【０００１】[0001]
【産業上の利用分野】本発明は、固体表面の有機物によ
る汚れを光触媒機能により分解して、固体表面の汚れを
浄化する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying dirt on a solid surface by decomposing dirt on a solid surface with an organic substance by a photocatalytic function.
【０００２】[0002]
【従来の技術】タバコの煙粒子やヤニ、排気ガス中に含
まれる炭化水素、ばい煙、種々の油脂分、花粉、虫など
の死骸などの有機物は、空気中に浮遊したり飛散したり
して自動車、電車、建造物、電気機器などの壁面、床、
天井、屋根、ドア、窓ガラスなどの固体表面に付着し、
固体表面を汚す。また、固体表面に動物の体の一部が接
触し動物の皮膚から分泌される脂が付着して汚れが生ず
る場合もある。さらに、前記の有機物や動物の皮膚から
分泌される脂が付着した固体表面は泥、土やほこりが付
着し易く、汚れがより一層ひどくなる。これらの固体表
面に生じた汚れは、機械や人力により水洗したりあるい
は拭き取ったりして取り除いているのが現状である。2. Description of the Related Art Organic matter such as cigarette smoke particles and tars, hydrocarbons contained in exhaust gas, soot, various oils and fats, pollen, carcasses such as insects are suspended or scattered in the air. Walls, floors of cars, trains, buildings, electrical equipment, etc.
Attaches to solid surfaces such as ceilings, roofs, doors and window glass,
Soil solid surfaces. In addition, a part of the animal's body comes into contact with the solid surface, and the fat secreted from the skin of the animal adheres to the solid surface to cause stains. Furthermore, mud, dirt, and dust are likely to be attached to the solid surface to which the above-mentioned organic matter and fat secreted from the skin of animals are attached, so that the dirt becomes more severe. Under the present circumstances, the stains generated on these solid surfaces are removed by washing or wiping with water by a machine or human power.
【０００３】[0003]
【発明が解決しようとする課題】水洗したりあるいは拭
き取ったりする前記の清掃作業は、汚れが生じるたびに
行う必要があり、また、乾燥作業が必要になったりする
ため、手間や時間がかかる面倒な作業である。The above-mentioned cleaning work such as washing with water or wiping off needs to be carried out every time dirt is generated, and also requires drying work, which is troublesome and time-consuming. It is a task.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記の清
掃作業に代わる、簡便、かつ、容易な方法を探索した結
果、空気中に存在している有機物や動物の皮膚から分泌
される脂により汚れを生ずる恐れのある固体表面に光半
導体粒子を担持し、次いで、該光半導体粒子に紫外線を
含有した光を照射して、該固体表面に付着した該有機物
や動物の皮膚から分泌される脂を分解し浄化することが
できることを見出し、本発明を完成した。Means for Solving the Problems As a result of searching for a simple and easy method as an alternative to the above-mentioned cleaning work, the present inventors have secreted from organic matter existing in the air and the skin of animals. An optical semiconductor particle is carried on a solid surface that may be contaminated by oil, and then the optical semiconductor particle is irradiated with light containing ultraviolet rays to be secreted from the organic matter or animal skin adhered to the solid surface. The present invention has been completed based on the finding that oils and fats can be decomposed and purified.
【０００５】すなわち、本発明は、空気中に存在してい
る有機物や動物の皮膚から分泌される脂が固体表面に付
着して生ずる固体表面の汚れを簡便、かつ容易に浄化
し、汚れの付着を防止する方法を提供する。That is, the present invention is capable of simply and easily purifying dirt on a solid surface caused by adhesion of organic substances existing in the air or fats secreted from the skin of animals to the solid surface, and to attach dirt. To provide a way to prevent
【０００６】本発明は、空気中に存在している有機物や
人、犬、猫などの動物の皮膚から分泌される脂の付着に
より汚れを生ずる恐れのある固体表面に光半導体粒子を
担持し、次いで、該光半導体粒子に紫外線を含有した光
を照射して、該固体表面に付着した該有機物や動物の皮
膚から分泌される脂を分解して、固体表面を浄化する。
本発明において、固体表面に付着して汚れを生ずる、空
気中に存在している有機物としては、たとえば、タバコ
の煙粒子やヤニ、排気ガス中に含まれる炭化水素、ばい
煙、種々の油脂分、花粉、虫などの死骸などの種々の炭
素化合物が挙げられる。また、前記の固体は、金属、合
金、セラミックス、ガラス、プラッスチックス、ゴム、
木、紙などの材質によって作製されているものであり、
固体の大きさや形には特に制限されない。しかも、塗装
した固体でも用いることができる。具体的には、自動
車、電車などの交通機関、テーブル、キャビネットなど
の家具、テレビ、電子レンジ、ワードプロセッサー、コ
ンピューターなどの電気機器、建造物などの壁面、床、
天井、屋根、ドア、窓ガラスやブラウン管、受像管、画
面などのディスプレイさらにはカメラレンズ用の光学フ
ィルターなどが挙げられる。本発明は、空気中に存在し
ている有機物や動物の皮膚から分泌される脂の付着によ
る汚れが目立つガラス、特に交通機関のフロントガラス
を含めた窓ガラスや建造物の窓ガラスへの適用が好まし
い。また、本発明は、静電気により空気中に存在してい
る有機物や動物の皮膚から分泌される脂が強固に付着し
易い電気機器のディスプレイへの適用が好ましい。According to the present invention, optical semiconductor particles are carried on a solid surface which may be contaminated by adhesion of organic substances existing in the air and fats secreted from the skin of animals such as humans, dogs and cats, Next, the photo-semiconductor particles are irradiated with light containing ultraviolet rays to decompose the organic substances adhering to the solid surface and the fats secreted from the skin of animals to purify the solid surface.
In the present invention, as an organic substance existing in the air, which adheres to a solid surface to generate dirt, for example, tobacco smoke particles and tars, hydrocarbons contained in exhaust gas, soot, various oils and fats, Examples include various carbon compounds such as pollen and carcasses of insects. Further, the solid is a metal, alloy, ceramics, glass, plastics, rubber,
It is made of wood, paper, etc.
The size or shape of the solid is not particularly limited. Moreover, it is possible to use a painted solid. Specifically, transportation such as automobiles and trains, furniture such as tables and cabinets, televisions, microwave ovens, word processors, electrical equipment such as computers, walls such as buildings, floors,
Examples include ceilings, roofs, doors, window glass and cathode ray tubes, picture tubes, displays such as screens, and optical filters for camera lenses. INDUSTRIAL APPLICABILITY The present invention is applicable to glass in which stains due to the adhesion of oils secreted from organic matter existing in the air and the skin of animals are conspicuous, particularly to window glasses including windshields for transportation and window glasses for buildings. preferable. Further, the present invention is preferably applied to a display of an electric device to which organic matter existing in the air due to static electricity or fat secreted from the skin of an animal is easily adhered firmly.
【０００７】これらの固体の表面に担持する光半導体粒
子とは、そのバンドギャップ以上のエネルギーを持つ波
長の光を照射すると光励起により伝導帯に電子を、価電
子帯に正孔を生じる物質をいい、この光励起により生じ
た電子の持つ強い還元力や正孔の持つ強い酸化力は、従
来から悪臭ガスの分解、水の浄化、水の分解などに利用
されている。光半導体粒子としては、たとえば、酸化チ
タン、酸化亜鉛、酸化タングステン、酸化鉄、チタン酸
ストロンチウムなどの公知の金属化合物半導体を、単一
または２種以上を組み合わせて用いることができる。特
に、高い光触媒機能を有し、化学的に安定であり、か
つ、無害である酸化チタンが好ましい。本発明において
は、光半導体粒子を固体表面に担持させて、固体表面に
光半導体粒子の層を形成させることもできる。光半導体
粒子の層は透明性を有するものが好ましく、可視領域の
５５０ｎｍの波長の光を基準として、光拡散透過率が５
０％以上、特に７０％以上であるものが好ましい。The photo-semiconductor particles carried on the surface of these solids are substances that generate electrons in the conduction band and holes in the valence band by photoexcitation when irradiated with light having a wavelength having an energy larger than the band gap. The strong reducing power of electrons and the strong oxidizing power of holes generated by this photoexcitation have been conventionally used for decomposition of malodorous gas, water purification, water decomposition, and the like. As the optical semiconductor particles, for example, known metal compound semiconductors such as titanium oxide, zinc oxide, tungsten oxide, iron oxide, and strontium titanate can be used alone or in combination of two or more kinds. In particular, titanium oxide, which has a high photocatalytic function, is chemically stable, and is harmless, is preferable. In the present invention, the photosemiconductor particles can be supported on the solid surface to form a layer of the photosemiconductor particles on the solid surface. The layer of optical semiconductor particles preferably has transparency, and has a light diffusion transmittance of 5 based on light having a wavelength of 550 nm in the visible region.
It is preferably 0% or more, and particularly preferably 70% or more.
【０００８】前記の光半導体粒子を固体表面に担持する
には、３００〜６００℃程度の温度に加熱した固体表面
に、熱分解して光半導体粒子となる金属塩を溶解させた
アルコール溶液、または有機金属化合物を溶解させた有
機溶媒系の溶液をスプレーする方法、揮発性の金属ハロ
ゲン化物や有機金属化合物などを高温で熱分解するＣＶ
Ｄ法、金属のアルコキシドやアセチルアセトナートを有
機溶媒に溶解した液に固体を浸漬し、引上げ、次いで、
乾燥し、焼成するゾル−ゲル法、真空下、金属または金
属酸化物を抵抗加熱あるいは電子ビーム加熱により気化
させ、加熱した固体に光半導体粒子を沈着させる真空蒸
着法、減圧下、プラズマを利用したスパッタ法などの方
法が用いられる。In order to support the above-mentioned photo-semiconductor particles on a solid surface, an alcohol solution in which a metal salt which is thermally decomposed to become photo-semiconductor particles is dissolved on the solid surface heated to a temperature of about 300 to 600 ° C., or A method of spraying an organic solvent-based solution in which an organometallic compound is dissolved, and a CV for thermally decomposing volatile metal halides and organometallic compounds at high temperatures
Method D, immersing the solid in a liquid prepared by dissolving a metal alkoxide or acetylacetonate in an organic solvent, pulling it up, and then
Sol-gel method of drying and baking, vacuum deposition method of vaporizing metal or metal oxide by resistance heating or electron beam heating under vacuum, and depositing optical semiconductor particles on the heated solid, under reduced pressure, using plasma A method such as a sputtering method is used.
【０００９】また、本発明においては、光半導体粒子を
公知の方法によって得、次いで、得られた光半導体粒子
を下記の方法によっても固体表面に担持することができ
る。光半導体粒子を、たとえば、水、アルコール、トル
エンなどの溶媒に懸濁させる。必要に応じて分散剤や結
着剤を加えても良い。得られた懸濁液を、たとえば、含
浸法、ディップコーティング法、スピナーコーティング
法、ローラーコーティング法、ワイヤーバーコーティン
グ法、リバースロールコーティング法などの塗布方法や
スプレーコーティング法などの吹き付け方法などを用い
て、固体表面の塗布し、あるいは吹き付けし、次いで、
乾燥して光半導体粒子を担持させる。付着した光半導体
粒子は必要に応じて焼成しても良く、この焼成により、
光半導体粒子を固体表面に強固に接着させることができ
る。前記の焼成は１００℃以上、好ましくは２００〜８
００℃、特に好ましくは３００〜８００℃の温度に焼成
するのが適当である。前記の光半導体粒子の光触媒機能
を向上させるために、該光半導体粒子の表面に白金、
金、銀、銅、パラジウム、ロジウム、ルテニウムなどの
金属、酸化ルテニウム、酸化ニッケルなどの金属酸化物
を被覆してもよい。Further, in the present invention, the photosemiconductor particles can be obtained by a known method, and then the obtained photosemiconductor particles can be supported on the solid surface by the following method. The optical semiconductor particles are suspended in a solvent such as water, alcohol or toluene. You may add a dispersing agent and a binder as needed. The obtained suspension is applied, for example, by a coating method such as an impregnation method, a dip coating method, a spinner coating method, a roller coating method, a wire bar coating method, a reverse roll coating method or a spraying method such as a spray coating method. , Coating or spraying on a solid surface, then
It is dried to support the optical semiconductor particles. The adhered optical semiconductor particles may be fired if necessary, and by this firing,
The optical semiconductor particles can be firmly adhered to the solid surface. The firing is performed at 100 ° C. or higher, preferably 200 to 8
It is suitable to calcine at a temperature of 00 ° C, particularly preferably 300 to 800 ° C. In order to improve the photocatalytic function of the photosemiconductor particles, platinum is formed on the surface of the photosemiconductor particles,
A metal such as gold, silver, copper, palladium, rhodium, or ruthenium, or a metal oxide such as ruthenium oxide or nickel oxide may be coated.
【００１０】５５０ｎｍの波長の光拡散透過率が５０％
以上、特に７０％以上である光半導体粒子の層は、前記
のスプレー法、ＣＶＤ法、ゾル−ゲル法、真空蒸着法、
スパッタ法などの反応条件を適宜設定したり、あるい
は、前記の光半導体粒子を塗布し、あるいは吹き付けす
る場合には、用いる光半導体粒子の粒子径を適宜選択す
ることにより得られる。Light diffusion transmittance of 50% at a wavelength of 550 nm
Above, especially 70% or more of the layer of optical semiconductor particles, the above-mentioned spray method, CVD method, sol-gel method, vacuum deposition method,
When the reaction conditions such as the sputtering method are appropriately set, or when the above-mentioned optical semiconductor particles are applied or sprayed, they can be obtained by appropriately selecting the particle diameter of the optical semiconductor particles to be used.
【００１１】次に、固体表面に担持した光半導体粒子
に、その光半導体粒子のバンドギャップ以上のエネルギ
ーを持つ波長の光を照射する。前記の光としては、紫外
線を含有した光が挙げられ、たとえば、太陽光や蛍光
灯、ブラックライト、ハロゲンランプ、キセノンフラッ
シュランプ、水銀灯などの光を用いることができる。特
に、３００〜４００ｎｍの近紫外線を含有した光が好ま
しい。光の照射量や照射時間などは処理する有機物や動
物の皮膚から分泌される脂の量などによって適宜設定で
きる。このようにして、空気中に存在していた有機物や
動物の皮膚から分泌される脂を分解することができ、固
体表面に付着した汚れを浄化し、汚れの付着を防止する
ことができる。Next, the photo-semiconductor particles supported on the solid surface are irradiated with light having a wavelength having an energy larger than the band gap of the photo-semiconductor particles. Examples of the above-mentioned light include light containing ultraviolet rays, and for example, sunlight, fluorescent lamps, black lights, halogen lamps, xenon flash lamps, mercury lamps and the like can be used. Particularly, light containing near-ultraviolet rays of 300 to 400 nm is preferable. The irradiation amount and irradiation time of light can be appropriately set according to the organic matter to be treated and the amount of fat secreted from the skin of the animal. In this way, the organic substances existing in the air and the fats secreted from the skin of animals can be decomposed, the dirt adhering to the solid surface can be purified, and the adhesion of dirt can be prevented.
【００１２】[0012]
実施例１ ８０ｇ／ｌの硫酸チタニル溶液１リットルを８５℃に加
熱し、この温度で３時間保持し、硫酸チタニルを加水分
解して酸化チタン粒子を得た。このようにして得られた
酸化チタン粒子を濾過し、洗浄した後、水に分散させ
て、ＴｉＯ2基準で２００ｇ／ｌの懸濁液とした。次い
で、この懸濁液に硝酸水溶液を添加し、該懸濁液のｐＨ
を１．０にした後、オートクレーブに入れ、１８０℃の
温度で１３時間、飽和水蒸気圧下で水熱処理を行った。
次に、水熱処理後の酸化チタン粒子の懸濁液に、該酸化
チタン粒子のＴｉＯ2基準に対して、ポリエチレングリ
コール（平均分子量２００００）を４０重量％添加し、
６０℃の温度に加熱した後、この懸濁液をドクターブレ
ード（間隙６０μｍ）を用いてガラス板（縦５ｃｍ、横
５ｃｍ）に塗布し、自然乾燥した後、４５０℃の温度で
３時間焼成して、酸化チタン粒子の層をガラス板に担持
した。Example 1 1 liter of a 80 g / l titanyl sulfate solution was heated to 85 ° C. and kept at this temperature for 3 hours to hydrolyze the titanyl sulfate to obtain titanium oxide particles. The titanium oxide particles thus obtained were filtered, washed, and then dispersed in water to obtain a suspension of 200 g / l based on TiO2 . Then, a nitric acid aqueous solution is added to this suspension to adjust the pH of the suspension.
Was set to 1.0 and then put in an autoclave and subjected to hydrothermal treatment at a temperature of 180 ° C. for 13 hours under saturated steam pressure.
Next, to the suspension of titanium oxide particles after the hydrothermal treatment, 40% by weight of polyethylene glycol (average molecular weight 20000) was added with respect to the TiO2 standard of the titanium oxide particles,
After heating to a temperature of 60 ° C., this suspension was applied to a glass plate (length 5 cm, width 5 cm) using a doctor blade (gap 60 μm), naturally dried, and then calcined at a temperature of 450 ° C. for 3 hours. Then, the layer of titanium oxide particles was supported on the glass plate.
【００１３】前記のガラス板に担持した酸化チタン粒子
はアナタース型結晶を有し、その酸化チタン粒子の層の
膜厚は７．５μｍであった。また、５５０ｎｍの波長で
の光拡散透過率は、使用したガラス板が９０％であった
のに対し、酸化チタン粒子の層を担持したガラス板では
８０％であった。The titanium oxide particles supported on the glass plate had anatase type crystals, and the layer thickness of the titanium oxide particles was 7.5 μm. The light diffusion transmittance at a wavelength of 550 nm was 90% for the glass plate used, whereas it was 80% for the glass plate carrying the layer of titanium oxide particles.
【００１４】次に、前記の酸化チタン粒子を担持したガ
ラス板の表面の浄化を下記のようにして調べた。有機物
は、食用油の主成分であり、食用油使用時に空気中に飛
散して、壁などを茶色に着色して汚すリノール酸トリグ
リセリドを用いた。このリノール酸トリグリセリドをガ
ラス板１ｃｍ2当たり０．１ｍｇ塗布した後、紫外光強
度が７ｍＷ／ｃｍ2になるようにブラックライトを照射
した。ブラックライト照射前と後のガラス板の重量減少
から、リノール酸トリグリセリドの分解率を算出した。
この結果、ブラックライトを２時間照射した時点での分
解率は９０％であり、ブラックライトを３時間照射した
時点での分解率は１００％であった。Next, the purification of the surface of the glass plate carrying the above-mentioned titanium oxide particles was examined as follows. The organic substance is the main component of edible oil, and linoleic acid triglyceride which scatters in the air when the edible oil is used and stains the walls and the like brown is used. 0.1 mg of this linoleic acid triglyceride was applied per 1 cm2 of glass plate, and then black light was irradiated so that the ultraviolet light intensity became 7 mW / cm2 . The decomposition rate of linoleic acid triglyceride was calculated from the weight loss of the glass plate before and after black light irradiation.
As a result, the decomposition rate after irradiation with black light for 2 hours was 90%, and the decomposition rate after irradiation with black light for 3 hours was 100%.
【００１５】なお、酸化チタン粒子を担持していないガ
ラス板を用いること以外は実施例と同様にしてリノール
酸トリグリセリドの分解試験を行った結果、ブラックラ
イトを３時間照射した時点での分解率は０％であった。A decomposition test of linoleic acid triglyceride was carried out in the same manner as in Example except that a glass plate not supporting titanium oxide particles was used. As a result, the decomposition rate at the time of irradiation with black light for 3 hours was It was 0%.
【００１６】さらに、酸化チタン粒子の層を担持した前
記のガラス板を手で触り、該ガラス板の表面に人の手か
ら分泌した脂を１．５ｍｇ付着させた後、紫外光強度が
７ｍＷ／ｃｍ2になるようにブラックライトを照射し
た。ブラックライト照射前と後のガラス板の重量減少か
ら、人の手から分泌される脂の分解率を算出した。この
結果、ブラックライトを２時間照射した時点での分解率
は１００％であった。Further, after touching the glass plate carrying a layer of titanium oxide particles with a hand and depositing 1.5 mg of human-secreted fat on the surface of the glass plate, an ultraviolet light intensity of 7 mW / It was irradiated with black light so as to have a cm2 . The decomposition rate of fat secreted from human hands was calculated from the weight loss of the glass plate before and after black light irradiation. As a result, the decomposition rate when irradiated with black light for 2 hours was 100%.
【００１７】[0017]
【発明の効果】本発明は、空気中に存在している有機物
や動物の皮膚から分泌される脂の付着により汚れを生ず
る恐れのある固体表面に光半導体粒子を担持し、次い
で、該光半導体粒子に紫外線を含有した光を照射し、該
固体表面に付着した該有機物や動物の皮膚から分泌され
る脂を分解して固体表面の汚れを浄化し、汚れの付着を
防止する方法であって、たとえば、タバコの煙粒子やヤ
ニ、排気ガス中に含まれる炭化水素、ばい煙、種々の油
脂分、花粉、虫などの死骸などの空気中に存在している
有機物や動物の皮膚から分泌される脂などによって汚れ
た固体表面を簡便、かつ、容易に浄化することができる
ので、工業用途ばかりでなく一般家庭用の浄化方法とし
て極めて有用な方法である。特に、本発明は、空気中に
存在している有機物や動物の皮膚から分泌される脂の付
着による汚れが甚だしい交通機関または建造物の窓ガラ
スや電気機器のディスプレイの表面の浄化に最適であ
る。INDUSTRIAL APPLICABILITY According to the present invention, optical semiconductor particles are carried on a solid surface which may be contaminated by adhesion of organic substances existing in the air or fats secreted from the skin of animals, and then the optical semiconductor is carried out. A method of irradiating particles with light containing ultraviolet rays to decompose the organic substances adhering to the solid surface and the oil secreted from the skin of animals to purify the dirt on the solid surface and prevent the adhesion of dirt. , For example, cigarette smoke particles and tars, hydrocarbons contained in exhaust gas, soot, various oils and fats, pollen, carcasses of insects, etc. Since a solid surface soiled with oil or the like can be easily and easily purified, it is a very useful method not only for industrial use but also for general household use. In particular, the present invention is most suitable for cleaning the surface of a display of a window glass or an electric device of a transportation system or a building which is extremely contaminated by adhesion of organic substances existing in the air or secretion of fats secreted from animal skin. .
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5222169AJPH0751646A (en) | 1993-08-12 | 1993-08-12 | Method for cleaning off contaminant on solid matter surface |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5222169AJPH0751646A (en) | 1993-08-12 | 1993-08-12 | Method for cleaning off contaminant on solid matter surface |
| Publication Number | Publication Date |
|---|---|
| JPH0751646Atrue JPH0751646A (en) | 1995-02-28 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5222169APendingJPH0751646A (en) | 1993-08-12 | 1993-08-12 | Method for cleaning off contaminant on solid matter surface |
| Country | Link |
|---|---|
| JP (1) | JPH0751646A (en) |
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| JPH08196903A (en)* | 1995-01-24 | 1996-08-06 | Agency Of Ind Science & Technol | Porous photocatalyst and manufacture thereof |
| JPH08267646A (en)* | 1995-03-30 | 1996-10-15 | Toto Ltd | Stainproof member |
| JPH08277147A (en)* | 1995-03-31 | 1996-10-22 | Nippon Muki Co Ltd | Plate glass |
| JPH0971437A (en)* | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Window glass |
| JPH0972761A (en)* | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Cover glass for instrument |
| JPH09129012A (en)* | 1995-03-31 | 1997-05-16 | Toshiba Lighting & Technol Corp | Photocatalysts, fluorescent lamps and lighting fixtures |
| JPH09168722A (en)* | 1995-10-17 | 1997-06-30 | Ebara Corp | Method and apparatus for preventing pollution of local space |
| JPH09173783A (en)* | 1995-10-27 | 1997-07-08 | Matsushita Electric Ind Co Ltd | Flat glass, resin plate, manufacturing method thereof and pollutant removal method |
| JPH09215568A (en)* | 1996-02-14 | 1997-08-19 | Toto Ltd | Plastic mirror |
| JPH09226054A (en)* | 1995-06-14 | 1997-09-02 | Toto Ltd | Antifouling crystallized glass |
| JPH09228602A (en)* | 1995-12-22 | 1997-09-02 | Toto Ltd | Architectural material for external wall and leaning method of the building material |
| JPH09232096A (en)* | 1995-12-22 | 1997-09-05 | Toto Ltd | Electrification preventing method, and electrification preventive composite material |
| JPH09231821A (en)* | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
| JPH09230493A (en)* | 1995-12-22 | 1997-09-05 | Toto Ltd | Camera |
| JPH09251804A (en)* | 1996-03-14 | 1997-09-22 | Toshiba Lighting & Technol Corp | Lighting equipment |
| JPH1031434A (en)* | 1996-02-29 | 1998-02-03 | Toshiba Lighting & Technol Corp | Light emitting diode, display unit and display device |
| JPH10130037A (en)* | 1996-10-24 | 1998-05-19 | Toto Ltd | Vehicle window glass having stain proofing property in combination with water drop-sticking preventing property |
| JPH117249A (en)* | 1997-06-18 | 1999-01-12 | Sony Corp | Display device and filter for display device |
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| US6090489A (en)* | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
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| US6387844B1 (en) | 1994-10-31 | 2002-05-14 | Akira Fujishima | Titanium dioxide photocatalyst |
| WO2002090008A1 (en)* | 2001-05-01 | 2002-11-14 | Center For Advanced Science And Technology Incubation, Ltd. | Structure cleaning method and anticorrosion method, and structure using them |
| US6524664B1 (en) | 1996-03-21 | 2003-02-25 | Toto Ltd. | Photocatalytically hydrophilifying and hydrophobifying material |
| US6830785B1 (en) | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| JP2005213142A (en)* | 1995-09-15 | 2005-08-11 | Saint-Gobain Glass France | Substrate provided with photocatalyst coating |
| JP2012168044A (en)* | 2011-02-15 | 2012-09-06 | Yokogawa Electric Corp | Turbidimeter/colorimeter |
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|---|---|---|---|---|
| JPS60187322A (en)* | 1984-03-06 | 1985-09-24 | Toyota Central Res & Dev Lab Inc | How to purify waste |
| JPH04174679A (en)* | 1990-11-06 | 1992-06-22 | Nippon Zeon Co Ltd | Optically reactive harmful substance removing agent and harmful substance removal method using same |
| JPH06278241A (en)* | 1992-09-22 | 1994-10-04 | Takenaka Komuten Co Ltd | Building material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60187322A (en)* | 1984-03-06 | 1985-09-24 | Toyota Central Res & Dev Lab Inc | How to purify waste |
| JPH04174679A (en)* | 1990-11-06 | 1992-06-22 | Nippon Zeon Co Ltd | Optically reactive harmful substance removing agent and harmful substance removal method using same |
| JPH06278241A (en)* | 1992-09-22 | 1994-10-04 | Takenaka Komuten Co Ltd | Building material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07163887A (en)* | 1993-12-15 | 1995-06-27 | Nikon Corp | Antifungal method of object and object protected by the method |
| US6939611B2 (en) | 1994-10-31 | 2005-09-06 | Kanagawa Academy Of Science And Technology | Window glass employing titanium dioxide photocatalyst |
| JP3258023B2 (en)* | 1994-10-31 | 2002-02-18 | 財団法人神奈川科学技術アカデミー | Titanium oxide photocatalyst structure and method for producing the same |
| US6387844B1 (en) | 1994-10-31 | 2002-05-14 | Akira Fujishima | Titanium dioxide photocatalyst |
| US7327074B2 (en) | 1994-10-31 | 2008-02-05 | Kanagawa Academy Of Science And Technology | Illuminating devices employing titanium dioxide photocatalysts |
| US7157840B2 (en) | 1994-10-31 | 2007-01-02 | Kanagawa Academy Of Science And Technology | Illuminating devices employing titanium dioxide photocatalysts |
| JPH08196903A (en)* | 1995-01-24 | 1996-08-06 | Agency Of Ind Science & Technol | Porous photocatalyst and manufacture thereof |
| US6013372A (en)* | 1995-03-20 | 2000-01-11 | Toto, Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with superhydrophilic photocatalytic surface, and method of making thereof |
| US6830785B1 (en) | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| JPH08267646A (en)* | 1995-03-30 | 1996-10-15 | Toto Ltd | Stainproof member |
| 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 | Photocatalysts, fluorescent lamps and lighting fixtures |
| JPH09226054A (en)* | 1995-06-14 | 1997-09-02 | Toto Ltd | Antifouling crystallized glass |
| JPH0972761A (en)* | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Cover glass for instrument |
| JPH0971437A (en)* | 1995-09-05 | 1997-03-18 | Nippon Soda Co Ltd | Window glass |
| JP2005213142A (en)* | 1995-09-15 | 2005-08-11 | Saint-Gobain Glass France | Substrate provided with photocatalyst coating |
| JPH09168722A (en)* | 1995-10-17 | 1997-06-30 | Ebara Corp | Method and apparatus for preventing pollution of local space |
| JPH09173783A (en)* | 1995-10-27 | 1997-07-08 | Matsushita Electric Ind Co Ltd | Flat glass, resin plate, manufacturing method thereof and pollutant removal method |
| JPH09232096A (en)* | 1995-12-22 | 1997-09-05 | Toto Ltd | Electrification preventing method, and electrification preventive composite material |
| US6090489A (en)* | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
| JPH09231821A (en)* | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
| JPH09230493A (en)* | 1995-12-22 | 1997-09-05 | Toto Ltd | Camera |
| JPH09228602A (en)* | 1995-12-22 | 1997-09-02 | Toto Ltd | Architectural material for external wall and leaning method of the building material |
| JPH09215568A (en)* | 1996-02-14 | 1997-08-19 | Toto Ltd | Plastic mirror |
| JPH1031434A (en)* | 1996-02-29 | 1998-02-03 | Toshiba Lighting & Technol Corp | Light emitting diode, display unit and display device |
| JPH09251804A (en)* | 1996-03-14 | 1997-09-22 | Toshiba Lighting & Technol Corp | Lighting equipment |
| US6524664B1 (en) | 1996-03-21 | 2003-02-25 | Toto Ltd. | Photocatalytically hydrophilifying and hydrophobifying material |
| US6165256A (en)* | 1996-07-19 | 2000-12-26 | Toto Ltd. | Photocatalytically hydrophilifiable coating composition |
| JPH10130037A (en)* | 1996-10-24 | 1998-05-19 | Toto Ltd | Vehicle window glass having stain proofing property in combination with water drop-sticking preventing property |
| US6337129B1 (en) | 1997-06-02 | 2002-01-08 | Toto Ltd. | Antifouling member and antifouling coating composition |
| JPH117249A (en)* | 1997-06-18 | 1999-01-12 | Sony Corp | Display device and filter for display device |
| JP2001121643A (en)* | 2000-08-17 | 2001-05-08 | Toto Ltd | Antistaining member |
| WO2002090008A1 (en)* | 2001-05-01 | 2002-11-14 | Center For Advanced Science And Technology Incubation, Ltd. | Structure cleaning method and anticorrosion method, and structure using them |
| JP2012168044A (en)* | 2011-02-15 | 2012-09-06 | Yokogawa Electric Corp | Turbidimeter/colorimeter |
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