JPH09228545A - Glass block and its cleaning method - Google Patents

Glass block and its cleaning method

Info

Publication number
JPH09228545A
JPH09228545A JP8282810A JP28281096A JPH09228545A JP H09228545 A JPH09228545 A JP H09228545A JP 8282810 A JP8282810 A JP 8282810A JP 28281096 A JP28281096 A JP 28281096A JP H09228545 A JPH09228545 A JP H09228545A
Authority
JP
Japan
Prior art keywords
glass block
layer
surface layer
photocatalyst
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP8282810A
Other languages
Japanese (ja)
Inventor
Makoto Hayakawa
信 早川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toto Ltd
Original Assignee
Toto Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=18438979&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPH09228545(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Toto Ltd filed Critical Toto Ltd
Priority to JP8282810A priority Critical patent/JPH09228545A/en
Publication of JPH09228545A publication Critical patent/JPH09228545A/en
Pending legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
    • F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
    • F24F8/22—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Finishing Walls (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Prevention Of Fouling (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Building Environments (AREA)
  • Refuge Islands, Traffic Blockers, Or Guard Fence (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Greenhouses (AREA)
  • Bridges Or Land Bridges (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Detergent Compositions (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Panels For Use In Building Construction (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

PROBLEM TO BE SOLVED: To self-clean a glass block by forming a surface layer containing a photocatalytic particle on a glass block base, and setting water wet angle to a specified value. SOLUTION: A surface layer containing photocatalyst particles is formed on the surface of a glass block base, the surface layer is optically excited and made highly hydrophilic and the hydrophilic property of the surface is enhanced more than liphophilic property. The surface of the surface layer is set so as to show a hydrophilic property of 10 deg. or less, in terms of contact angle with water, preferably 5 deg. or less according to the optical excitation of the photocatalyst. Silica, solid acid, or silicon is contained in the surface layer as occasion demands to bring the water wet angle close to 0 deg., and the hydrophilic keeping property when held in a dark place is improved. Further, a protecting layer capable of being made hydrophilic is provided on the surface of the surface layer. Thus, when the glass surface is exposed to rain, an adhered sediment or contaminant can be washed away by raindrops.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、ガラスブロック、
及びその清浄化方法に関する。TECHNICAL FIELD The present invention relates to a glass block,
And its cleaning method.

【０００２】[0002]

【従来の技術】ガラスブロック建材は、水拭き程度で
は、手垢等による油脂汚れが容易には充分に洗浄されな
い。また、高層ビルに利用した場合には、清掃しないと
汚れやすく、その清掃は高所作業であり、重労働である
と同時に危険を伴う。2. Description of the Related Art A glass block building material cannot be easily washed sufficiently with oil and grease stains due to hand stains, etc., just by wiping it with water. Further, when it is used for a high-rise building, it is easy to get dirty unless it is cleaned, and the cleaning is a work at a high place, which is a heavy work and is accompanied by danger.

【０００３】[0003]

【発明の解決すべき課題】本発明の目的は、降雨により
自己清浄化（セルフクリーニング）される表面を有する
ガラスブロック、及びガラスブロックの清浄化方法を提
供することにある。本発明の他の目的は、散水や水濯ぎ
程度で簡単に清掃可能な表面を有するガラスブロック、
及びその清浄化方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a glass block having a surface that is self-cleaning (self-cleaning) by rainfall, and a method of cleaning the glass block. Another object of the present invention is a glass block having a surface that can be easily cleaned by watering or rinsing.
And a method for cleaning the same.

【０００４】[0004]

【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 the photocatalyst is irradiated with light having an energy larger than the energy gap between the valence band upper end and the conduction band lower end of the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. The action of either or both of them probably imparts polarity to the surface and collects polar components such as water and hydroxyl groups. 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.

【０００５】本発明では、ガラスブロック基材の表面
に、光触媒粒子を含有する表面層を備えたセルフクリー
ニング性ガラスブロックを提供する。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するので、ガラスブロックの
表面が降雨にさらされた時に付着堆積物及び／又は汚染
物が雨滴により洗い流されるのが可能となる。The present invention provides a self-cleaning glass block having a surface layer containing photocatalyst particles on the surface of a glass block substrate. By providing a surface layer containing a photocatalyst, in response to photoexcitation of the photocatalyst,
The surface of the surface layer exhibits hydrophilicity, which allows the deposition deposits and / or contaminants to be washed away by raindrops when the surface of the glass block is exposed to rainfall.

【０００６】本発明では、ガラスブロック基材の表面
に、光触媒粒子を含有する表面層を備えた易清掃性ガラ
スブロックを提供する。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
は親水性を呈するので、ガラスブロックの表面を水で洗
浄するのが容易になる。The present invention provides an easily-cleanable glass block having a surface layer containing photocatalyst particles on the surface of a glass block substrate. By providing the surface layer containing the photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, so that the surface of the glass block can be easily washed with water.

【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。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 ability of silica to 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 silicone, by photoexcitation of the photocatalyst, at least a part of the organic group bonded to the silicon atom in the silicone is replaced with a hydroxyl group, and a physically adsorbed water layer is formed on the organic group, so that the surface is It exhibits a high degree of hydrophilicity close to a water wetting angle of 0 °, and improves the hydrophilicity maintaining ability 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。本発明におけるガラスブロックの表面に
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、ガラスブロックの表面は、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、表面の親
水性が親油性より強まる。それにより、ガラスブロック
の表面が降雨にさらされた時に付着堆積物及び／又は汚
染物が雨滴により洗い流されるようになる。さらに、ガ
ラスブロックの表面を水で洗浄するのが容易になる。BEST MODE FOR CARRYING OUT THE INVENTION Next, a specific structure of the present invention will be described. On the surface of the glass block in the present invention, as shown in FIG. 1 or 2, a layer containing a photocatalyst is formed on the surface of the base material. By taking such a surface structure, the surface of the glass block is highly hydrophilized in response to photoexcitation of the photocatalyst. Thereby, the hydrophilicity of the surface becomes stronger than the lipophilicity. This causes the deposits and / or contaminants to be washed away by raindrops when the surface of the glass block is exposed to rainfall. Further, it becomes easy to wash the surface of the glass block with water.

【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 is composed of only the 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 shows hydrophilicity in a state where the pollutant in the environment is not adsorbed, the pollutant is rejected by a photoexcitation effect of a photocatalyst mixed into the surface layer other than the inorganic oxide,
By forming the adsorbed water layer, a uniform water film can be formed.

【００１２】本発明におけるガラスブロックは、例え
ば、無蓋の箱型のガラスを１対準備し、 対向させて、
４００℃以上の温度で接触部を融着して作製する。The glass block in the present invention is prepared, for example, by preparing a pair of open-ended box-shaped glass and facing them,
It is manufactured by fusing the contact portion at a temperature of 400 ° C. or higher.

【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、常夜灯、室内照明、蛍光灯、メタルハライドラン
プ、ブラックライトランプ、キセノンランプ、水銀灯な
ど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、０．０１ｍ
Ｗ／ｃｍ２以上だと好ましく、０．１ｍＷ／ｃｍ２以上
だとより好ましい。A photocatalyst is a photocatalyst of electrons in the valence band when irradiated with light (excitation light) having an energy (that is, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. A substance that is excited (photoexcited) to generate conduction electrons and holes. For example, anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, and oxide oxide. Diiron, strontium titanate and the like can be preferably used. Here, as the light source used for the photoexcitation of the photocatalyst, sunlight; street lights, night lights, indoor lighting, fluorescent lights, metal halide lamps, black light lamps, xenon lamps, mercury lamps and the like can be preferably used. In order for the substrate surface to be highly hydrophilic by photoexcitation of the photocatalyst, the illuminance of the excitation light must be
It may be 0.001 mW / cm 2 or more, but 0.01 m
It is preferably at least W / cm 2, more preferably at least 0.1 mW / cm 2 .

【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 film thickness of the surface layer containing the photocatalyst is 0.4.
It is preferable that the thickness is less than or equal to μm. Then, white turbidity 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 and 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.

【００１６】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が添加されていて
もよい。この場合も光触媒以外に固体酸を添加した場合
に、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 may be added to the surface layer. Also in this case, when a solid acid is added in addition to the photocatalyst, the acidity of the solid acid is improved, so that the hydrophilicity retention property is also improved, the water film of the attached water is further promoted, and the photocatalyst is excited for a long period of time. Is also improved when not irradiated.

【００１７】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 alkali network modifying ions such as sodium (soda lime glass, parallel plate 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.

【００１８】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、セルフクリーニング性、水による易清掃性に
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. Particularly, for the self-cleaning property and the easy cleaning property with water, as disclosed in PCT / JP96 / 00734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less.

【００１９】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 preferably used.

【００２０】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, the production method in the case where the surface layer is composed of only the photocatalyst will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. 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 Titanium alkoxide (tetraethoxy titanium, tetramethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, etc.), titanium acetate, titanium chelate, etc. are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.). , After diluting with a non-aqueous solvent such as alcohol (ethanol, propanol, butanol, etc.), while partially or completely proceeding the hydrolysis, the mixture is spray-coated, dip-coated, Apply by methods such as flow coating method, spin coating method, roll coating method,
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 evaporation method An amorphous titanium oxide layer is formed on the surface of a substrate 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.

【００２１】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、デイップコー
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 by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, for example, there are the following three methods. One method is the sol coating firing method, the other is the organic titanate method, the other is 4
This is a functional silane method. (1) Sol coating firing method A mixed solution of anatase type titanium oxide sol and silica sol is applied to the surface of a substrate by a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method or the like, and then baked. To do. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, and other organic titanates are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol. 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 anatase type titanium oxide sol is spray-coated or dip-coated on the surface of a substrate. , A flow coating method, a spin coating method, a roll coating method, or the like, and if necessary, hydrolyzing to form silanol, and then silanol is subjected to dehydration condensation polymerization by a method such as heating.

【００２２】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 by taking as an example the case where the photocatalyst is anatase type titanium oxide and the solid acid is TiO 2 / WO 3 . In this case, the ammonia solution of tungstic acid and anatase type titanium oxide sol are mixed, and if necessary, a mixture diluted with a diluent (water, ethanol, etc.) is spray-coated or dip-coated on the surface of the substrate. Law,
It is applied by a method such as a flow coating method, a spin coating method, a roll coating method or the like, and baked. Other methods include electron beam evaporation and hydrolysis and dehydration polycondensation of organic titanates such as titanium alkoxide, titanium acetate and titanium chelate to crystallize amorphous titanium oxide and produce TiO 2 / WO 3 composite oxide. Heat treatment is performed at a temperature.

【００２３】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 composed of a photocatalyst and silicone will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. The method in this case is to mix a coating composed of uncured or partially cured silicone or a precursor of silicone and anatase type titanium oxide sol, and hydrolyze the precursor of silicone as needed, and then mix the mixture. Spray coating method on the surface of the substrate,
It is applied by a method such as a dip coating method, a flow coating method, a spin coating method, a roll coating method, etc., and a hydrolyzate of a silicone precursor is subjected to dehydration polycondensation by a method such as heating to obtain anatase type titanium oxide particles. A surface layer made of silicone is formed. The formed surface layer, by photoexcitation of anatase type titanium oxide by irradiation with light including ultraviolet rays, at least a part of the organic group bonded to the silicon atom in the silicone molecule is substituted with a hydroxyl group, and further on it. A physically adsorbed water layer is formed,
It exhibits a high degree of hydrophilicity. Here, the precursor of silicone includes methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, and 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.

【００２４】[0024]

【実施例】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を被着し、そ
の後５００℃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（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、＃１試料を得た。
比較のため、１０ｃｍ角のソーダライムガラス板＃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、水滴は表面にややなじむ
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４０゜であった。[Examples] Amorphous titanium oxide was crystallized by depositing amorphous titanium oxide on the surface of a 10 cm square soda lime glass plate by an electron beam evaporation method and then firing at a temperature of 500 ° C. Titanium oxide was produced. Anatase type titanium oxide film thickness is 100 nm
Met. Further, tungstic acid dissolved in 25% ammonia water was applied thereon at 0.6 μg / cm 2 in terms of tungstic acid weight, and then baked at a temperature of 500 ° C. Next, after leaving this glass plate in a dark place for several days, an ultraviolet light source (Sankyo Denki, Black Light Blue (BLB))
The surface of the sample was irradiated with ultraviolet rays for about 1 hour using a fluorescent lamp at an ultraviolet illuminance of 0.5 mW / cm 2 to obtain a # 1 sample.
For comparison, a 10 cm square soda lime glass plate # 2 sample was also prepared. First, a water drop was dropped on the # 1 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 from the micro syringe onto the sample surface, it was observed that the water droplet spread uniformly on the sample surface in a water film shape. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the # 2 sample, when a water droplet was dropped from the microsyringe on the surface of the sample, the water droplet slightly adapted to the surface, but did not reach a uniform water film shape. The contact angle with water after 30 seconds was 40 °.

【００２５】次に、＃１試料の表面にオレイン酸を塗布
し、試料表面を水平姿勢に保持しながら夫々の試料を水
槽に満たした水の中に浸漬した。その結果、＃１試料で
は、オレイン酸は丸くなり、軽くこすると表面から離脱
した。Next, oleic acid was applied to the surface of the # 1 sample, and each sample was immersed in water filled in a water tank while keeping the sample surface in a horizontal posture. As a result, in the # 1 sample, the oleic acid became round, and lightly rubbed off from the surface.

【００２６】次に、疎水性カーボンブラック１重量部、
親水性カーボンブラック１重量部からなる粉体混合物を
１．０５ｇ／リッターの濃度で水に懸濁させたスラリー
を調製した。４５度に傾斜させた＃１試料に上記スラリ
ー１５０ｍｌを流下させて１５分間乾燥させ、次いで蒸
留水１５０ｍｌを流下させて１５分間乾燥させ、このサ
イクルを２５回反復した。試験前後の色差変化を，色差
計（東京電色）を用いて計測した。色差は日本工業規格
（ＪＩＳ）Ｈ０２０１に従い、ΔＥ＊表示を用いた。そ
の結果、＃１試料の色差変化は０．６に止まった。Next, 1 part by weight of hydrophobic carbon black,
A slurry was prepared by suspending a powder mixture consisting of 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. 150 ml of the above slurry was made to flow down on a # 1 sample inclined at 45 degrees and dried for 15 minutes, then 150 ml of distilled water was made to flow down and dried for 15 minutes, and this cycle was repeated 25 times. The color difference change before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was represented by ΔE * according to Japanese Industrial Standard (JIS) H0201. As a result, the color difference change of the # 1 sample was only 0.6.

【００２９】[0029]

【発明の効果】本発明では、ガラスブロック基材の表面
に、光触媒粒子を含有する表面層を備えるようにするこ
とにより、ガラスブロック表面は、光触媒の光励起に応
じて高度の親水性を呈し、降雨により自己清浄化（セル
フクリーニング）され、或いは散水や水濯ぎや水拭き程
度で清掃可能になる。INDUSTRIAL APPLICABILITY In the present invention, by providing the surface of the glass block substrate with the surface layer containing photocatalyst particles, the glass block surface exhibits a high degree of hydrophilicity in response to photoexcitation of the photocatalyst, It is self-cleaning (self-cleaning) by rainfall, or it can be cleaned by spraying water, rinsing water, or wiping with water.

【図面の簡単な説明】[Brief description of drawings]

【図１】 本発明に係るガラスブロックの表面構造を示
す図。FIG. 1 is a diagram showing a surface structure of a glass block according to the present invention.

【図２】 本発明に係るガラスブロックの他の表面構造
を示す図。FIG. 2 is a diagram showing another surface structure of the glass block according to the present invention.

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 ガラスブロック基材の表面に、光触媒粒
子を含有する表面層を備え、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、以てガラスブロック
の前記層が降雨にさらされた時に付着堆積物及び／又は
汚染物が雨滴により洗い流されるのを可能にするセルフ
クリーニング性ガラスブロック。1. A surface layer of a glass block substrate is provided with a surface layer containing photocatalyst particles, and the surface of the layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, whereby the layer of the glass block is rained. A self-cleaning glass block that allows adherent deposits and / or contaminants to be washed away by raindrops when exposed to water. 【請求項２】 ガラスブロック基材の表面に、光触媒粒
子を含有する表面層を備え、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、以てガラスブロック
の前記層表面を水で洗浄するのが容易になる易清掃性ガ
ラスブロック。2. The surface of a glass block substrate is provided with a surface layer containing photocatalyst particles, and the surface of the layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, and thus the surface of the layer of the glass block is Easy-to-clean glass block that is easy to wash with water. 【請求項３】 前記表面層には、さらにシリカが含有さ
れていることを特徴とする請求項１、２に記載のガラス
ブロック。3. The glass block according to claim 1, wherein the surface layer further contains silica. 【請求項４】 前記表面層には、さらに固体酸が含有さ
れていることを特徴とする請求項１、２に記載のガラス
ブロック。4. The glass block according to claim 1, wherein the surface layer further contains a solid acid. 【請求項５】 前記表面層には、さらにシリコーンが含
有されていることを特徴とする請求項１、２に記載のガ
ラスブロック。5. The glass block according to claim 1, wherein the surface layer further contains silicone. 【請求項６】 前記表面層の表面は、前記光触媒の光励
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１〜５に記載のガラ
スブロック。6. The surface according to claim 1, wherein the surface of the surface layer exhibits hydrophilicity of 10 ° or less in terms of contact angle with water in response to photoexcitation of the photocatalyst. Glass block. 【請求項７】 前記表面層の表面は、前記光触媒の光励
起に応じて、水との接触角に換算して５゜以下の親水性
を呈することを特徴とする請求項１〜５に記載のガラス
ブロック。7. The surface of the surface layer exhibits hydrophilicity of 5 ° or less in terms of contact angle with water in response to photoexcitation of the photocatalyst. Glass block. 【請求項８】 前記表面層の表面に、さらに親水化可能
な保護層が設けられていることを特徴とする請求項１〜
７に記載のガラスブロック。8. A hydrophilic protective layer is further provided on the surface of the surface layer.
The glass block according to 7. 【請求項９】 請求項１〜８に記載のガラスブロックを
準備する工程と；前記ガラスブロックを前記層表面が降
雨の当たるように配置する工程と；前記ガラスブロック
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する工程と；前記ガラスブロッ
クを降雨にさらして、前記層の表面に付着する堆積物及
び／又は汚染物を雨滴により洗い流させる工程；からな
るガラスブロックのセルフクリーニング方法。9. A step of preparing the glass block according to claim 1; a step of arranging the glass block such that the surface of the layer is exposed to rainfall; a photocatalyst contained in a surface layer of the glass block. By optically exciting
A method of self-cleaning a glass block, which comprises: making the surface of the layer hydrophilic; exposing the glass block to rainfall to wash away deposits and / or contaminants adhering to the surface of the layer by raindrops. . 【請求項１０】 請求項１〜８に記載のガラスブロック
を準備する工程と；前記ガラスブロックの表面層に含有
される光触媒を光励起することにより、前記層の表面を
親水性にする工程と；前記ガラスブロックを水で濯ぐ又
は水拭きすることにより、前記層の表面に付着する堆積
物及び／又は汚染物を表面から釈放させて水により洗い
流す工程；からなるガラスブロックの清浄化方法。10. A step of preparing the glass block according to claim 1; a step of making a surface of the layer hydrophilic by photoexciting a photocatalyst contained in a surface layer of the glass block; A method for cleaning a glass block, comprising the steps of rinsing or wiping the glass block with water to release deposits and / or contaminants adhering to the surface of the layer from the surface and washing with water.
JP8282810A 1995-12-22 1996-09-18 Glass block and its cleaning method Pending JPH09228545A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8282810A JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP7-354649 1995-12-22
JP35464995 1995-12-22
JP8282810A JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method

Publications (1)

Publication Number Publication Date
JPH09228545A true JPH09228545A (en) 1997-09-02

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
JP13653596A Expired - Lifetime JP3339304B2 (en) 1995-12-22 1996-05-30 Painted object and painting method
JP8136777A Pending JPH09227178A (en) 1995-12-22 1996-05-30 Laminated glass and its production
JP13782996A Ceased JP3189682B2 (en) 1995-12-22 1996-05-31 Antifouling material
JP8168643A Pending JPH09232096A (en) 1995-12-22 1996-06-06 Electrification preventing method, and electrification preventive composite material
JP8145265A Pending JPH09225276A (en) 1995-12-22 1996-06-07 Separating membrane and formation of surface layer to separating membrane
JP8168662A Pending JPH09225389A (en) 1995-12-22 1996-06-10 Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture
JP8158518A Pending JPH09225021A (en) 1995-12-22 1996-06-19 Medical material
JP8195184A Expired - Lifetime JP3003581B2 (en) 1995-12-22 1996-06-20 A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor
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
JP8272808A Pending JPH09229724A (en) 1995-12-22 1996-09-07 Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover
JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
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
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
JP8281225A Pending JPH09230107A (en) 1995-12-22 1996-09-17 Anti-fogging glass lens and its anti-fogging method
JP8281222A Pending JPH09230106A (en) 1995-12-22 1996-09-17 Anti-fogging camera filter and its anti-fogging method
JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8281220A Expired - Lifetime JP3003593B2 (en) 1995-12-22 1996-09-17 Photocatalytic hydrophilic member
JP8282806A Pending JPH09228057A (en) 1995-12-22 1996-09-18 Wheel and its cleaning method
JP8246180A Pending JPH09230493A (en) 1995-12-22 1996-09-18 Camera
JP8282808A Pending JPH09228765A (en) 1995-12-22 1996-09-18 Blind and manufacture thereof
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
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
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method
JP8282810A Pending JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method
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
JP28281296A Expired - Lifetime JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them
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
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
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
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
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
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
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
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
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
JP2000181287A Expired - Fee Related JP3465664B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

Family Applications Before (33)

Application Number Title Priority Date Filing Date
JP8083499A Pending JPH09231821A (en) 1995-12-22 1996-04-05 Luminaire and method for maintaining illuminance
JP13408196A Expired - Lifetime JP3385850B2 (en) 1995-12-22 1996-04-19 Composite material with hydrophilicity
JP10079496A Expired - Lifetime JP3740736B2 (en) 1995-12-22 1996-04-23 HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD
JP15017196A Expired - Lifetime JP3760509B2 (en) 1995-12-22 1996-05-22 Greenhouse ceiling and its condensation prevention method
JP8150410A Pending JPH09225263A (en) 1995-12-22 1996-05-23 Air pollutant removing filter, air pollutant removing fan and ventilator using the fan
JP8156383A Pending JPH09231849A (en) 1995-12-22 1996-05-29 Insulator and dirt preventing method therefore
JP13653596A Expired - Lifetime JP3339304B2 (en) 1995-12-22 1996-05-30 Painted object and painting method
JP8136777A Pending JPH09227178A (en) 1995-12-22 1996-05-30 Laminated glass and its production
JP13782996A Ceased JP3189682B2 (en) 1995-12-22 1996-05-31 Antifouling material
JP8168643A Pending JPH09232096A (en) 1995-12-22 1996-06-06 Electrification preventing method, and electrification preventive composite material
JP8145265A Pending JPH09225276A (en) 1995-12-22 1996-06-07 Separating membrane and formation of surface layer to separating membrane
JP8168662A Pending JPH09225389A (en) 1995-12-22 1996-06-10 Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture
JP8158518A Pending JPH09225021A (en) 1995-12-22 1996-06-19 Medical material
JP8195184A Expired - Lifetime JP3003581B2 (en) 1995-12-22 1996-06-20 A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor
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
JP8272808A Pending JPH09229724A (en) 1995-12-22 1996-09-07 Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover
JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
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
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
JP8281225A Pending JPH09230107A (en) 1995-12-22 1996-09-17 Anti-fogging glass lens and its anti-fogging method
JP8281222A Pending JPH09230106A (en) 1995-12-22 1996-09-17 Anti-fogging camera filter and its anti-fogging method
JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8281220A Expired - Lifetime JP3003593B2 (en) 1995-12-22 1996-09-17 Photocatalytic hydrophilic member
JP8282806A Pending JPH09228057A (en) 1995-12-22 1996-09-18 Wheel and its cleaning method
JP8246180A Pending JPH09230493A (en) 1995-12-22 1996-09-18 Camera
JP8282808A Pending JPH09228765A (en) 1995-12-22 1996-09-18 Blind and manufacture thereof
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
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
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method

Family Applications After (37)

Application Number Title Priority Date Filing Date
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
JP28281296A Expired - Lifetime JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them
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
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
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
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
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
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
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
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
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
JP2000181287A Expired - Fee Related JP3465664B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

Country Status (1)

Country Link
JP (71) JPH09231821A (en)

Families Citing this family (197)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JPH09230105A (en) * 1995-12-22 1997-09-05 Toto Ltd Antifogging method and facility applied with the method
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance
JPH09227779A (en) * 1995-12-22 1997-09-02 Toto Ltd Rubber member for construction and impartment of hydrophilicity to surface thereof
JPH09186949A (en) * 1995-12-27 1997-07-15 Toshiba Lighting & Technol Corp Video equipment
JP3400259B2 (en) * 1996-08-26 2003-04-28 セントラル硝子株式会社 Hydrophilic coating and method for producing the same
JP3949788B2 (en) * 1996-09-17 2007-07-25 大野 隆司 Goods storage container
JP4305001B2 (en) * 1996-09-20 2009-07-29 株式会社日立製作所 Articles with a photocatalytic film
WO1998012048A1 (en) * 1996-09-20 1998-03-26 Hitachi, Ltd. Thin photocatalytic film and articles provided with the same
JPH10148705A (en) * 1996-11-21 1998-06-02 Hitachi Chem Co Ltd Antifog treatment
JP3467994B2 (en) * 1996-11-27 2003-11-17 松下電工株式会社 Silicone transfer film and transfer structure thereof
JPH10237352A (en) * 1997-02-24 1998-09-08 Tao:Kk Polyfunctional coating agent
JP4672822B2 (en) * 1997-02-24 2011-04-20 株式会社ティオテクノ Hydrophilic coating agent and surface hydrophilic substrate
JP3518251B2 (en) * 1997-05-20 2004-04-12 株式会社日立製作所 Oxide photocatalytic thin film and article provided with the same
JPH1190236A (en) * 1997-09-22 1999-04-06 Ebara Corp Photocatalyst and reaction device using photocatalyst
JPH11100695A (en) * 1997-09-26 1999-04-13 Nippon Alum Co Ltd Production of titanium material having photocatalytic activity
JPH11100526A (en) * 1997-09-29 1999-04-13 Toto Ltd Photocatalytic hydrophilic member and photocatalytic hydrophilic coating composition
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
WO1999052983A1 (en) * 1998-04-10 1999-10-21 Matsushita Electric Works, Ltd. 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
WO2000046154A1 (en) * 1999-02-04 2000-08-10 Japan Science And Technology Corporation 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
US6716513B1 (en) 1999-03-09 2004-04-06 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
EP1054047B1 (en) 1999-05-21 2003-03-26 JSR Corporation A coating composition, and a coated film and glass each having a coating layer comprised thereof
FR2794225B3 (en) * 1999-05-25 2001-06-15 Saint Gobain Vitrage REFRIGERATED ENCLOSURE DOOR WITH VACUUM WINDOWS
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
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
KR20010110722A (en) 2000-02-07 2001-12-13 하시모토 쯔토무 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
US6863933B2 (en) 2001-01-30 2005-03-08 The Procter And Gamble Company Method of hydrophilizing materials
CN1531465A (en) * 2001-03-21 2004-09-22 普利司通股份有限公司 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
US20040210309A1 (en) * 2001-10-11 2004-10-21 Denzer Alain J Osteophilic implants
JP2003135228A (en) * 2001-11-02 2003-05-13 Sanyo Electric Co Ltd Low temperature show case
WO2003069044A1 (en) * 2002-02-14 2003-08-21 Lg Electronics Inc. Door for washing machine and method for manufacturing the same
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
EP1518601A4 (en) 2002-06-03 2007-12-19 Asahi Chemical Ind 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
EP1551569B1 (en) 2002-09-26 2017-05-10 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
US8268340B2 (en) 2002-09-26 2012-09-18 Advanced Bio Prosthetic Surfaces, Ltd. Implantable materials having engineered surfaces 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
EP2837606A1 (en) 2004-09-20 2015-02-18 AGC Flat Glass North America, Inc. Anti-fog refrigeration door and method of making the same
JP2006091249A (en) 2004-09-22 2006-04-06 Murakami Corp Camera
JP2008525188A (en) * 2004-12-28 2008-07-17 カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ Automatic cleaning process of dirt by photocatalyst
KR100938794B1 (en) * 2005-02-18 2010-01-27 닛뽕소다 가부시키가이샤 Organic-inorganic composite body
EP1852183A4 (en) 2005-02-24 2011-06-29 Central Res Inst Elect Multifunctional material
CN101171357B (en) 2005-02-24 2010-05-19 财团法人电力中央研究所 Process for producing multifunctional material
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
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
JP4480014B2 (en) * 2005-02-28 2010-06-16 財団法人電力中央研究所 Rocket parts
JP4814534B2 (en) * 2005-02-28 2011-11-16 財団法人電力中央研究所 Manufacturing method of structural materials
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
JP4807724B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Rail vehicle manufacturing method
JP4541929B2 (en) * 2005-02-28 2010-09-08 財団法人電力中央研究所 Flying object
JP4843231B2 (en) * 2005-02-28 2011-12-21 財団法人電力中央研究所 Kitchen products
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
JP4958029B2 (en) * 2005-02-28 2012-06-20 一般財団法人電力中央研究所 Building materials
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
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
JP2008184357A (en) * 2007-01-30 2008-08-14 National Institute Of Advanced Industrial & Technology Method of making surface of oxide amphiphilic
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
JP5365500B2 (en) * 2009-12-24 2013-12-11 平岡織染株式会社 Non-flammable interior illuminated signboard
JP5365501B2 (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
CN104759297B (en) 2010-07-29 2018-02-23 Toto株式会社 Object with photo-catalyst coating and photocatalyst coating liquid
EP3009185B1 (en) * 2010-09-28 2017-08-16 Dow Global Technologies LLC Reactive flow static mixer with cross-flow obstructions and mixing method
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
JP6461573B2 (en) 2014-07-30 2019-01-30 三菱マテリアル株式会社 Oil / water separator / collector
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
CN106574166B (en) 2014-07-30 2018-10-02 三菱综合材料株式会社 Surface covering material, coated film and hydrophilic oil repellent material
CN106659948B (en) 2014-07-30 2019-08-16 三菱综合材料株式会社 Filter material, the manufacturing method of filter material, water process module and water treatment facilities
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
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
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
JP2017165612A (en) * 2016-03-16 2017-09-21 Ｔｏｗａ株式会社 Translucent material, low adhesion material and molding member
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
TWI785189B (en) * 2018-01-30 2022-12-01 美商菲爾薇解析公司 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
JP7499561B2 (en) * 2018-12-28 2024-06-14 ホヤ レンズ タイランド リミテッド Manufacturing method of eyeglass lenses
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
CN116235016A (en) 2020-10-21 2023-06-06 三菱电机株式会社 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)

* Cited by examiner, † Cited by third party
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
EP0923988B1 (en) * 1995-06-19 2008-04-09 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

Also Published As

Publication number Publication date
JPH09224874A (en) 1997-09-02
JPH09227162A (en) 1997-09-02
JPH09241038A (en) 1997-09-16
JPH09228022A (en) 1997-09-02
JPH09228326A (en) 1997-09-02
JP3613084B2 (en) 2005-01-26
JP3003593B2 (en) 2000-01-31
JP2001049828A (en) 2001-02-20
JP3844182B2 (en) 2006-11-08
JPH09227160A (en) 1997-09-02
JPH09229546A (en) 1997-09-05
JPH09227178A (en) 1997-09-02
JPH09226040A (en) 1997-09-02
JPH09230118A (en) 1997-09-05
JP3385850B2 (en) 2003-03-10
JP3414365B2 (en) 2003-06-09
JP2001129916A (en) 2001-05-15
JP2001049829A (en) 2001-02-20
JP2000127289A (en) 2000-05-09
JPH09230810A (en) 1997-09-05
JP3414367B2 (en) 2003-06-09
JPH09229585A (en) 1997-09-05
JPH09230031A (en) 1997-09-05
JPH09231821A (en) 1997-09-05
JPH09227156A (en) 1997-09-02
JP2000136370A (en) 2000-05-16
JP3760509B2 (en) 2006-03-29
JP3612896B2 (en) 2005-01-19
JP3882625B2 (en) 2007-02-21
JPH09228320A (en) 1997-09-02
JPH09227169A (en) 1997-09-02
JPH09228765A (en) 1997-09-02
JP3774955B2 (en) 2006-05-17
JPH09225021A (en) 1997-09-02
JPH09231849A (en) 1997-09-05
JPH09227159A (en) 1997-09-02
JP3740736B2 (en) 2006-02-01
JPH09224793A (en) 1997-09-02
JP2001122679A (en) 2001-05-08
JP2001081948A (en) 2001-03-27
JPH09230493A (en) 1997-09-05
JP2002302646A (en) 2002-10-18
JPH09226531A (en) 1997-09-02
JPH09229767A (en) 1997-09-05
JPH09225388A (en) 1997-09-02
JPH09228332A (en) 1997-09-02
JPH09230796A (en) 1997-09-05
JPH09231807A (en) 1997-09-05
JPH09225389A (en) 1997-09-02
JP2000141537A (en) 2000-05-23
JPH09225054A (en) 1997-09-02
JPH09224960A (en) 1997-09-02
JP3141802B2 (en) 2001-03-07
JPH09224800A (en) 1997-09-02
JPH09226042A (en) 1997-09-02
JP3613085B2 (en) 2005-01-26
JPH09230106A (en) 1997-09-05
JPH09226060A (en) 1997-09-02
JPH09227805A (en) 1997-09-02
JPH09225396A (en) 1997-09-02
JPH09228331A (en) 1997-09-02
JP2001089752A (en) 2001-04-03
JPH09229724A (en) 1997-09-05
JP2002030258A (en) 2002-01-31
JPH09227832A (en) 1997-09-02
JP3588205B2 (en) 2004-11-10
JPH09228057A (en) 1997-09-02
JP2001048679A (en) 2001-02-20
JP3189682B2 (en) 2001-07-16
JPH09227831A (en) 1997-09-02
JPH09231499A (en) 1997-09-05
JPH09224957A (en) 1997-09-02
JPH09224490A (en) 1997-09-02
JP3003581B2 (en) 2000-01-31
JPH09225387A (en) 1997-09-02
JP3697795B2 (en) 2005-09-21
JP3339304B2 (en) 2002-10-28
JP2003113345A (en) 2003-04-18
JP3588202B2 (en) 2004-11-10
JPH09226041A (en) 1997-09-02
JPH09232096A (en) 1997-09-05
JPH09230119A (en) 1997-09-05
JPH09228134A (en) 1997-09-02
JP3277983B2 (en) 2002-04-22
JP3303696B2 (en) 2002-07-22
JP3063968B2 (en) 2000-07-12
JPH09230108A (en) 1997-09-05
JP3173391B2 (en) 2001-06-04
JPH09230107A (en) 1997-09-05
JP3588206B2 (en) 2004-11-10
JPH09228602A (en) 1997-09-02
JPH09225263A (en) 1997-09-02
JPH09227161A (en) 1997-09-02
JP3348613B2 (en) 2002-11-20
JP3743075B2 (en) 2006-02-08
JP3465664B2 (en) 2003-11-10
JPH09225276A (en) 1997-09-02
JP3075195B2 (en) 2000-08-07

Similar Documents

Publication Publication Date Title
JPH09228545A (en) Glass block and its cleaning method
JPH10225351A (en) Flower vase
JPH10292565A (en) Roofing material for preventing icing and snow accretion
JPH10225393A (en) Bathtub
JPH10196068A (en) Snow accretion preventive roof material
JPH10199311A (en) Lighting system for tunnel
JPH10212139A (en) Window glass for construction
JPH10221503A (en) Glass lens
JPH1096659A (en) Weighing container

Legal Events

Date Code Title Description
A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20041021

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20041102

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20041227

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20050930