-12-22 | 1999-12-02 | Hydrophilic film and method for producing and using the same |
| JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
| JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
| JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
| JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
| JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
| JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
| JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
| JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
| JP2002020533A Expired - Fee Related JP3882625B2 (en) | 1995-12-22 | 2002-01-29 | Sound insulation wall and cleaning method for sound insulation wall |
| JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (71) | JPH09231821A (en) |
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| JPH09230105A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Antifogging method and facility applied with the method |
| KR100290066B1 (en) * | 1998-07-13 | 2001-05-15 | 김명신 | How to fix titanium dioxide, used as an air freshener, on activated carbon |
| WO2000053689A1 (en) * | 1999-03-09 | 2000-09-14 | Toto Ltd. | Hydrophilic member, method for preparation thereof, and coating agent and apparatus for preparation thereof |
| US6716513B1 (en) | 1999-03-09 | 2004-04-06 | Toto Ltd. | Hydrophilic member, method for preparation thereof, and coating agent and apparatus for preparation thereof |
| JP2009185107A (en) * | 2008-02-04 | 2009-08-20 | Pialex Technologies Corp | Hydrophilic coating material and hydrophilic coated object |
| JP2013096959A (en) * | 2011-11-04 | 2013-05-20 | Shiyouichi Yoshino | Radioactive decontamination method |
| CN112143299A (en) * | 2020-09-24 | 2020-12-29 | 南京长江涂料有限公司 | Long-acting self-cleaning high-weatherability fluorocarbon coating and preparation method thereof |
| CN112143299B (en) * | 2020-09-24 | 2022-02-01 | 南京长江涂料有限公司 | Long-acting self-cleaning high-weatherability fluorocarbon coating and preparation method thereof |
| CN113462273A (en) * | 2021-06-29 | 2021-10-01 | 广东康伴新材料科技有限公司 | High-wear-resistance high-hand-sensitivity rubber coating and preparation method thereof |
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