JP3063968B2 - Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror - Google Patents
Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirrorInfo
- Publication number
- JP3063968B2 JP3063968B2 JP8281223A JP28122396A JP3063968B2 JP 3063968 B2 JP3063968 B2 JP 3063968B2 JP 8281223 A JP8281223 A JP 8281223A JP 28122396 A JP28122396 A JP 28122396A JP 3063968 B2 JP3063968 B2 JP 3063968B2
- Authority
- JP
- Japan
- Prior art keywords
- vehicle mirror
- water
- surface layer
- mirror according
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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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)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Refuge Islands, Traffic Blockers, Or Guard Fence (AREA)
- Rear-View Mirror Devices That Are Mounted On The Exterior Of The Vehicle (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
- Road Signs Or Road Markings (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Panels For Use In Building Construction (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Detergent Compositions (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
- Bridges Or Land Bridges (AREA)
- Joining Of Glass To Other Materials (AREA)
- Greenhouses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Physical Vapour Deposition (AREA)
- Laser Surgery Devices (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、自動車のフェンダ
ーミラー、二輪車の後方確認ミラー等に利用できる車両
用ミラー及び車両用ミラーの防曇方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vehicle mirror which can be used as a fender mirror of an automobile, a rear view mirror of a motorcycle, and the like, and a method of defogging a vehicle mirror.
【0002】[0002]
【従来の技術】自動車のフェンダーミラー、オートバイ
の後方確認ミラー等の車両用ミラーが降雨や水しぶきを
受けて、離散した多数の水滴が表面に付着して、それら
の表面が翳り、ぼやけ、斑模様になり、或いは曇り、可
視性が失われることはしばしば経験されることである。
凝縮水滴が充分に細かく、それらの直径が可視光の波長
の1/2程度であれば、 水滴は光を散乱し、車両用ミ
ラーは見かけ上不透明となり、可視性が失われる。湿分
の凝縮が更に進行し、細かい凝縮水滴が互いに融合して
より大きな離散した水滴に成長すれば、水滴と表面との
界面並びに水滴と空気との界面における光の屈折によ
り、表面は翳り、ぼやけ、斑模様になり、或いは曇り、
可視性が失われる。ここで用いる“防曇”の用語は、こ
のような曇りや凝縮水滴の成長や水滴の付着による光学
的障害を防止する技術を広く意味する。2. Description of the Related Art A vehicle mirror such as a fender mirror of a car or a rear view mirror of a motorcycle receives rain and splashes, and a large number of discrete water droplets adhere to the surface, and the surfaces are shaded, blurred, and mottled. Loss of visibility, or cloudiness, is often experienced.
If the condensed water droplets are sufficiently fine and their diameter is on the order of one-half the wavelength of visible light, the water droplets will scatter light and the vehicle mirror will appear opaque and lose visibility. If the condensation of moisture progresses further, and fine condensed water droplets fuse with each other and grow into larger discrete water droplets, the surface becomes dark due to the refraction of light at the water droplet-surface interface and the water droplet-air interface, Blurred, mottled, or cloudy,
Loss of visibility. As used herein, the term "anti-fog" broadly refers to a technique for preventing optical hindrance due to such fogging, growth of condensed water droplets, and adhesion of water droplets.
【0003】周知のように、従来用いられている防曇方
法は、ポリエチレングリコールのような親水性化合物或
いはシリコーンのような撥水性化合物を含んだ防曇性組
成物を表面に塗布することである。しかし、この種の防
曇性被膜はあくまで一時的なもので、水洗や接触によっ
て容易に取除かれ、早期に効果を失うという難点があ
る。As is well known, a conventionally used anti-fog method is to apply an anti-fog composition containing a hydrophilic compound such as polyethylene glycol or a water-repellent compound such as silicone to the surface. . However, this kind of anti-fog coating is only temporary, and has the drawback that it is easily removed by washing or contact and loses its effect early.
【0004】[0004]
【発明の解決すべき課題】自動車のフェンダーミラー、
オートバイの後方確認ミラー等の車両用ミラーが降雨や
水しぶきを受けて、離散した多数の水滴が表面に付着し
て、それらの表面が翳り、ぼやけ、斑模様になり、或い
は曇り、可視性が失われると、自動車やオートバイの安
全運転上支障を来す。そこで本発明の目的は、高度な可
視性を実現することの可能な車両用ミラー及びその防曇
方法を提供することにある。本発明の他の目的は、長期
にわたって高度の親水性を維持し、防曇性を示すことの
可能な車両用ミラー及びその防曇方法を提供することに
ある。本発明の他の目的は、ほぼ恒久的に高度の親水性
を維持し、防曇性を示すことの可能な車両用ミラー及び
その防曇方法を提供することにある。SUMMARY OF THE INVENTION A fender mirror for an automobile,
Mirrors for vehicles such as motorcycle rear view mirrors are subject to rainfall and splashes, and a large number of discrete water droplets adhere to the surface, making those surfaces obscured, blurred, mottled, fogged, or lost visibility. If this happens, it will hinder the safe driving of cars and motorcycles. Accordingly, an object of the present invention is to provide a vehicle mirror capable of realizing a high degree of visibility and a method for preventing fog thereof. Another object of the present invention is to provide a vehicle mirror capable of maintaining a high degree of hydrophilicity over a long period of time and exhibiting anti-fog properties, and a method for preventing the same from occurring. It is another object of the present invention to provide a vehicle mirror capable of maintaining a high degree of hydrophilicity almost permanently and exhibiting anti-fog properties, and a method of preventing the same from occurring.
【0005】[0005]
【課題を解決するための手段】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、上記極性成分との協調的
な作用により、表面と前記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。また、一旦部材表面が高度に親水化されたなら
ば、部材を暗所に保持しても、表面の親水性はある程度
の期間持続する。SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst formed thereon, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. 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 band of the photocatalyst is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. By either or both actions, polarities are probably imparted to the surface and polar components such as water and hydroxyl groups are collected. Then, one or both of conduction electrons and holes and the above-mentioned polar component cooperate with each other to cut off a chemical bond between the surface and the contaminant chemically adsorbed on the surface, and to cause a chemical adsorbed water on the surface. Is adsorbed, and a physically adsorbed water layer is formed thereon. Further, once the surface of the member is highly hydrophilized, the hydrophilicity of the surface is maintained for a certain period even if the member is kept in a dark place.
【0006】本発明では、車両用ミラー基材の表面に、
実質的に透明な光触媒を含有する表面層を備えた防曇性
車両用ミラーを提供する。光触媒を含有する表面層を備
えることにより、光触媒の光励起に応じて、表面層の表
面は親水性を呈し、付着した湿分の凝縮水及び/又は水
滴が前記層の表面に一様に広がり、湿分凝縮水及び/又
は水滴によって曇り若しくは翳るのが防止されるように
なる。In the present invention, the surface of the vehicle mirror base material is
An antifogging vehicular mirror having a surface layer containing a substantially transparent photocatalyst is provided. By providing a surface layer containing a photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, and condensed water and / or water droplets of attached moisture uniformly spread on the surface of the layer, Moisture condensate and / or water droplets are prevented from clouding or overcasting.
【0007】本発明の好ましい態様においては、表面層
には、さらにシリカが含有されているようにする。シリ
カが含有されることにより、表面が水濡れ角0゜に近い
高度の親水性を呈しやすくなると共に、暗所に保持した
ときの親水維持性が向上する。その理由はシリカは構造
中に水を蓄えることができることと関係していると思わ
れる。[0007] In a preferred embodiment of the present invention, the surface layer further contains silica. By containing silica, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. The reason seems to be related to the fact that silica can store water in its structure.
【0008】本発明の好ましい態様においては、表面層
には、さらに固体酸が含有されているようにする。固体
酸が含有されることにより、表面が水濡れ角0゜に近い
高度の親水性を呈しやすくなると共に、暗所に保持した
ときの親水維持性が向上する。その理由は表面層に固体
酸が含有されると、表面の極性が、光の有無にかかわら
ず大きな状態にあるために、疎水性分子よりも極性分子
である水分子を選択的に吸着させやすい。そのため安定
な物理吸着水層が形成されやすく、暗所に保持しても、
表面の親水性をかなり長期にわたり高度に維持できる。In a preferred embodiment of the present invention, the surface layer further contains a solid acid. When the solid acid is contained, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when kept in a dark place is improved. The reason is that when a solid acid is contained in the surface layer, the polarity of the surface is large regardless of the presence or absence of light, so it is easier to selectively adsorb water molecules that are polar molecules than hydrophobic molecules. . Therefore, a stable physical adsorption water layer is easily formed, and even if it is kept in a dark place,
Surface hydrophilicity can be maintained at a high level for a fairly long time.
【0009】本発明の好ましい態様においては、表面層
には、さらにシリコーンが含有されているようにする。
シリコーンが含有されることにより、光触媒の光励起に
よって、シリコーン中のシリコン原子に結合する有機基
の少なくとも一部が水酸基に置換され、さらにその上に
物理吸着水層が形成されることにより、表面が水濡れ角
0゜に近い高度の親水性を呈するようになると共に、暗
所に保持したときの親水維持性が向上する。In a preferred embodiment of the present invention, the surface layer further contains silicone.
By containing the silicone, at least a part of the organic group bonded to the silicon atom in the silicone is replaced by a hydroxyl group by photoexcitation of the photocatalyst, and further, a physisorbed water layer is formed thereon, whereby the surface is formed. It exhibits a high degree of hydrophilicity near the water wetting angle of 0 °, and improves the hydrophilicity retention when kept in a dark place.
【0010】[0010]
【発明の実施の形態】次に、本発明の具体的な構成につ
いて説明する。本発明における防曇性車両用ミラー表面
には、図1又は図2に示すように、基材の表面に光触媒
を含む層が形成されている。このような表面構造をとる
ことで、車両用ミラー表面は、光触媒の光励起に応じて
高度に親水化されるのである。それにより、雰囲気の湿
分が凝縮して付着しても水滴状には成長せず、一様に水
膜化するようになり、湿分凝縮水及び/又は水滴によっ
て曇り若しくは翳るのが防止される。Next, a specific configuration of the present invention will be described. As shown in FIG. 1 or 2, a layer containing a photocatalyst is formed on the surface of a base material on the surface of the antifogging vehicle mirror according to the present invention. With such a surface structure, the surface of the vehicle mirror is highly hydrophilized in response to the photoexcitation of the photocatalyst. As a result, even if the moisture in the atmosphere condenses and adheres, it does not grow in the form of water droplets, but uniformly forms a water film, and is prevented from being clouded or overshadowed by the moisture condensed water and / or water droplets. You.
【0011】図1においては、表面層が光触媒のみから
なる場合には、光触媒は酸化物であることが好ましい。
そうすることにより、酸化物は環境中の汚染物質が吸着
していない状態では親水性を示すので、光励起作用によ
りその汚染物質を排斥させ、吸着水層を形成させること
で、親水性を呈しやすく、一様な水膜が形成できる。図
2において、Mは金属元素を示す。従って、図2の場
合、最表面は一般の無機酸化物からなる。この場合も、
酸化物は環境中の汚染物質が吸着していない状態では親
水性を示すので、上記無機酸化物以外に表面層に混入す
る光触媒性酸化チタンの光励起作用によりその汚染物質
を排斥させ、吸着水層を形成させることで、一様な水膜
が形成できる。In FIG. 1, when the surface layer comprises only a photocatalyst, the photocatalyst is preferably an oxide.
By doing so, the oxide shows hydrophilicity in the state where the pollutants in the environment are not adsorbed, so that the pollutants are rejected by the photoexcitation action and the adsorbed water layer is formed, so that the oxides easily exhibit hydrophilicity. A uniform water film can be formed. In FIG. 2, M represents a metal element. Therefore, in the case of FIG. 2, the outermost surface is made of a general inorganic oxide. Again,
Since the oxide is hydrophilic when the pollutants in the environment are not adsorbed, the photocatalytic titanium oxide mixed into the surface layer other than the inorganic oxide removes the contaminants by the photoexciting action, and the adsorbed water layer Is formed, a uniform water film can be formed.
【0012】本発明における車両用ミラー基材には、裏
面に反射コートを設けたガラス基材からなる鏡、裏面に
反射コートを設けた透明プラスチック基材からなる鏡、
プラスチック、ガラス、金属などからなる基材表面に反
射コートを設け、さらにその上に透明なハードコートを
設けた鏡、裏面に反射コートを設けた透明プラスチック
基材の上に透明なハードコートを設けた鏡等の、表面が
透明体からなる鏡が好適に利用できる。The mirror substrate for a vehicle according to the present invention includes a mirror made of a glass base material provided with a reflection coat on the back surface, a mirror made of a transparent plastic base material provided with a reflection coat on the back surface,
A mirror with a reflective coat on the surface of a substrate made of plastic, glass, metal, etc., and a transparent hard coat on a transparent plastic substrate with a reflective coat on the back A mirror whose surface is made of a transparent material, such as a mirror made of a transparent material, can be suitably used.
【0013】光触媒とは、その結晶の伝導帯と価電子帯
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)が生じて、伝導
電子と正孔を生成しうる物質をいい、例えば、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
こで光触媒の光励起に用いる光源としては、太陽光、街
灯、トンネル内照明、 常夜灯等の走行環境にある光源
を利用してもよいし、及び付属設備や携帯設備として、
励起光を照射しうる光源を使用してもよい。その場合使
用する光源には、例えば、蛍光灯、白熱電灯、メタルハ
ライドランプ、水銀ランプ、キセノンランプ、殺菌灯等
が好適に利用できる。光触媒の光励起により、基材表面
が高度に親水化されるためには、励起光の照度は、0.
001mW/cm2以上あればよいが、0.01mW/
cm2以上だと好ましく、0.1mW/cm2以上だと
より好ましい。[0013] A photocatalyst is formed by irradiating light (excitation light) having an energy (ie, shorter wavelength) larger than the energy gap between the conduction band and the valence band of the crystal when the electrons in the valence band are irradiated. A substance that can generate conduction electrons and holes by excitation (photoexcitation). Examples thereof include anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, bismuth trioxide, tungsten trioxide, and tungsten oxide. Ferrous iron, strontium titanate and the like can be suitably used. Here, as the light source used for photoexcitation of the photocatalyst, a light source in a traveling environment such as sunlight, street lamps, illumination in a tunnel, nightlights, etc. may be used, and as accessory equipment or portable equipment,
A light source that can emit excitation light may be used. As the light source used in this case, for example, a fluorescent lamp, an incandescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp, a germicidal lamp, or the like can be suitably used. In order for the surface of the base material to be highly hydrophilized by photoexcitation of the photocatalyst, the illuminance of the excitation light must be 0.
001 mW / cm 2 or more, but 0.01 mW / cm 2
cm 2 or more, more preferably 0.1 mW / cm 2 or more.
【0014】光触媒を含有する表面層の膜厚は、0.4
μm以下にするのが好ましい。そうすれば、光の乱反射
による白濁を防止することができ、表面層は実質的に透
明となる。さらに、光触媒を含有する表面層の膜厚を
0.2μm以下にすると一層好ましい。 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その透明度は向上す
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良い。The thickness of the surface layer containing the photocatalyst is 0.4
It is preferable that the thickness be not more than μm. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. More preferably, the thickness of the surface layer containing the photocatalyst is 0.2 μm or less. that way,
Coloring of the surface layer due to light interference can be prevented.
Also, the thinner the surface layer, the better its transparency. 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.
【0015】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、及び表面層と空気との界面における光の反射を
抑制できる。表面層の屈折率を2以下にするには、光触
媒に2以下の屈折率を有する物質を用いるか、或いは光
触媒が屈折率2以上の場合には、屈折率2以下の他の物
質を表面層に添加する。2以下の屈折率を有する光触媒
としては、酸化錫(屈折率1.9)等が利用できる。2
以上の屈折率を有する光触媒には、アナターゼ型酸化チ
タン(屈折率2.5) やルチル型酸化チタン(屈折率
2.7)があるが、この場合には屈折率2以下の他の物
質、例えば、炭酸カルシウム(屈折率1.6)、水酸化
カルシウム(屈折率1.6)、炭酸マグネシウム(屈折
率1.5)、炭酸ストロンチウム(屈折率1.5)、ド
ロマイト(屈折率1.7)、フッ化カルシウム(屈折率
1.4)、フッ化マグネシウム(屈折率1.4)、シリ
カ(屈折率1.5)、アルミナ(屈折率1.6)、ケイ
砂(屈折率1.6)、モンモリロナイト(屈折率1.
5)、カオリン(屈折率1.6)、セリサイト(屈折率
1.6)、ゼオライト(屈折率1.5)、酸化錫(屈折
率1.9)等を表面層に添加すればよい。It is preferable that the surface layer has a refractive index not so high as compared with the substrate. Preferably, the refractive index of the surface layer is 2 or less. Then, light reflection at the interface between the substrate and the surface layer and the interface between the surface layer and air can be suppressed. In order to reduce the refractive index of the surface layer to 2 or less, a substance having a refractive index of 2 or less is used for the photocatalyst, or if the photocatalyst has a refractive index of 2 or more, another substance having a refractive index of 2 or less is used for the surface layer. To be added. As a photocatalyst having a refractive index of 2 or less, tin oxide (refractive index: 1.9) or the like can be used. 2
Photocatalysts having the above refractive index include anatase type titanium oxide (refractive index 2.5) and rutile type titanium oxide (refractive index 2.7). In this case, other substances having a refractive index of 2 or less, For example, calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5), dolomite (refractive index 1.7) ), Calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), silica (refractive index 1.5), alumina (refractive index 1.6), silica sand (refractive index 1.6) ), Montmorillonite (refractive index 1.
5), kaolin (refractive index 1.6), sericite (refractive index 1.6), zeolite (refractive index 1.5), tin oxide (refractive index 1.9) and the like may be added to the surface layer.
【0016】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や黴を暗所でも死滅させる
ことができる。A metal such as Ag, Cu or Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.
【0017】上記表面層には、Pt、Pd、Ru、R
h、Ir、Os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、光触媒の酸化還元
活性を増強でき、脱臭浄化作用等が向上する。また、光
触媒以外に固体酸を添加した場合には、白金族金属の添
加により固体酸の酸度が向上するので、親水維持性も向
上し、付着水の水膜化がより促進されると共に、ある程
度長期間光触媒に励起光が照射されない場合の親水維持
性も向上する。上記表面層には、Moを添加することが
できる。光触媒以外に固体酸を添加した場合に、Moを
添加すると固体酸の酸度が向上するので、親水維持性も
向上し、付着水の水膜化がより促進されると共に、ある
程度長期間光触媒に励起光が照射されない場合の親水維
持性も向上する。The surface layer includes Pt, Pd, Ru, R
A platinum group metal such as h, Ir, Os can be added. The surface layer to which the metal is added can enhance the oxidation-reduction activity of the photocatalyst and improve the deodorizing and purifying action and the like. In addition, when a solid acid is added in addition to the photocatalyst, the acidity of the solid acid is improved by the addition of a platinum group metal, so that the hydrophilicity is also improved, and the formation of a water film on the attached water is further promoted. The hydrophilicity when the excitation light is not irradiated to the photocatalyst for a long period of time is also improved. Mo can be added to the surface layer. When a solid acid is added in addition to the photocatalyst, the addition of Mo increases the acidity of the solid acid, so that the hydrophilicity is also improved, and the formation of a water film on the attached water is further promoted. The hydrophilicity when light is not irradiated is also improved.
【0018】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(ソーダライムガラス、並板ガラ
ス等)の場合には、基材と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。When the substrate is a glass containing an alkali network modifying ion such as sodium (soda lime glass, side-by-side glass, etc.), an intermediate layer such as silica may be formed between the substrate and the surface layer. Good. 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.
【0019】親水性とは、表面に水を滴下したときにな
じみやすい性質をいい、一般に水濡れ角が90゜未満の
状態をいう。本発明における高度の親水性とは、表面に
水を滴下したときに非常になじみやすい性質をいい、よ
り具体的には水濡れ角が10゜以下程度になる状態をい
う。特に、防曇性にはPCT/JP96/00734に
開示したように、水濡れ角が10゜以下であると好まし
く、5゜以下ではより好ましい。The term "hydrophilic" refers to the property of being easily conformed when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The term “high hydrophilicity” in the present invention refers to a property that is highly compatible when water is dropped on the surface, and more specifically, a state where the water wetting angle is about 10 ° or less. In particular, as disclosed in PCT / JP96 / 00734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less, as disclosed in PCT / JP96 / 00734.
【0020】本発明における固体酸には、硫酸担持Al
2O3、硫酸担持TiO2、硫酸担持ZrO2、硫酸担
持SnO2、硫酸担持Fe2O3、硫酸担持SiO2、
硫酸担持HfO2、TiO2/WO3、WO3/SnO
2、WO3/ZrO2、WO3/Fe2O3、SiO2
・Al2O3、TiO2/SiO2、TiO2/Al2
O3、TiO2/ZrO2等が好適に利用できる。The solid acid used in the present invention includes sulfuric acid-supported Al.
2 O 3 , sulfuric acid supported TiO 2 , sulfuric acid supported ZrO 2 , sulfuric acid supported SnO 2 , sulfuric acid supported Fe 2 O 3 , sulfuric acid supported SiO 2 ,
Sulfuric acid supporting HfO 2 , TiO 2 / WO 3 , WO 3 / SnO
2 , WO 3 / ZrO 2 , WO 3 / Fe 2 O 3 , SiO 2
· Al 2 O 3, TiO 2 / SiO 2, TiO 2 / Al 2
O 3 , TiO 2 / ZrO 2 and the like can be suitably used.
【0021】次に、表面層の形成方法について説明す
る。まず、表面層が光触媒のみからなる場合の製法につ
いて、光触媒がアナターゼ型酸化チタンの場合を例にと
り説明する。この場合の方法は、大別して3つの方法が
ある。1つの方法はゾル塗布焼成法であり、他の方法は
有機チタネート法であり、他の方法は電子ビーム蒸着法
である。 (1)ゾル塗布焼成法 アナターゼ型酸化チタンゾルを、基材表面に、スプレー
コーティング法、ディップコーティング法、フローコー
ティング法、スピンコーティング法、ロールコーティン
グ法等の方法で塗布し、焼成する。 (2)有機チタネート法 チタンアルコキシド(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)、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤(塩酸、エチルアミン
等)を添加し、アルコール(エタノール、プロパノー
ル、ブタノール等)などの非水溶媒で希釈した後、部分
的に加水分解を進行させながら又は完全に加水分解を進
行させた後、混合物をスプレーコーティング法、ディッ
プコーティング法、フローコーティング法、スピンコー
ティング法、ロールコーティング法等の方法で塗布し、
乾燥させる。乾燥により、有機チタネートの加水分解が
完遂して水酸化チタンが生成し、水酸化チタンの脱水縮
重合により無定型酸化チタンの層が基材表面に形成され
る。その後、アナターゼの結晶化温度以上の温度で焼成
して、無定型酸化チタンをアナターゼ型酸化チタンに相
転移させる。 (3)電子ビーム蒸着法 酸化チタンのターゲットに電子ビームを照射することに
より、基材表面に無定型酸化チタンの層を形成する。そ
の後、アナターゼの結晶化温度以上の温度で焼成して、
無定型酸化チタンをアナターゼ型酸化チタンに相転移さ
せる。Next, a method for forming the surface layer will be described. First, a production method in the case where the surface layer is composed of only a photocatalyst will be described with reference to an example in which the photocatalyst is an anatase type titanium oxide. In this case, there are roughly three methods. One method is a sol coating and firing method, the other method is an organic titanate method, and the other method is an electron beam evaporation method. (1) Sol-coating and firing method Anatase-type titanium oxide sol is applied to the surface of a substrate by a method such as spray coating, dip coating, flow coating, spin coating, or roll coating, and then fired. (2) Organic titanate method A hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) is added to an organic titanate such as titanium alkoxide (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, etc. , After diluting with a non-aqueous solvent such as alcohol (ethanol, propanol, butanol, etc.) and then partially or completely allowing hydrolysis to proceed, the mixture is spray-coated, dip-coated, Apply by flow coating, spin coating, roll coating, etc.
dry. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Electron Beam Deposition Method An amorphous titanium oxide layer is formed on the surface of a base material by irradiating a titanium oxide target with an electron beam. After that, firing at a temperature higher than the crystallization temperature of anatase,
Phase transition of amorphous titanium oxide to anatase titanium oxide.
【0022】次に、表面層が光触媒とシリカからなる場
合について、光触媒がアナターゼ型酸化チタンの場合を
例にとり説明する。この場合の方法は、例えば、以下の
3つの方法がある。1つの方法はゾル塗布焼成法であ
り、他の方法は有機チタネート法であり、他の方法は4
官能性シラン法である。 (1)ゾル塗布焼成法 アナターゼ型酸化チタンゾルとシリカゾルとの混合液
を、基材表面にスプレーコーティング法、ディップコー
ティング法、フローコーティング法、スピンコーティン
グ法、ロールコーティング法等の方法で塗布し、焼成す
る。 (2)有機チタネート法 チタンアルコキシド(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)、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤(塩酸、エチルアミン
等)とシリカゾルを添加し、アルコール(エタノール、
プロパノール、ブタノール等)などの非水溶媒で希釈し
た後、部分的に加水分解を進行させながら又は完全に加
水分解を進行させた後、混合物をスプレーコーティング
法、ディップコーティング法、フローコーティング法、
スピンコーティング法、ロールコーティング法等の方法
で塗布し、乾燥させる。乾燥により、有機チタネートの
加水分解が完遂して水酸化チタンが生成し、水酸化チタ
ンの脱水縮重合により無定型酸化チタンの層が基材表面
に形成される。その後、アナターゼの結晶化温度以上の
温度で焼成して、無定型酸化チタンをアナターゼ型酸化
チタンに相転移させる。 (3)4官能性シラン法 テトラアルコキシシラン(テトラエトキシシラン、テト
ラプロポキシシラン、テトラブトキシシラン、テトラメ
トキシシラン等)とアナターゼ型酸化チタンゾルとの混
合物を基材の表面にスプレーコーティング法、ディップ
コーティング法、フローコーティング法、スピンコーテ
ィング法、ロールコーティング法等の方法で塗布し、必
要に応じて加水分解させてシラノールを形成した後、加
熱等の方法でシラノールを脱水縮重合に付す。Next, the case where the surface layer is composed of a photocatalyst and silica will be described with reference to the case where the photocatalyst is an anatase type titanium oxide. In this case, for example, there are the following three methods. One method is a sol coating and baking method, the other is an organic titanate method, and the other is a 4 method.
This is a functional silane method. (1) Sol coating and baking method A mixture of anatase-type titanium oxide sol and silica sol is applied to the substrate surface by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, and a roll coating method, and then fired. I do. (2) Organic titanate method A hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol are added to an organic titanate such as titanium alkoxide (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, etc. Add alcohol (ethanol,
After diluting with a non-aqueous solvent such as propanol, butanol, etc., and then allowing the hydrolysis to proceed partially or completely, the mixture is spray-coated, dip-coated, flow-coated,
It is applied by a method such as spin coating or roll coating and dried. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Tetrafunctional silane method A mixture of tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.) and an anatase-type titanium oxide sol is spray-coated on the surface of the substrate, and dip-coated. After applying by a method such as a flow coating method, a spin coating method, and a roll coating method, and hydrolyzing as necessary to form a silanol, the silanol is subjected to dehydration condensation polymerization by a method such as heating.
【0023】次に、表面層が光触媒と固体酸からなる場
合について、光触媒がアナターゼ型酸化チタン、固体酸
がTiO2/WO3の場合を例にとり説明する。この場
合の1つの方法は、タングステン酸のアンモニア溶解液
とアナターゼ型酸化チタンゾルとを混合し、必要に応じ
て希釈液(水、エタノール等)で希釈した混合物を基材
の表面にスプレーコーティング法、ディップコーティン
グ法、フローコーティング法、スピンコーティング法、
ロールコーティング法等の方法で塗布し、焼成する。他
の方法は、電子ビーム蒸着や、チタンアルコキシド、チ
タンアセテート、チタンキレート等の有機チタネートの
加水分解及び脱水縮重合により、無定型酸化チタン被膜
を形成後、タングステン酸を塗布し、無定型酸化チタン
が結晶化し、かつTiO2/WO3複合酸化物が生成す
る温度で熱処理する。Next, the case where the surface layer is composed of a photocatalyst and a solid acid will be described, taking as an example the case where the photocatalyst is an anatase type titanium oxide and the solid acid is TiO 2 / WO 3 . One method in this case is a spray coating method in which an ammonia solution of tungstic acid is mixed with an anatase-type titanium oxide sol, and a mixture diluted with a diluent (water, ethanol, etc.) is coated on the surface of the base material as necessary. Dip coating method, flow coating method, spin coating method,
It is applied by a method such as a roll coating method and baked. Another method is to form an amorphous titanium oxide film by electron beam evaporation or hydrolysis and dehydration polycondensation of an organic titanate such as titanium alkoxide, titanium acetate, and titanium chelate, and then apply tungstic acid to form the amorphous titanium oxide. Is heat-treated at a temperature at which TiO 2 / WO 3 composite oxide is formed.
【0024】次に、表面層が光触媒とシリコーンからな
る場合について、光触媒がアナターゼ型酸化チタンの場
合を例にとり説明する。この場合の方法は、未硬化の若
しくは部分的に硬化したシリコーン又はシリコーンの前
駆体からなる塗料とアナターゼ型酸化チタンゾルとを混
合し、シリコーンの前駆体を必要に応じて加水分解させ
た後、混合物を基材の表面にスプレーコーティング法、
ディップコーティング法、フローコーティング法、スピ
ンコーティング法、ロールコーティング法等の方法で塗
布し、加熱等の方法でシリコーンの前駆体の加水分解物
を脱水縮重合に付して、アナターゼ型酸化チタン粒子と
シリコーンからなる表面層を形成する。形成された表面
層は、紫外線を含む光の照射によりアナターゼ型酸化チ
タンが光励起されることにより、シリコーン分子中のケ
イ素原子に結合した有機基の少なくとも一部を水酸基に
置換され、さらにその上に物理吸着水層が形成されて、
高度の親水性を呈する。ここでシリコーンの前駆体に
は、メチルトリメトキシシラン、メチルトリエトキシシ
ラン、メチルトリブトキシシラン、メチルトリプロポキ
シシラン、エチルトリメトキシシラン、エチルトリエト
キシシラン、エチルトリブトキシシラン、エチルトリプ
ロポキシシラン、フェニルトリメトキシシラン、フェニ
ルトリエトキシシラン、フェニルトリブトキシシラン、
フェニルトリプロポキシシラン、ジメチルジメトキシシ
ラン、ジメチルジエトキシシラン、ジメチルジブトキシ
シラン、ジメチルジプロポキシシラン、ジエチルジメト
キシシラン、ジエチルジエトキシシラン、ジエチルジブ
トキシシラン、ジエチルジプロポキシシラン、フェニル
メチルジメトキシシラン、フェニルメチルジエトキシシ
ラン、フェニルメチルジブトキシシラン、フェニルメチ
ルジプロポキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、及びそれらの加水分解物、それらの混
合物が好適に利用できる。Next, the case where the surface layer is made of a photocatalyst and silicone will be described with reference to the case where the photocatalyst is anatase type titanium oxide. The method in this case is to mix a coating of uncured or partially cured silicone or a silicone precursor with an anatase-type titanium oxide sol, hydrolyze the silicone precursor if necessary, and then mix the mixture. Spray coating method on the surface of the substrate,
Dip coating method, flow coating method, spin coating method, applied by a method such as roll coating method, by subjecting the hydrolyzate of the silicone precursor to dehydration polycondensation by a method such as heating, anatase type titanium oxide particles and A surface layer made of silicone is formed. In the formed surface layer, at least a part of the organic group bonded to the silicon atom in the silicone molecule is replaced with a hydroxyl group by photoexcitation of the anatase type titanium oxide by irradiation with light including ultraviolet rays, and further thereon. The physical adsorption water layer is formed,
It exhibits a high degree of hydrophilicity. Here, silicone precursors include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,
Phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, a hydrolyzate thereof, and a mixture thereof can be suitably used.
【0025】その他、上記コーティングを塗布したフィ
ルムを基材表面にセッケン水等の透明接着剤で貼着して
もよい。ここでフィルム基材には、ポリエチレンテレフ
タレート、ポリエステル、ポリエチレン等のプラスチッ
ク製フィルムが好適に利用できる。In addition, the film coated with the above coating may be adhered to the surface of the substrate with a transparent adhesive such as soap water. Here, a plastic film such as polyethylene terephthalate, polyester, or polyethylene can be suitably used as the film substrate.
【0026】[0026]
実施例1.(+無定型シリカ) テトラエトキシシラン(和光純薬)0.69gとアナタ
ーゼ型酸化チタンゾル(日産化学、TA−15、平均粒
径10nm)1.07gとエタノール29.88gと、
純水0.36gを混合し、コーティング液を調製した。
このコーティング液をフローコーティング法により、1
0cm角のガラス鏡基材(板ガラスの裏面に反射コート
層と樹脂層が形成された基材)上に塗布した。このガラ
ス鏡板を約20分間約150℃の温度に保持することに
より、テトラエトキシシランを加水分解と脱水縮重合に
付し、アナターゼ型酸化チタン粒子が無定型シリカで結
着されたコーティングをガラス鏡板表面に形成した。こ
のコーティング中の、酸化チタンとシリカとの重量比は
1であった。このガラス鏡板を数日間暗所に放置した
後、紫外線光源(三共電気、ブラックライトブルー(B
LB)蛍光灯)を用いて試料の表面に0.5mW/cm
2の紫外線照度で約1時間紫外線を照射し、#1試料を
得た。比較のため、10cm角のガラス鏡板を数日間暗
所に放置した#2試料も準備した。まず、#1試料と#
2試料に水滴を滴下し、滴下後の様子の観察及び水との
接触角の測定を行った。ここで水との接触角は接触角測
定器(協和界面科学、CA−X150)を用い、滴下後
30秒後の水との接触角で評価した。その結果#1試料
はマイクロシリンジから試料表面に水滴を滴下される
と、水滴が一様に水膜状に試料表面を拡がる様子が観察
された。また30秒後の水との接触角は約0゜まで高度
に親水化されていた。それに対し、#2試料ではマイク
ロシリンジから試料表面に水滴を滴下されると、水滴は
表面になじんでいくものの、一様に水膜状になるまでに
は至らなかった。また30秒後の水との接触角は30゜
であった。次に、#1試料と#2試料に息を吹きかけ曇
り発生の有無を調べた。その結果#2試料では曇りが生
じたのに対し、#1試料では曇りは生じなかった。さら
に、#1試料を、その後2日間暗所に放置し、#3試料
を得た。そして#3試料について、同様に水との接触角
を接触角測定器により測定した。その結果、#3試料に
マイクロシリンジから試料表面に水滴を滴下されると、
#1試料と同様に、水滴が一様に水膜状に試料表面を拡
がる様子が観察された。また水との接触角は約3゜に維
持された。次に#3試料について息を吹きかけた後の曇
り発生の有無を観察した。その結果、曇りは観察されな
かった。Embodiment 1 FIG. (+ Amorphous silica) tetraethoxysilane (Wako Pure Chemical) 0.69 g, anatase type titanium oxide sol (Nissan Chemical Co., TA-15, average particle diameter 10 nm) 1.07 g and ethanol 29.88 g,
0.36 g of pure water was mixed to prepare a coating solution.
This coating solution is applied to the 1
It was applied onto a 0 cm square glass mirror substrate (a substrate having a reflection coating layer and a resin layer formed on the back surface of a sheet glass). By holding the glass head at a temperature of about 150 ° C. for about 20 minutes, tetraethoxysilane is subjected to hydrolysis and dehydration polycondensation, and a coating in which anatase-type titanium oxide particles are bound with amorphous silica is applied to the glass head. Formed on the surface. The weight ratio of titanium oxide to silica in this coating was 1. After leaving this glass head plate in a dark place for several days, an ultraviolet light source (Sankyo Denki, Black Light Blue (B
LB) Fluorescent light) was applied to the surface of the sample at 0.5 mW / cm.
The sample was irradiated with ultraviolet light at an ultraviolet illuminance of 2 for about 1 hour to obtain a # 1 sample. For comparison, a # 2 sample in which a 10 cm square glass head plate was left in a dark place for several days was also prepared. First, # 1 sample and #
Drops of water were dropped on the two samples, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated by using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. As a result, when a water drop was dropped on the sample surface from the microsyringe of the # 1 sample, it was observed that the water droplet spread uniformly on the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the micro syringe, the water droplet adapted to the surface, but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °. Next, the samples # 1 and # 2 were blown to examine whether or not fogging occurred. As a result, fogging occurred in the # 2 sample, but no fogging occurred in the # 1 sample. Further, the # 1 sample was left in a dark place for two days thereafter, to obtain a # 3 sample. Then, for the # 3 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water drop is dropped on the sample surface from the micro syringe on the # 3 sample,
As in the case of the # 1 sample, it was observed that the water droplet spread uniformly on the sample surface in a water film shape. The contact angle with water was maintained at about 3 °. Next, the presence or absence of fogging after spraying was observed for the # 3 sample. As a result, no fogging was observed.
【0027】実施例2.(+TiO2/WO3) 10cm角のソーダライムガラス板の表面に電子ビーム
蒸着法により無定型酸化チタン膜を被着し、その後50
0℃の温度で焼成することにより、無定型酸化チタンを
結晶化させてアナターゼ型酸化チタンを生成させた。ア
ナターゼ型酸化チタン被膜の膜厚は100nmであっ
た。さらに、その上に25%アンモニア水に溶解させた
タングステン酸を、タングステン酸重量に換算して0.
6μg/cm2を塗布後、500℃の温度で焼成した。
次に、このガラス板の裏面に真空蒸着によりアルミニ
ウムの反射コーティングを形成して鏡を製作した。この
ガラス鏡板を数日間暗所に放置した後、BLB蛍光灯を
用いて試料の表面に0.5mW/cm2の紫外線照度で
約1時間紫外線を照射し、#4試料を得た。比較のた
め、10cm角のガラス鏡板を数日間暗所に放置した実
施例1で用いた#2試料も準備した。まず、#4試料と
#2試料に水滴を滴下し、滴下後の様子の観察及び水と
の接触角の測定を行った。その結果#4試料はマイクロ
シリンジから試料表面に水滴を滴下されると、水滴が一
様に水膜状に試料表面を拡がる様子が観察された。また
30秒後の水との接触角は約0゜まで高度に親水化され
ていた。それに対し、#2試料ではマイクロシリンジか
ら試料表面に水滴を滴下されると、水滴は表面になじん
でいくものの、一様に水膜状になるまでには至らなかっ
た。また30秒後の水との接触角は30゜であった。次
に、#4試料と#2試料に息を吹きかけ曇り発生の有無
を調べた。その結果#2試料では曇りが生じたのに対
し、#4試料では曇りは生じなかった。さらに、#4試
料を、その後2日間暗所に放置し、#5試料を得た。そ
して#5試料について、同様に水との接触角を接触角測
定器により測定した。その結果、#5試料にマイクロシ
リンジから試料表面に水滴を滴下されると、#4試料と
同様に、水滴が一様に水膜状に試料表面を拡がる様子が
観察された。また水との接触角は約1゜に維持された。
次に#5試料について息を吹きかけた後の曇り発生の有
無を観察した。その結果、曇りは観察されなかった。Embodiment 2 FIG. (+ TiO 2 / WO 3 ) An amorphous titanium oxide film is deposited on the surface of a 10 cm square soda lime glass plate by electron beam evaporation, and then 50
By firing at a temperature of 0 ° C., the amorphous titanium oxide was crystallized to produce anatase type titanium oxide. The film thickness of the anatase type titanium oxide film was 100 nm. Furthermore, tungstic acid dissolved in 25% aqueous ammonia was added thereto and converted to a tungstic acid weight of 0.1%.
After applying 6 μg / cm 2 , it was baked at a temperature of 500 ° C.
Next, a mirror was manufactured by forming an aluminum reflective coating on the back surface of the glass plate by vacuum evaporation. After leaving this glass head plate in a dark place for several days, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour using a BLB fluorescent lamp to obtain a # 4 sample. For comparison, a # 2 sample used in Example 1 in which a 10 cm square glass end plate was left in a dark place for several days was also prepared. First, a water drop was dropped on the # 4 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. As a result, when a water drop was dropped on the sample surface from the microsyringe of the # 4 sample, it was observed that the water droplet spread uniformly on the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °. Next, the samples # 4 and # 2 were blown to examine whether or not fogging occurred. As a result, fogging occurred in the # 2 sample, but no fogging occurred in the # 4 sample. Further, the # 4 sample was left in a dark place for two days thereafter to obtain a # 5 sample. Then, for the # 5 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water droplet was dropped on the sample surface from the microsyringe on the # 5 sample, it was observed that the water droplet spread uniformly over the sample surface in the form of a water film, similarly to the # 4 sample. The contact angle with water was maintained at about 1 °.
Next, the presence or absence of fogging after blowing on the # 5 sample was observed. As a result, no fogging was observed.
【0028】実施例3.(+TiO2/無定型シリカ、
フィルム貼着) まず、10cm角のポリエチレンテレフタレート(PE
T)フィルムを、コロナ放電処理後、プライマー(信越
化学、PC−7A)をフローコーティング法で塗布し、
120℃で5分熱処理することにより、プライマー層を
形成した。次に、プライマー層をコロナ放電処理後、シ
リコーンハードコーティング液をフローコーティング法
で塗布し、120℃で10分熱処理することにより、ハ
ードコーティング層を形成した。次に、ハードコーティ
ング層をコロナ放電処理後、光触媒コーティング液(酸
化チタン13重量部とテトラエトキシシラン7重量部を
水とアルコールの混合溶媒中に分散させた混合液)をフ
ローコーティング法で塗布し、常温で10分乾燥させて
光触媒性フィルムを得た。このフィルムの裏側にセッケ
ン水を塗布し、10cm角の鏡基材表面に貼着した。こ
のガラス鏡板を数日間暗所に放置した後、BLB蛍光灯
を用いて試料の表面に0.5mW/cm2の紫外線照度
で約1時間紫外線を照射し、#6試料を得た。比較のた
め、10cm角のガラス鏡板を数日間暗所に放置した実
施例1で用いた#2試料も準備した。まず、#6試料と
#2試料に水滴を滴下し、滴下後の様子の観察及び水と
の接触角の測定を行った。ここで水との接触角は接触角
測定器(協和界面科学、CA−X150)を用い、滴下
後30秒後の水との接触角で評価した。その結果#6試
料はマイクロシリンジから試料表面に水滴を滴下される
と、水滴が一様に水膜状に試料表面を拡がる様子が観察
された。また30秒後の水との接触角は約0゜まで高度
に親水化されていた。それに対し、#2試料ではマイク
ロシリンジから試料表面に水滴を滴下されると、水滴は
表面になじんでいくものの、一様に水膜状になるまでに
は至らなかった。また30秒後の水との接触角は30゜
であった。次に、#6試料と#2試料に息を吹きかけ曇
り発生の有無を調べた。その結果#2試料では曇りが生
じたのに対し、#6試料では曇りは生じなかった。さら
に、#6試料を、その後2日間暗所に放置し、#7試料
を得た。そして#7試料について、同様に水との接触角
を接触角測定器により測定した。その結果、#7試料に
マイクロシリンジから試料表面に水滴を滴下されると、
#6試料と同様に、水滴が一様に水膜状に試料表面を拡
がる様子が観察された。また水との接触角は約3゜に維
持された。次に#7試料について息を吹きかけた後の曇
り発生の有無を観察した。その結果、曇りは観察されな
かった。Embodiment 3 FIG. (+ TiO2 / amorphous silica,
First, a 10 cm square polyethylene terephthalate (PE)
T) After the film is subjected to a corona discharge treatment, a primer (Shin-Etsu Chemical, PC-7A) is applied by a flow coating method,
Heat treatment was performed at 120 ° C. for 5 minutes to form a primer layer. Next, after the primer layer was subjected to corona discharge treatment, a silicone hard coating solution was applied by a flow coating method, and heat-treated at 120 ° C. for 10 minutes to form a hard coating layer. Next, after the hard coating layer is subjected to corona discharge treatment, a photocatalyst coating liquid (a mixed liquid in which 13 parts by weight of titanium oxide and 7 parts by weight of tetraethoxysilane are dispersed in a mixed solvent of water and alcohol) is applied by a flow coating method. After drying at room temperature for 10 minutes, a photocatalytic film was obtained. Soap water was applied to the back side of this film and adhered to a 10 cm square mirror substrate surface. After leaving the glass end plate in a dark place for several days, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour using a BLB fluorescent lamp to obtain a # 6 sample. For comparison, a # 2 sample used in Example 1 in which a 10 cm square glass end plate was left in a dark place for several days was also prepared. First, a water drop was dropped on the # 6 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. As a result, when a water drop was dropped on the sample surface from the microsyringe of the # 6 sample, it was observed that the water droplet spread uniformly on the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °. Next, the samples # 6 and # 2 were blown to examine whether or not fogging occurred. As a result, fogging occurred in the # 2 sample, but no fogging occurred in the # 6 sample. Further, the # 6 sample was left in a dark place for 2 days to obtain a # 7 sample. Then, for the # 7 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water drop is dropped on the sample surface from the micro syringe on the # 7 sample,
As in the case of the # 6 sample, it was observed that water droplets spread uniformly on the sample surface in the form of a water film. The contact angle with water was maintained at about 3 °. Next, the presence or absence of fogging after blowing on the # 7 sample was observed. As a result, no fogging was observed.
【0029】[0029]
【発明の効果】本発明では、車両用ミラー表面に、実質
的に透明な光触媒性酸化チタン粒子を含有する表面層を
備えることにより、光触媒の光励起に応じて、表面層の
表面は親水性を呈し、付着した湿分の凝縮水及び/又は
水滴が前記層の表面に一様に広がり、降雨や水しぶきを
受けても、湿分凝縮水及び/又は水滴によって曇り若し
くは翳るのが防止されるようになり、視界性が確保され
るようになる。According to the present invention, by providing a surface layer containing substantially transparent photocatalytic titanium oxide particles on the surface of a vehicle mirror, the surface of the surface layer becomes hydrophilic in response to photoexcitation of the photocatalyst. Present and condensed moisture condensed water and / or water droplets spread evenly on the surface of the layer, and are prevented from being clouded or overshadowed by the moisture condensed water and / or water droplets even when subjected to rainfall or splashing. And visibility is secured.
【図1】 本発明に係る車両用ミラーの表面構造を示す
図。FIG. 1 is a diagram showing a surface structure of a vehicle mirror according to the present invention.
【図2】 本発明に係る車両用ミラーの他の表面構造を
示す図。FIG. 2 is a diagram showing another surface structure of the vehicle mirror according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI C09D 1/00 C09D 1/00 5/00 5/00 C09K 3/18 C09K 3/18 G02B 1/10 G02B 5/08 F 5/08 1/10 Z 審査官 出口 昌哉 (56)参考文献 特開 昭63−5301(JP,A) 特開 平7−256088(JP,A) 特開 平7−164971(JP,A) 特開 平4−174679(JP,A) 特開 平6−296874(JP,A) 特開 平7−286114(JP,A) 特開 昭55−106261(JP,A) 特開 平6−246165(JP,A) 特開 平7−60132(JP,A) 特開 昭63−100042(JP,A) 特開 平8−119673(JP,A) 特開 平8−164334(JP,A) 特開 平9−225303(JP,A) 特許2756474(JP,B1) 特許2865065(JP,B2) 特許2924902(JP,B2) 特許2943768(JP,B2) 特許2917525(JP,B2) 米国特許3640712(US,A) 国際公開95/11751(WO,A1) 欧州特許出願公開633064(EP,A 1) (58)調査した分野(Int.Cl.7,DB名) B60S 1/02 B60S 1/60 B60R 1/06 B01J 35/02 C08J 7/04 C09D 1/00 C09D 5/00 C09K 3/18 G02B 1/10 G02B 5/08 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C09D 1/00 C09D 1/00 5/00 5/00 C09K 3/18 C09K 3/18 G02B 1/10 G02B 5/08 F 5 / 08 1/10 Z Examiner Masaya Deguchi (56) References JP-A-63-5301 (JP, A) JP-A-7-256088 (JP, A) JP-A-7-164971 (JP, A) JP JP-A-4-174679 (JP, A) JP-A-6-296874 (JP, A) JP-A-7-286114 (JP, A) JP-A-55-106261 (JP, A) JP-A-6-246165 (JP) JP-A-7-60132 (JP, A) JP-A-63-100042 (JP, A) JP-A-8-119673 (JP, A) JP-A-8-164334 (JP, A) 9-225303 (JP, A) Patent 2756474 (JP, B1) Patent 2865065 (JP, B2) Patent 2294902 (JP, B2) Patent 2943768 (JP, B2) Patent 2917525 (JP, B2) US Patent 3640712 (US, A) International Publication No. WO 95/11751 (WO, A1) European Patent Application Publication 633064 (EP, A1) (58) Int.Cl. 7 , DB name) B60S 1/02 B60S 1/60 B60R 1/06 B01J 35/02 C08J 7/04 C09D 1/00 C09D 5/00 C09K 3/18 G02B 1/10 G02B 5/08
Claims (21)
酸化タングステン、酸化第二鉄、チタン酸ストロンチウ
ムからなる群から選ばれた光触媒粒子を含有する実質的
に透明な表面層を 備え、 前記光触媒の光励起に応じて、前記層の表面は親水性を
呈し、以て付着した湿分の凝縮水及び水滴もしくは湿分
の凝縮水又は水滴が前記層の表面に一様に広がり、湿分
凝縮水及び水滴もしくは湿分凝縮水又は水滴によって曇
り若しくは翳るのが防止されるようになった防曇性車両
用ミラー。Claims: 1. A mirror substrate for a vehicle, comprising: titanium oxide, tin oxide, zinc oxide, bismuth trioxide,
Tungsten oxide, ferric oxide, strontium titanate
Substantially containing photocatalyst particles selected from the group consisting of
A transparent surface layer, and the surface of the layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, whereby condensed water and water droplets or moisture condensed water or water droplets adhered to the surface of the layer. Anti-fogging vehicle mirror, which spreads evenly over the surface and is prevented from being fogged or overshadowed by moisture condensed water and water droplets or moisture condensed water or water droplets.
れていることを特徴とする請求項1に記載の防曇性車両
用ミラー。2. The antifogging vehicle mirror according to claim 1, wherein the surface layer further contains silica.
れていることを特徴とする請求項1に記載の防曇性車両
用ミラー。3. The antifogging vehicle mirror according to claim 1, wherein the surface layer further contains a solid acid.
有されていることを特徴とする請求項1に記載の防曇性
車両用ミラー。4. The antifogging vehicle mirror according to claim 1, wherein the surface layer further contains silicone.
起に応じて、水との接触角に換算して10゜以下の親水
性を呈することを特徴とする請求項1〜4に記載の防曇
性車両用ミラー。5. The surface according to claim 1, wherein the surface of the surface layer exhibits hydrophilicity of 10 ° or less in terms of a contact angle with water in response to photoexcitation of the photocatalyst. Anti-fog vehicle mirror.
ることを特徴とする請求項1〜5に記載の防曇性車両用
ミラー。6. The antifogging vehicle mirror according to claim 1, wherein the thickness of the surface layer is 0.4 μm or less.
ることを特徴とする請求項1〜5に記載の防曇性車両用
ミラー。7. The antifogging vehicle mirror according to claim 1, wherein the thickness of the surface layer is 0.2 μm or less.
な保護層が設けられていることを特徴とする請求項1〜
5に記載の防曇性車両用ミラー。8. The method according to claim 1, wherein a protective layer capable of being made hydrophilic is further provided on the surface of the surface layer.
6. The antifogging vehicle mirror according to 5.
を特徴とする請求項1〜8に記載の防曇性車両用ミラ
ー。9. The antifogging vehicle mirror according to claim 1, wherein the refractive index of the surface layer is 2 or less.
ラーを備えた自動車。10. An automobile provided with the anti-fogging vehicle mirror according to claim 1. Description:
ラーを備えた二輪車。11. A two-wheeled vehicle comprising the anti-fogging vehicle mirror according to claim 1.
酸化タングステン、酸化第二鉄、チタン酸ストロンチウ
ムからなる群から選ばれた光触媒粒子を含有する実質的
に透明な表面層を 備えてなり、 車両用ミラー表面に貼着すると、車両用ミラー表面が前
記光触媒の光励起に応じて、親水性を呈し、以て付着し
た湿分の凝縮水及び水滴もしくは湿分の凝縮水又は水滴
が前記層の表面に一様に広がり、湿分凝縮水及び水滴も
しくは湿分の凝縮水又は水滴によって曇り若しくは翳る
のが防止されるようになる、車両用ミラー用防曇性フィ
ルム。12. The method according to claim 12, wherein the surface of the film base material includes titanium oxide, tin oxide, zinc oxide, bismuth trioxide,
Tungsten oxide, ferric oxide, strontium titanate
Substantially containing photocatalyst particles selected from the group consisting of
When attached to the surface of the vehicle mirror, the surface of the vehicle mirror exhibits hydrophilicity in response to the photoexcitation of the photocatalyst, and condensed water and water droplets or moisture of the attached moisture. Anti-fog for vehicle mirrors, so that condensed water or water droplets spread evenly over the surface of the layer and are prevented from being clouded or overshadowed by moisture condensed water and water droplets or water condensed water or water droplets. Film.
されていることを特徴とする請求項12に記載の車両用
ミラー用防曇性フィルム。13. The antifogging film for a vehicle mirror according to claim 12, wherein the surface layer further contains silica.
されていることを特徴とする請求項12に記載の車両用
ミラー用防曇性フィルム。14. The antifogging film for a vehicle mirror according to claim 12, wherein the surface layer further contains a solid acid.
含有されていることを特徴とする請求項12に記載の車
両用ミラー用防曇性フィルム。15. The antifogging film for a vehicle mirror according to claim 12, wherein the surface layer further contains silicone.
励起に応じて、水との接触角に換算して10゜以下の親
水性を呈することを特徴とする請求項12〜15に記載
の車両用ミラー用防曇性フィルム。16. The surface according to claim 12, wherein the surface of the surface layer exhibits a hydrophilicity of 10 ° or less in terms of a contact angle with water in response to photoexcitation of the photocatalyst. Anti-fog film for vehicle mirrors.
あることを特徴とする請求項12〜16に記載の車両用
ミラー用防曇性フィルム。17. The antifogging film for a vehicle mirror according to claim 12, wherein the thickness of the surface layer is 0.4 μm or less.
あることを特徴とする請求項12〜16に記載の車両用
ミラー用防曇性フィルム。18. The antifogging film for a vehicle mirror according to claim 12, wherein said surface layer has a thickness of 0.2 μm or less.
能な保護層が設けられていることを特徴とする請求項1
2〜16に記載の車両用ミラー用防曇性フィルム。19. The method according to claim 1, wherein a protective layer that can be further hydrophilized is provided on the surface of the surface layer.
17. The anti-fog film for a vehicle mirror according to 2 to 16.
とを特徴とする請求項12〜19に記載の車両用ミラー
用防曇性フィルム。20. The antifogging film for a vehicle mirror according to claim 12, wherein the refractive index of the surface layer is 2 or less.
る工程、前記車両用ミラーの表面層に含有される光触媒
を光励起することにより、前記層の表面を親水性にな
し、以て付着した湿分の凝縮水及び水滴もしくは湿分の
凝縮水又は水滴が前記層の表面に一様に広がらせる工
程;からなる車両用ミラーの防曇方法。21. The step of preparing a vehicle mirror according to claim 1, wherein a photocatalyst contained in a surface layer of the vehicle mirror is photoexcited to make the surface of the layer hydrophilic and adhered. The condensed water and water droplets or the condensed water or water droplets of the moisture spread uniformly on the surface of the layer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8281223A 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 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7-354649 | 1995-12-22 | ||
JP35464995 | 1995-12-22 | ||
JP8281223A 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09230118A JPH09230118A (en) | 1997-09-05 |
JP3063968B2 true JP3063968B2 (en) | 2000-07-12 |
Family
ID=18438979
Family Applications (71)
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 |
JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
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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 |
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 |
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 |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
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 |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
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 |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
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 |
JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
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 |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
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 |
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 |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
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 |
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 |
JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
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 |
JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
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 |
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 |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
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 (25)
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 |
JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
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 |
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 |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
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 |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
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 |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
Family Applications After (45)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
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 |
JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
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 |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
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 |
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 |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
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 |
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 |
JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
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 |
JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
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 |
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 |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
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 |
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JP (71) | JPH09231821A (en) |
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JP3996682B2 (en) * | 1997-10-20 | 2007-10-24 | 日本デコール株式会社 | Decorative sheet having organic substance decomposing function and method for producing the same |
JPH11152447A (en) * | 1997-11-21 | 1999-06-08 | Toto Ltd | Surface-treating agent for forming photocatalyzing coating film, and formation of photocatalyzing coating film using the surface-treating agent |
KR100740055B1 (en) * | 1997-12-25 | 2007-10-18 | 산젠 가꼬 가부시키가이샤 | Anti-fogging laminates |
JPH11197516A (en) * | 1998-01-09 | 1999-07-27 | Takenaka Komuten Co Ltd | Photocatalyst material and its production |
AU2546599A (en) * | 1998-02-10 | 1999-08-30 | Toto Ltd. | Coating material for forming photocatalytic hydrophilic film, method of forming photocatalytic hydrophilic film, and photocatalytic hydrophilic member |
JPH11263950A (en) * | 1998-03-16 | 1999-09-28 | Nippon Carbide Ind Co Inc | Transparent adhesive sheet for preventing dew condensation and dew condensation-preventing deflective sign |
CN1263544A (en) * | 1998-04-10 | 2000-08-16 | 松下电工株式会社 | Inorganic coating composition and hydrophilic inorganic coating film |
JPH11347482A (en) * | 1998-06-12 | 1999-12-21 | Dainippon Toryo Co Ltd | Production of joint part coated porcelain tile panel |
CH693138A5 (en) * | 1998-06-19 | 2003-03-14 | Unaxis Trading Ag | Laminated glass and method for making a coated plastic film therefor. |
KR100290066B1 (en) * | 1998-07-13 | 2001-05-15 | 김명신 | How to fix titanium dioxide, used as an air freshener, on activated carbon |
TW473400B (en) | 1998-11-20 | 2002-01-21 | Asahi Chemical Ind | Modified photocatalyst sol |
JP2000226234A (en) * | 1998-12-03 | 2000-08-15 | Toto Ltd | Hydrophilic member |
JP3340688B2 (en) * | 1999-01-28 | 2002-11-05 | シャープ株式会社 | Air conditioner |
EP1023910A1 (en) * | 1999-01-29 | 2000-08-02 | Institut Straumann AG | Preparation of osteophilic surfaces for metallic prosthetic devices anchorable to bone |
EP1182169A4 (en) * | 1999-02-04 | 2004-12-15 | Japan Science & Tech Agency | Process for producing anatase titania or composite oxide containing anatase titania |
JP2000234892A (en) * | 1999-02-12 | 2000-08-29 | Zexel Corp | Method for reducing heat exchanger and heat exchanger manufactured by that method |
EP1174479A4 (en) | 1999-03-09 | 2009-08-19 | Toto Ltd | Hydrophilic member, method for preparation thereof, and coating agent and apparatus for preparation thereof |
JP4029516B2 (en) * | 1999-03-18 | 2008-01-09 | 株式会社Inax | Photocatalytic tile |
KR100308818B1 (en) * | 1999-04-01 | 2001-09-26 | 이계안 | Hydrophilic coating glass coated with porous thin layer of TiO2 |
JP4345941B2 (en) * | 1999-04-16 | 2009-10-14 | ベック株式会社 | Coating method |
DE60001764T2 (en) | 1999-05-21 | 2003-11-13 | Jsr Corp | Coating agents and films and glass coated with them |
JP2000334309A (en) * | 1999-05-25 | 2000-12-05 | Shinichi Harigai | Photocatalyst |
JP2000334308A (en) * | 1999-05-25 | 2000-12-05 | Shinichi Harigai | Cafrrier for photocatalyst and photocatalyst using the same |
FR2794225B3 (en) * | 1999-05-25 | 2001-06-15 | Saint Gobain Vitrage | REFRIGERATED ENCLOSURE DOOR WITH VACUUM WINDOWS |
JP4513141B2 (en) * | 1999-06-21 | 2010-07-28 | パナソニック株式会社 | air purifier |
JP4507302B2 (en) * | 1999-08-10 | 2010-07-21 | 凸版印刷株式会社 | High refractive index composition |
EP1081108B1 (en) | 1999-09-02 | 2004-02-25 | Central Glass Company, Limited | Article with photocatalytic film |
JP2001080974A (en) * | 1999-09-08 | 2001-03-27 | Fuji Photo Film Co Ltd | Composite base plate material and method for producing the same |
WO2001025362A1 (en) * | 1999-10-01 | 2001-04-12 | Nippon Soda Co., Ltd. | Sheet for transferring photocatalyst |
JP2001164117A (en) * | 1999-12-07 | 2001-06-19 | Toppan Printing Co Ltd | High-refractive-index composition and antireflection laminate |
TW468053B (en) * | 1999-12-14 | 2001-12-11 | Nissan Chemical Ind Ltd | Antireflection film, process for forming the antireflection film, and antireflection glass |
US6603320B2 (en) | 2000-02-07 | 2003-08-05 | Organo Corporation | Electric conductometer, electrode for measuring electric conductivity, and method for producing the same |
US8632583B2 (en) | 2011-05-09 | 2014-01-21 | Palmaz Scientific, Inc. | Implantable medical device having enhanced endothelial migration features and methods of making the same |
US6866937B2 (en) | 2000-08-22 | 2005-03-15 | Central Glass Company, Limited | Glass plate with oxide film and process for producing same |
KR100631104B1 (en) * | 2000-11-03 | 2006-10-02 | 한국유리공업주식회사 | Hydrophilic glass coated with metal oxide and method for producing it |
JP2002159910A (en) * | 2000-11-27 | 2002-06-04 | Cleanup Corp | Method for forming photocatalytic coating film on surface of base material |
JP4755756B2 (en) * | 2000-12-20 | 2011-08-24 | 日本テトラパック株式会社 | Photocatalytic material |
BR0206737A (en) | 2001-01-30 | 2004-02-03 | Procter & Gamble | Coating compositions for surface modification |
WO2002074451A1 (en) * | 2001-03-21 | 2002-09-26 | Bridgestone Corporation | Method for forming antifouling coating and antifouling material having antifouling coating |
JP2002285036A (en) * | 2001-03-23 | 2002-10-03 | Seiichi Rengakuji | Photocatalyst supported aluminum material and its manufacturing method |
KR100393733B1 (en) * | 2001-03-28 | 2003-08-06 | 홍국선 | Ceramic Compositions for superhydrophilic coating and its manufacturing method |
US6827966B2 (en) * | 2001-05-30 | 2004-12-07 | Novartis Ag | Diffusion-controllable coatings on medical device |
JP2005505352A (en) * | 2001-10-11 | 2005-02-24 | シュトラウマン・ホールディング・アクチェンゲゼルシャフト | Osteophilic implant |
JP2003135228A (en) * | 2001-11-02 | 2003-05-13 | Sanyo Electric Co Ltd | Low temperature show case |
DE60307053T2 (en) * | 2002-02-14 | 2007-02-15 | Lg Electronics Inc. | DOOR FOR WASHING MACHINE AND METHOD FOR THE PRODUCTION THEREOF |
US6938546B2 (en) | 2002-04-26 | 2005-09-06 | Mitsubishi Heavy Industries, Ltd. | Printing press, layered formation and making method thereof, and printing plate and making method thereof |
JP4282597B2 (en) | 2002-06-03 | 2009-06-24 | 旭化成ケミカルズ株式会社 | Photocatalyst composition |
JP4169557B2 (en) * | 2002-09-19 | 2008-10-22 | 旭化成ケミカルズ株式会社 | Photocatalyst |
JP4069369B2 (en) | 2002-09-25 | 2008-04-02 | 信越化学工業株式会社 | Antireflection film and method of manufacturing antireflection film |
CA2499976C (en) | 2002-09-26 | 2013-06-11 | Advanced Bio Prosthetic Surfaces, Ltd. | Implantable materials having engineered surfaces and method of making same |
US8268340B2 (en) | 2002-09-26 | 2012-09-18 | Advanced Bio Prosthetic Surfaces, Ltd. | Implantable materials having engineered surfaces and method of making same |
US8679517B2 (en) | 2002-09-26 | 2014-03-25 | Palmaz Scientific, Inc. | Implantable materials having engineered surfaces made by vacuum deposition and method of making same |
JP2003231204A (en) * | 2002-12-09 | 2003-08-19 | Toto Ltd | Functional material and functional coating composition |
JP3707737B2 (en) * | 2003-03-06 | 2005-10-19 | 重岡 誠司 | Outdoor heat exchanger |
DE10325768A1 (en) * | 2003-06-05 | 2004-12-23 | Chemetall Gmbh | Coating system for glass surfaces, process for its production and its application |
JP4493290B2 (en) * | 2003-06-23 | 2010-06-30 | 菊治 山下 | Artificial biomaterial and method for producing the same |
US20050040151A1 (en) | 2003-08-20 | 2005-02-24 | Robert Dyrdek | Heated side window glass |
JP2005096336A (en) * | 2003-09-26 | 2005-04-14 | Lintec Corp | Process film for ceramic green sheet production and its production method |
JP2005186353A (en) * | 2003-12-25 | 2005-07-14 | Murakami Corp | Anti-fogging element |
JP4995428B2 (en) * | 2004-03-10 | 2012-08-08 | 東海旅客鉄道株式会社 | Titanium oxide coating formation method |
JP2008510186A (en) * | 2004-08-10 | 2008-04-03 | 日本板硝子株式会社 | LCD mirror system and method |
JP4758086B2 (en) * | 2004-09-09 | 2011-08-24 | タキロン株式会社 | Construction structure using a sealing material used for polycarbonate resin parts with photocatalytic function |
NZ554581A (en) | 2004-09-20 | 2011-03-31 | Agc Flat Glass Na Inc | Anti-fog refrigeration door and method of making the same |
JP2006091249A (en) | 2004-09-22 | 2006-04-06 | Murakami Corp | Camera |
WO2006070395A1 (en) * | 2004-12-28 | 2006-07-06 | Council Of Scientific And Industrial Research | Photocatalytic auto-cleaning process of stains |
WO2006088079A1 (en) * | 2005-02-18 | 2006-08-24 | Nippon Soda Co., Ltd. | Organic-inorganic composite body |
CN101163550B (en) | 2005-02-24 | 2012-04-25 | 财团法人电力中央研究所 | Multifunctional material |
ES2320485T3 (en) | 2005-02-24 | 2009-05-22 | Central Research Institute Of Electric Power Industry | PROCEDURE TO PRODUCE A MULTIFUNCTIONAL MATERIAL. |
JP4814534B2 (en) * | 2005-02-28 | 2011-11-16 | 財団法人電力中央研究所 | Manufacturing method of structural materials |
JP4807724B2 (en) * | 2005-02-28 | 2011-11-02 | 財団法人電力中央研究所 | Rail vehicle manufacturing method |
JP4480014B2 (en) * | 2005-02-28 | 2010-06-16 | 財団法人電力中央研究所 | Rocket parts |
JP4843231B2 (en) * | 2005-02-28 | 2011-12-21 | 財団法人電力中央研究所 | Kitchen products |
JP4771359B2 (en) * | 2005-02-28 | 2011-09-14 | 財団法人電力中央研究所 | Playground equipment |
JP4807723B2 (en) * | 2005-02-28 | 2011-11-02 | 財団法人電力中央研究所 | Manufacturing method of heat-resistant member |
JP4807725B2 (en) * | 2005-02-28 | 2011-11-02 | 財団法人電力中央研究所 | Manufacturing method of energy generating equipment |
JP4958029B2 (en) * | 2005-02-28 | 2012-06-20 | 一般財団法人電力中央研究所 | Building materials |
JP4807722B2 (en) * | 2005-02-28 | 2011-11-02 | 財団法人電力中央研究所 | Manufacturing method for environmentally resistant equipment |
JP4541929B2 (en) * | 2005-02-28 | 2010-09-08 | 財団法人電力中央研究所 | Flying object |
JP4995425B2 (en) * | 2005-02-28 | 2012-08-08 | 一般財団法人電力中央研究所 | Irrigation apparatus, irrigation member, manufacturing method thereof, and irrigation system |
JP2006247760A (en) * | 2005-03-08 | 2006-09-21 | Disco Abrasive Syst Ltd | Machining apparatus |
TW200631899A (en) | 2005-03-09 | 2006-09-16 | Tokai Ryokaku Tetsudo Kk | Titanium oxide-coating agent, and forming method for titanium oxide-coating film |
JP4659494B2 (en) * | 2005-03-23 | 2011-03-30 | 株式会社ミクニ | Infrared transmitting window material, infrared sensor unit, and combustion apparatus |
US7757629B2 (en) * | 2005-04-14 | 2010-07-20 | Transitions Optical, Inc. | Method and apparatus for coating an optical article |
KR100796718B1 (en) * | 2005-08-10 | 2008-01-21 | 요시노리 나카가와 | Method for manufacturing photoelectro-chemical cell and photoelectro-chemical cell |
JP3795515B1 (en) * | 2005-08-10 | 2006-07-12 | 善典 中川 | Manufacturing method of semiconductor photoelectrochemical cell |
ES2397093T3 (en) | 2005-11-04 | 2013-03-04 | Tokuyama Corporation | Coating machine |
JP5004561B2 (en) * | 2005-11-30 | 2012-08-22 | 株式会社トクヤマ | Coating equipment |
GB0602933D0 (en) | 2006-02-14 | 2006-03-22 | Pilkington Automotive Ltd | Vehicle glazing |
EP1829991A1 (en) * | 2006-03-02 | 2007-09-05 | UGINE & ALZ FRANCE | Stainless steel plate coated with self-cleaning coating. |
JP2007247166A (en) * | 2006-03-14 | 2007-09-27 | Sumitomo Chemical Co Ltd | Road mirror |
JP2007262498A (en) * | 2006-03-28 | 2007-10-11 | National Institute Of Advanced Industrial & Technology | Color-controlled titanium alloy bolt and nut |
JP4849525B2 (en) * | 2006-04-04 | 2012-01-11 | 花王株式会社 | Resin composition |
JP2007277935A (en) * | 2006-04-07 | 2007-10-25 | Sekisui Jushi Co Ltd | Indicating body for road |
JP2008013833A (en) * | 2006-07-07 | 2008-01-24 | National Institute Of Advanced Industrial & Technology | Titanium alloy member which develops controlled color |
JP4966614B2 (en) * | 2006-09-14 | 2012-07-04 | Mkvドリーム株式会社 | Agricultural film |
JP2008114760A (en) * | 2006-11-06 | 2008-05-22 | Asahi Glass Co Ltd | Vehicle with anti-fogging glass and set of vehicle window glass |
JP4823045B2 (en) * | 2006-12-12 | 2011-11-24 | 旭化成ケミカルズ株式会社 | Water-based photocatalytic composition |
JP2008184357A (en) * | 2007-01-30 | 2008-08-14 | National Institute Of Advanced Industrial & Technology | Method of making surface of oxide amphiphilic |
JP5064817B2 (en) * | 2007-01-30 | 2012-10-31 | トヨタ自動車株式会社 | Method for preventing contamination of automobile wheel and automobile wheel |
US7659226B2 (en) | 2007-02-26 | 2010-02-09 | Envont Llc | Process for making photocatalytic materials |
JP2008260667A (en) * | 2007-04-13 | 2008-10-30 | Univ Of Electro-Communications | Method for manufacturing titanium oxide thin film and resin product with titanium oxide thin film |
KR100809030B1 (en) * | 2007-05-08 | 2008-03-03 | 주식회사 에임하이글로벌 | Board for road facilities and preparation method thereof |
JP2009002979A (en) * | 2007-06-19 | 2009-01-08 | Mitsubishi Electric Corp | Video display device and its manufacturing method |
JP5510911B2 (en) * | 2007-08-17 | 2014-06-04 | 株式会社伸興サンライズ | Composite interior coating material for buildings |
JP2007327071A (en) * | 2007-08-23 | 2007-12-20 | Kawasaki Heavy Ind Ltd | Method for producing hydrophilic coating composition |
JP2009090641A (en) | 2007-09-20 | 2009-04-30 | Fujifilm Corp | Anticlouding cover and cover for meter using it |
JP5705398B2 (en) * | 2007-12-05 | 2015-04-22 | トヨタ自動車株式会社 | Vehicle wheels and wheel caps |
JP5145023B2 (en) * | 2007-12-19 | 2013-02-13 | 住友軽金属工業株式会社 | Fin material for heat exchanger and manufacturing method thereof |
US7910085B2 (en) | 2007-12-28 | 2011-03-22 | Tdk Corporation | Process for production of iron oxyhydroxide particles |
JP4993745B2 (en) * | 2007-12-28 | 2012-08-08 | 株式会社アルバック | Deposition equipment |
JP2009185107A (en) * | 2008-02-04 | 2009-08-20 | Pialex Technologies Corp | Hydrophilic coating material and hydrophilic coated object |
KR101104262B1 (en) * | 2008-12-31 | 2012-01-11 | 주식회사 노루홀딩스 | Article wih self-cleaning effect and method of preparation thereof |
JP5267308B2 (en) * | 2009-04-28 | 2013-08-21 | 信越化学工業株式会社 | Photocatalyst coating liquid that provides a photocatalytic thin film excellent in photoresponsiveness and the photocatalytic thin film |
US20110008612A1 (en) * | 2009-07-10 | 2011-01-13 | Korea University Research And Business Foundation | Self-cleaning surfaces |
JP5365501B2 (en) * | 2009-12-24 | 2013-12-11 | 平岡織染株式会社 | Non-flammable interior illuminated signboard |
JP5365500B2 (en) * | 2009-12-24 | 2013-12-11 | 平岡織染株式会社 | Non-flammable interior illuminated signboard |
JP5411791B2 (en) * | 2010-04-23 | 2014-02-12 | 三菱レイヨン株式会社 | Manufacturing method of laminated resin plate |
CN101830644B (en) * | 2010-05-14 | 2012-11-14 | 中国科学院上海技术物理研究所 | High-stability car coated glass membrane system |
JP5810294B2 (en) * | 2010-07-27 | 2015-11-11 | パナソニックIpマネジメント株式会社 | Rainwater collecting wall material |
JP5711744B2 (en) | 2010-07-29 | 2015-05-07 | Toto株式会社 | INORGANIC MATERIAL HAVING PHOTOCATALYST LAYER, PROCESS FOR PRODUCING THE SAME, AND PHOTOCATALYST COATING LIQUID FOR INORGANIC MATERIAL |
CN103140288B (en) | 2010-07-29 | 2015-03-11 | Toto株式会社 | Photocatalyst coated body and photocatalyst coating liquid |
EP2621620B1 (en) * | 2010-09-28 | 2016-04-06 | Dow Global Technologies LLC | Reactive flow static mixer with cross-flow obstructions and method for mixing |
JP2012086104A (en) * | 2010-10-15 | 2012-05-10 | Asahi Kasei Chemicals Corp | Photocatalyst composition |
JP2012087213A (en) * | 2010-10-19 | 2012-05-10 | Nippon Parkerizing Co Ltd | Hydrophilic film for metal material, hydrophilization-treating agent, and hydrophilization-treating method |
US8728563B2 (en) | 2011-05-03 | 2014-05-20 | Palmaz Scientific, Inc. | Endoluminal implantable surfaces, stents, and grafts and method of making same |
WO2013024897A1 (en) * | 2011-08-18 | 2013-02-21 | 株式会社インパクト | Guidance display board |
JP2013096959A (en) * | 2011-11-04 | 2013-05-20 | Shiyouichi Yoshino | Radioactive decontamination method |
JP5250685B2 (en) * | 2011-11-25 | 2013-07-31 | パナソニック株式会社 | Camera cover and camera |
KR20130118456A (en) * | 2012-04-20 | 2013-10-30 | 호서대학교 산학협력단 | Ozone contactor with static mixer |
JP6171275B2 (en) * | 2012-07-02 | 2017-08-02 | 大日本印刷株式会社 | Transparent film and method for producing the same |
JP6028495B2 (en) * | 2012-09-27 | 2016-11-16 | Toto株式会社 | Photocatalyst member |
CN102923836A (en) * | 2012-11-15 | 2013-02-13 | 常州大学 | Method for treating washing wastewater by using composite-film modified sintered gangue ceramsite |
JP6105998B2 (en) * | 2013-03-26 | 2017-03-29 | パナホーム株式会社 | Method for producing photocatalyst composition and method for producing photocatalyst |
CN105732125B (en) * | 2013-11-30 | 2018-03-13 | 国网河南省电力公司平顶山供电公司 | A kind of porcelain and glass insulator low-temperature resistance coating |
EP3103777B1 (en) * | 2014-02-05 | 2021-03-24 | AGC Inc. | Laminated glass production method |
CN104047343A (en) * | 2014-06-20 | 2014-09-17 | 欧士玺 | Mobile toilet capable of recycling water |
JP5909604B1 (en) | 2014-07-30 | 2016-04-26 | 三菱マテリアル株式会社 | Surface coating material, coating film and hydrophilic oil-repellent material |
JP6461573B2 (en) | 2014-07-30 | 2019-01-30 | 三菱マテリアル株式会社 | Oil / water separator / collector |
EP3175899B1 (en) | 2014-07-30 | 2019-03-13 | Mitsubishi Materials Corporation | Filter medium, method for producing filter medium, water treatment module, and water treatment device |
CN106574165B (en) | 2014-07-30 | 2018-10-19 | 三菱综合材料株式会社 | Hydrophilic oil-repellent agent and its manufacturing method and surface covering material, coated film, resin combination, water-oil separating filter material, porous body |
KR101942261B1 (en) * | 2014-09-24 | 2019-01-28 | (주)엘지하우시스 | Visible light active photocatalyst tile |
KR101642870B1 (en) * | 2014-10-21 | 2016-08-29 | 가천대학교 산학협력단 | Endoscope |
JP2016104681A (en) * | 2014-12-01 | 2016-06-09 | 大日本印刷株式会社 | Method for producing laminated glass, and laminated glass |
JP6366813B2 (en) | 2015-02-27 | 2018-08-01 | 富士フイルム株式会社 | Gas separation asymmetric membrane, gas separation module, gas separation device, and gas separation method |
CN104720649B (en) * | 2015-03-18 | 2017-03-01 | 杭州桑莱特卫浴有限公司 | A kind of bathroom cabinet and its production method |
CN104848985B (en) * | 2015-06-05 | 2017-03-08 | 合肥工业大学 | A kind of vacuum detecting method based on infrared laser spectroscopy and system |
JPWO2017022075A1 (en) * | 2015-08-04 | 2017-08-03 | 三菱電機株式会社 | Elevator car panels |
JP2017090380A (en) * | 2015-11-16 | 2017-05-25 | 株式会社デンソーウェーブ | Laser radar device, window member for laser radar device, and control program for laser radar device |
CN105349042A (en) * | 2015-11-20 | 2016-02-24 | 杨京广 | Silicon carbide coating and use method thereof |
CN105444486A (en) * | 2015-12-31 | 2016-03-30 | 广西路桥工程集团有限公司 | Multi-way valve circulation system for cooling system |
JP6811415B2 (en) * | 2016-01-29 | 2021-01-13 | パナソニックIpマネジメント株式会社 | urinal |
JP2017165612A (en) * | 2016-03-16 | 2017-09-21 | Towa株式会社 | Translucent material, low adhesion material and molding member |
CN105694688B (en) * | 2016-03-16 | 2017-09-26 | 曲阜师范大学 | A kind of fast preparation method of high intensity super-hydrophobic coat |
CN107313490A (en) * | 2016-04-26 | 2017-11-03 | 厦门致杰智能科技有限公司 | A kind of Split intelligent toilet seat |
CN105860692A (en) * | 2016-04-29 | 2016-08-17 | 南京晨光艺术工程有限公司 | Self-cleaning Buddha statue |
CN106242314A (en) * | 2016-08-23 | 2016-12-21 | 张洪建 | A kind of glass copper-plating technique |
CN108261086A (en) * | 2017-01-03 | 2018-07-10 | 佛山市顺德区美的电热电器制造有限公司 | The preparation method of Anti-fog mirror, cooking apparatus and Anti-fog mirror |
JP6814473B2 (en) * | 2017-02-28 | 2021-01-20 | 国立大学法人東北大学 | Photocatalytic functional member and its manufacturing method |
JP6428864B2 (en) * | 2017-07-03 | 2018-11-28 | 大日本印刷株式会社 | Transparent film and method for producing the same |
KR102138411B1 (en) * | 2017-07-07 | 2020-07-27 | 주식회사 엘지화학 | Coating composition including the same, organic light emitting device using the same and method of manufacturing the same |
JP2019070247A (en) * | 2017-10-06 | 2019-05-09 | スリーエム イノベイティブ プロパティズ カンパニー | Window film |
MX2023000863A (en) * | 2018-01-30 | 2023-03-01 | Viavi Solutions Inc | Optical device having optical and mechanical properties. |
CN108383396A (en) * | 2018-02-27 | 2018-08-10 | 张家港外星人新材料科技有限公司 | The double-deck film glass with anti-reflection film and antistatic automatically cleaning film and its preparation method |
CN110157224A (en) * | 2018-03-14 | 2019-08-23 | 成都今天化工有限公司 | A method of preparing nano ceramics anti-pollution flashover coating |
JP2019158247A (en) * | 2018-03-14 | 2019-09-19 | 株式会社デンソー | Heat exchanger |
PL425045A1 (en) * | 2018-03-28 | 2019-10-07 | Uniwersytet Jagielloński | Method for producing nanoporous semiconducting layers of metal oxides |
KR101917149B1 (en) | 2018-05-17 | 2018-11-09 | 주식회사 대수하이테크 | Anti-fouling coating composition having excellent weatherability |
JP7086744B2 (en) * | 2018-06-22 | 2022-06-20 | 株式会社東芝 | Camera system |
JP7329909B2 (en) * | 2018-06-28 | 2023-08-21 | 小林製薬株式会社 | Coating agent for toilet bowl |
JP2020069684A (en) * | 2018-10-30 | 2020-05-07 | 三井化学株式会社 | Multilayer structure |
JP7290938B2 (en) * | 2018-12-11 | 2023-06-14 | イビデン株式会社 | Manufacturing method of cover for infrared detection element |
JP2020106751A (en) * | 2018-12-28 | 2020-07-09 | ホヤ レンズ タイランド リミテッドHOYA Lens Thailand Ltd | Spectacle lens |
CN109667139B (en) * | 2018-12-31 | 2021-06-29 | 盐城工学院 | Anti-ultraviolet self-cleaning composition and preparation method and application thereof |
WO2020202593A1 (en) * | 2019-04-03 | 2020-10-08 | 株式会社ワンアンドオンリー | Antistatic agent, antistatic method, antistatic coating film, resin composition for forming antistatic layer and antistatic method |
US11747272B2 (en) | 2019-06-10 | 2023-09-05 | Analog Devices, Inc. | Gas detection using differential path length measurement |
CN112811829A (en) * | 2020-04-30 | 2021-05-18 | 法国圣戈班玻璃公司 | Antifogging glass, vehicle and method for manufacturing antifogging glass |
US11821836B2 (en) | 2020-07-13 | 2023-11-21 | Analog Devices, Inc. | Fully compensated optical gas sensing system and apparatus |
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 |
WO2022085105A1 (en) | 2020-10-21 | 2022-04-28 | 三菱電機株式会社 | Heat exchanger, and method for manufacturing heat exchanger |
CN113311444B (en) * | 2021-06-22 | 2022-08-02 | 山东高速建设管理集团有限公司 | Water film identification and treatment device and use 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 |
Family Cites Families (73)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5211321B2 (en) * | 1972-04-11 | 1977-03-30 | ||
JPS49124166A (en) * | 1973-02-07 | 1974-11-27 | ||
JPS5826052A (en) * | 1981-08-06 | 1983-02-16 | Asahi Glass Co Ltd | Glass body provided with alkali diffusion preventing silicon oxide film |
JPS59145808A (en) * | 1983-02-09 | 1984-08-21 | 財団法人鉄道総合技術研究所 | Cloudiness-proof road mirror |
JPS60151250A (en) * | 1984-01-12 | 1985-08-09 | Matsushita Electric Ind Co Ltd | Enamel film backed phosphor |
JPS60210641A (en) * | 1984-02-22 | 1985-10-23 | Unitika Ltd | Antifogging plastic molding |
JPS6183106A (en) * | 1984-10-01 | 1986-04-26 | Giken Kogyo Kk | Method of preventing contamination of surface of solid material to be brought into contact with water |
JPS6191042A (en) * | 1984-10-08 | 1986-05-09 | Toyota Motor Corp | Anti-fogging glass and its production |
JPS61133125A (en) * | 1984-11-29 | 1986-06-20 | Tsutomu Kagitani | Denitration process using ultraviolet ray |
JPS621750A (en) * | 1985-06-27 | 1987-01-07 | Toray Silicone Co Ltd | Room temperature curing organopolysiloxane composition |
JPH0647668B2 (en) * | 1985-12-16 | 1994-06-22 | 三菱化成ビニル株式会社 | Anti-fog composition |
JPH0615407B2 (en) * | 1986-05-07 | 1994-03-02 | 株式会社資生堂 | Optical semiconductor and its manufacturing method |
JPS635301A (en) * | 1986-06-25 | 1988-01-11 | Matsushita Electric Works Ltd | Reflecting mirror |
JPS6363726A (en) * | 1986-09-05 | 1988-03-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Composition for surface treatment |
JPS6381176A (en) * | 1986-09-24 | 1988-04-12 | Yoshio Ichikawa | Composition for coating |
JPS63100042A (en) * | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
JPS63246167A (en) * | 1987-04-02 | 1988-10-13 | チタン工業株式会社 | White deodorant and its production |
JPH01169866A (en) * | 1987-12-25 | 1989-07-05 | Hitachi Ltd | Discharge lamp |
JPH06102155B2 (en) * | 1988-02-29 | 1994-12-14 | 株式会社日立製作所 | Deodorant, deodorant manufacturing method, deodorizing method, deodorizing device, and refrigeration cycle device equipped with this deodorizing device |
JP2856754B2 (en) * | 1989-02-17 | 1999-02-10 | 株式会社東芝 | Ultraviolet-suppressed luminescence source, coating agent for ultraviolet-suppressed luminescence source, and method for producing ultraviolet-suppressed luminescence source |
JPH0787891B2 (en) * | 1989-04-14 | 1995-09-27 | 日本ゼオン株式会社 | Removing agent and method for removing oxidizable harmful substances |
JPH0330314U (en) * | 1989-07-31 | 1991-03-26 | ||
DE4023267A1 (en) * | 1990-07-21 | 1992-01-23 | Hoechst Ag | PLATE, FILM OR TAPE-BASED CARRIER MATERIAL FOR OFFSET PRINT PLATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
JP2618287B2 (en) * | 1990-11-06 | 1997-06-11 | 日本ゼオン株式会社 | Photoreactive harmful substance remover and harmful substance removal method using the same |
JPH04206201A (en) * | 1990-11-29 | 1992-07-28 | Honda Motor Co Ltd | Resin lens headlamp for vehicle |
JPH04225301A (en) * | 1990-12-27 | 1992-08-14 | Seiko Epson Corp | Optical product having clouding preventive performance |
JP3224865B2 (en) * | 1991-08-14 | 2001-11-05 | 東レ合成フィルム株式会社 | Agricultural coating film and method for producing the same |
JP2883761B2 (en) * | 1991-12-06 | 1999-04-19 | 工業技術院長 | Antibacterial growth inhibitor |
JP2913966B2 (en) * | 1991-12-10 | 1999-06-28 | 市光工業株式会社 | Vehicle lighting |
JPH05209072A (en) * | 1992-01-29 | 1993-08-20 | Japan Synthetic Rubber Co Ltd | Method for treating substrate surface |
JPH05232566A (en) * | 1992-02-24 | 1993-09-10 | Olympus Optical Co Ltd | Optical member |
JP3340149B2 (en) * | 1992-04-28 | 2002-11-05 | セントラル硝子株式会社 | Hydrophilic coating and method for forming the coating |
JPH06293519A (en) * | 1992-07-28 | 1994-10-21 | Ishihara Sangyo Kaisha Ltd | Production of titanium oxide particles and film |
JP3036247B2 (en) * | 1992-08-14 | 2000-04-24 | 東陶機器株式会社 | Lighting equipment |
JPH06190340A (en) * | 1992-09-11 | 1994-07-12 | Sekisui Jushi Co Ltd | Coated metal body |
JPH06278241A (en) * | 1992-09-22 | 1994-10-04 | Takenaka Komuten Co Ltd | Building material |
DE4235996A1 (en) * | 1992-10-24 | 1994-04-28 | Degussa | Titanium dioxide mixed oxide produced by flame hydrolysis, process for its preparation and use |
JP3316048B2 (en) * | 1992-11-06 | 2002-08-19 | 株式会社竹中工務店 | Building material and manufacturing method thereof |
JP3496229B2 (en) * | 1993-02-19 | 2004-02-09 | 日本電池株式会社 | Method for producing photocatalyst body |
JP2878922B2 (en) * | 1993-03-04 | 1999-04-05 | シャープ株式会社 | In-vehicle camera device |
JPH06266289A (en) * | 1993-03-10 | 1994-09-22 | Dainippon Ink & Chem Inc | Manufacture of durable display body |
JPH06315614A (en) * | 1993-03-11 | 1994-11-15 | Agency Of Ind Science & Technol | Method for removing contaminants and cleaning material |
JPH085660B2 (en) * | 1993-04-13 | 1996-01-24 | 工業技術院長 | Method for producing silica gel containing titanium oxide ultrafine particles dispersed therein |
AU676299B2 (en) * | 1993-06-28 | 1997-03-06 | Akira Fujishima | Photocatalyst composite and process for producing the same |
JP3115745B2 (en) * | 1993-07-12 | 2000-12-11 | 富士写真フイルム株式会社 | Photosensitive material |
JPH0751646A (en) * | 1993-08-12 | 1995-02-28 | Ishihara Sangyo Kaisha Ltd | Method for cleaning off contaminant on solid matter surface |
JP3279755B2 (en) * | 1993-08-24 | 2002-04-30 | 松下精工株式会社 | Photocatalyst and method for supporting photocatalyst |
JP3499585B2 (en) * | 1993-09-21 | 2004-02-23 | 日揮ユニバーサル株式会社 | Ethylene decomposition photocatalyst |
JP2517874B2 (en) * | 1993-09-30 | 1996-07-24 | 工業技術院長 | Method for producing titanium oxide thin film photocatalyst |
JP3334767B2 (en) * | 1993-10-20 | 2002-10-15 | 日新製鋼株式会社 | Building materials with moisture absorption and release functions |
JP2602022Y2 (en) * | 1993-11-25 | 1999-12-20 | 旭光学工業株式会社 | Dew condensation removal device in camera |
JPH07149520A (en) * | 1993-11-29 | 1995-06-13 | Hoya Corp | Coating composition |
JPH07164607A (en) * | 1993-12-13 | 1995-06-27 | Mitsubishi Chem Corp | Agricultural film |
JPH07168001A (en) * | 1993-12-15 | 1995-07-04 | Nikon Corp | Mildew-proofing optical equipment |
JP3488496B2 (en) * | 1993-12-21 | 2004-01-19 | 日揮ユニバーサル株式会社 | Poison-resistant deodorizing photocatalyst |
JP3391543B2 (en) * | 1993-12-27 | 2003-03-31 | 花王株式会社 | Hydrophilizing agent and hydrophilizing method |
JP2883000B2 (en) * | 1994-03-29 | 1999-04-19 | 三菱重工業株式会社 | Automobile sound insulation wall cleaning device |
JP3693363B2 (en) * | 1994-03-30 | 2005-09-07 | 松下エコシステムズ株式会社 | Supporting method for forming a photocatalyst layer |
JPH07331120A (en) * | 1994-06-10 | 1995-12-19 | Hitachi Ltd | Coating for removing nitrogen oxide and its use |
JP2832239B2 (en) * | 1994-06-21 | 1998-12-09 | 三井金属鉱業株式会社 | Lighting equipment with photocatalytic function |
JPH0810576A (en) * | 1994-07-05 | 1996-01-16 | Ebara Res Co Ltd | Removing method of harmful gas and device therefor |
JPH08119673A (en) * | 1994-10-21 | 1996-05-14 | Kansai Paint Co Ltd | Hydrophilization treatment of glass |
JPH08277147A (en) * | 1995-03-31 | 1996-10-22 | Nippon Muki Co Ltd | Plate glass |
JPH09129012A (en) * | 1995-03-31 | 1997-05-16 | Toshiba Lighting & Technol Corp | Photocatalyst, fluorescent lamp and luminaire |
JP3101537B2 (en) * | 1995-05-10 | 2000-10-23 | ワイケイケイ株式会社 | Antifouling building material and exterior building material unit |
JPH0929103A (en) * | 1995-05-17 | 1997-02-04 | Toshiba Lighting & Technol Corp | Photocatalytic body, photocatalytic device, light source and lightening equipment |
JPH08313705A (en) * | 1995-05-22 | 1996-11-29 | Seiko Epson Corp | Anti-clouding article and its production |
JP3127827B2 (en) * | 1995-06-14 | 2001-01-29 | 東陶機器株式会社 | Anti-fog seal |
EP1955768A1 (en) * | 1995-06-19 | 2008-08-13 | Nippon Soda Co., Ltd. | Photocatalyst-carrying structure and photocatalyst coating material |
JPH0990889A (en) * | 1995-09-27 | 1997-04-04 | Toshiba Lighting & Technol Corp | Sign body and externally illuminated sign device |
JPH09173783A (en) * | 1995-10-27 | 1997-07-08 | Matsushita Electric Ind Co Ltd | Sheet glass and resin plate and their production and method for removing contaminant |
JP4237830B2 (en) * | 1995-12-20 | 2009-03-11 | 日本曹達株式会社 | Photocatalyst-carrying lighting fixture |
JPH09231821A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
-
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- 1996-04-05 JP JP8083499A patent/JPH09231821A/en active Pending
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