JPH09228765A - Blind and manufacture thereof - Google Patents

Blind and manufacture thereof

Info

Publication number
JPH09228765A
JPH09228765A JP8282808A JP28280896A JPH09228765A JP H09228765 A JPH09228765 A JP H09228765A JP 8282808 A JP8282808 A JP 8282808A JP 28280896 A JP28280896 A JP 28280896A JP H09228765 A JPH09228765 A JP H09228765A
Authority
JP
Japan
Prior art keywords
blind
layer
water
photocatalyst
surface layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP8282808A
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=JPH09228765(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 JP8282808A priority Critical patent/JPH09228765A/en
Publication of JPH09228765A publication Critical patent/JPH09228765A/en
Pending legal-status Critical Current

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Classifications

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

Landscapes

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

Abstract

PROBLEM TO BE SOLVED: To make easy cleaning of blind by providing a surface layer containing an optical catalyst particles on the surface of blind base material. SOLUTION: On the surface of blind base material a surface layer containing optical catalyst particles of such as an anatase type titanium oxide or the like is formed. This layer shows a hydrophilic characteristic of 10 degrees or below by the conversion to the contac angle of water according to optical excitation of optical catalyst. By containing silica in this layer, the surface is liable to show a hydrophilic characteristic of the level near 0 degrees in wetting angle. Also, by containing solid acid of such as surfuric acid carrier Al2 O3 , the surface is liable to show the wet angle of the level near 0 degrees. Accordingly the blind surface shows the hydrophilic characteristic according to the optical excitation of optical catalyst so that the cleaning can be made by spraying or scattering water, linsing, or a light wiping operation with a wet cloth.

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、ブラインド、及び
その清掃方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blind and a cleaning method therefor.

【０００２】[0002]

【従来の技術】窓の日よけに用いるブラインドは、大気
中に浮遊する煤塵の堆積や油汚れにより汚れやすい。2. Description of the Related Art Blinds used for window shades are liable to be contaminated by accumulation of dust and oil stains floating in the atmosphere.

【０００３】[0003]

【発明の解決すべき課題】このようなブラインドは頻繁
に清掃されることが希なため、その汚れはかなり強固に
付着する。そのため、清掃作業はかなりの重労働にな
り、時間がかかるという問題があった。本発明の目的
は、散水や水濯ぎ、又は軽い水拭き程度で簡単に清掃可
能な表面を有するブラインド、及びその清掃方法を提供
することにある。本発明の他の目的は、取り外して雨天
に屋外に配置しておくだけで、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ブライン
ド、及びブラインドの清掃方法を提供することにある。Since such blinds are rarely cleaned frequently, their dirt adheres fairly strongly. Therefore, there is a problem that the cleaning work is considerably heavy work and takes time. It is an object of the present invention to provide a blind having a surface which can be easily cleaned by sprinkling water, rinsing water, or wiping with a light water, and a cleaning method thereof. It is another object of the present invention to provide a blind having a surface that is self-cleaning (self-cleaning) by rainfall and a method for cleaning the blind simply by removing and placing it outdoors in the rain.

【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、ブラインド基材の表面に、光
触媒粒子を含有する表面層を備えた易清掃性ブラインド
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、ブラインドの表面を散水や水濯ぎ、又は軽
い水拭き程度で水で洗浄するのが容易になる。The present invention provides an easy-cleaning blind having a surface layer containing photocatalyst particles on the surface of a blind substrate. By providing a surface layer containing a photocatalyst, in response to photoexcitation of the photocatalyst, since the surface of the surface layer exhibits hydrophilicity, it is possible to wash the surface of the blind with water with a water spray or water rinsing, or a light water wipe. It will be easier.

【０００６】本発明では、ブラインド基材の表面に、光
触媒粒子を含有する表面層を備えた易清掃性ブラインド
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、ブラインドを取り外して降雨にさらされる
ようにし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 an easy-cleaning blind having a surface layer containing photocatalyst particles on the surface of a blind substrate. By providing a surface layer containing a photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, so that when the blinds are removed and exposed to rainfall, adhered deposits and / or contaminants are removed. It can be washed away by raindrops.

【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。本発明におけるブラインドの表面には、
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、ブラインドの表面は、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、ブラインドの表面を水
で洗浄するのが容易になる。さらに、ブラインドの表面
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。BEST MODE FOR CARRYING OUT THE INVENTION Next, a specific structure of the present invention will be described. The surface of the blind in the present invention,
As shown in FIG. 1 or FIG. 2, a layer containing a photocatalyst is formed on the surface of the substrate. By taking such a surface structure, the surface of the blind is highly hydrophilized in response to photoexcitation of the photocatalyst. Thereby, the hydrophilicity of the surface becomes stronger than the lipophilicity. This makes it easier to wash the surface of the blind with water. Moreover, when the surface of the blind is exposed to rainfall, the deposits and / or contaminants become washed away by the raindrops.

【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】本発明におけるブラインドは、アルミニウ
ム塗装板等の塗装鋼板、アクリル塗装板等の塗装プラス
チック板等が好適に利用できる。As the blind in the present invention, a coated steel plate such as an aluminum coated plate, a coated plastic plate such as an acrylic coated plate, or the like can be preferably used.

【００１３】光触媒とは、その結晶の伝導帯と価電子帯
との間のエネルギーギャップよりも大きなエネルギー
（すなわち短い波長）の光（励起光）を照射したとき
に、価電子帯中の電子の励起（光励起）が生じて、伝導
電子と正孔を生成しうる物質をいい、例えば、アナター
ゼ型酸化チタン、ルチル型酸化チタン、酸化錫、酸化亜
鉛、三酸化二ビスマス、三酸化タングステン、酸化第二
鉄、チタン酸ストロンチウム等が好適に利用できる。こ
こで光触媒の光励起に用いる光源としては、太陽光；街
灯、常夜灯等の環境にある光源；や一般照明が利用でき
る。一般照明としては蛍光灯、白熱電灯、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、０．０
１ｍＷ／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 a light source used for photoexcitation of the photocatalyst, sunlight; a light source in an environment such as a street light or a night light; and general lighting can be used. As general lighting, a fluorescent lamp, an incandescent lamp, a metal halide lamp, a black light lamp, a xenon lamp, a mercury lamp, etc. can be preferably used. By photoexcitation of photocatalyst,
In order to make the surface of the base material highly hydrophilic, the illuminance of the excitation light may be 0.001 mW / cm 2 or more, but 0.0
It is preferably 1 mW / cm 2 or more, and 0.1 mW / cm 2
The above is more preferable.

【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】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.

【００１８】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。In the present invention, the solid acid 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.

【００１９】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 only of 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.

【００２０】次に、表面層が光触媒とシリカからなる場
合について、光触媒がアナターゼ型酸化チタンの場合を
例にとり説明する。この場合の方法は、例えば、以下の
３つの方法がある。１つの方法はゾル塗布焼成法であ
り、他の方法は有機チタネート法であり、他の方法は４
官能性シラン法である。 （１）ゾル塗布焼成法 アナターゼ型酸化チタンゾルとシリカゾルとの混合液
を、基材表面にスプレーコーティング法、ディップコー
ティング法、フローコーティング法、スピンコーティン
グ法、ロールコーティング法等の方法で塗布し、焼成す
る。 （２）有機チタネート法 チタンアルコキシド（テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等）、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤（塩酸、エチルアミン
等）とシリカゾルを添加し、アルコール（エタノール、
プロパノール、ブタノール等）などの非水溶媒で希釈し
た後、部分的に加水分解を進行させながら又は完全に加
水分解を進行させた後、混合物をスプレーコーティング
法、ディップコーティング法、フローコーティング法、
スピンコーティング法、ロールコーティング法等の方法
で塗布し、乾燥させる。乾燥により、有機チタネートの
加水分解が完遂して水酸化チタンが生成し、水酸化チタ
ンの脱水縮重合により無定型酸化チタンの層が基材表面
に形成される。その後、アナターゼの結晶化温度以上の
温度で焼成して、無定型酸化チタンをアナターゼ型酸化
チタンに相転移させる。 （３）４官能性シラン法 テトラアルコキシシラン（テトラエトキシシラン、テト
ラプロポキシシラン、テトラブトキシシラン、テトラメ
トキシシラン等）とアナターゼ型酸化チタンゾルとの混
合物を基材の表面にスプレーコーティング法、ディップ
コーティング法、フローコーティング法、スピンコーテ
ィング法、ロールコーティング法等の方法で塗布し、必
要に応じて加水分解させてシラノールを形成した後、加
熱等の方法でシラノールを脱水縮重合に付す。Next, the case where the surface layer is composed of a photocatalyst and silica will be described 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 and baking method A mixture of anatase-type titanium oxide sol and silica sol is applied to the substrate surface by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, and a roll coating method, and then fired. I do. (2) Organic titanate method 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.

【００２１】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。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.

【００２２】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.

【００２３】[0023]

【実施例】まず、１０ｃｍ角のアルミニウム板表面に、
プライマー塗料（東芝シリコーン、 ＰＨ９３をトルエ
ン溶媒で６倍に希釈した塗料）をスプレーコーティング
法にて塗布後室温で乾燥させて、基板をプライマー樹脂
層で被覆した。次に、シリコーン系ハードコーティング
剤（東芝シリコーン、トスガード）をフローコーティン
グ法にて塗布し、９０℃で３時間乾燥し、プライマー樹
脂層の上にハードコート層を形成した。さらに、ハード
コート層表面を、コロナ表面処理装置（春日電機）によ
り、電極にワイヤー電極を用い、電極先端と試料表面と
のギャップ２ｍｍ、電圧２６ｋＶ、周波数３９ｋＨｚ、
試料送り速度４．２ｍ／分の条件で、高周波コロナ放電
処理して＃１試料を得た。一方、アナターゼ型酸化チタ
ンゾル５６重量部（日産化学、ＴＡ−１５、平均粒径１
２ｎｍ）とシリカゾル３３重量部（日本合成ゴム、グラ
スカＡ液）を混合し、エタノールで希釈後、更にメチル
トリメトキシシラン１１重量部（日本合成ゴム、グラス
カＢ液）を添加し、酸化チタン含有塗料組成物を調整し
た。上記塗料組成物を、＃１試料に、フローコーティン
グ法にて塗布し、９０℃で３時間熱処理して硬化させ、
＃２試料を得た。この＃２試料を、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０．６ｍＷ／ｃｍ２の紫外線照度で約４８
時間紫外線を照射し、＃３試料を得た。比較のため、１
０ｃｍ角のアルミニウム塗装板試料も準備した。まず、
＃３試料とアルミニウム塗装板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＃３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、アルミニウム塗装板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７０゜であった。Example First, on a surface of a 10 cm square aluminum plate,
A primer coating (Toshiba Silicone, a coating in which PH93 was diluted 6 times with a toluene solvent) was applied by a spray coating method and then dried at room temperature to coat the substrate with a primer resin layer. Next, a silicone-based hard coating agent (Toshiba Silicone, Tosgard) was applied by a flow coating method and dried at 90 ° C. for 3 hours to form a hard coat layer on the primer resin layer. Further, the surface of the hard coat layer was treated with a corona surface treatment device (Kasuga Denki) using a wire electrode as an electrode, the gap between the electrode tip and the sample surface was 2 mm, the voltage was 26 kV, and the frequency was 39 kHz.
A high frequency corona discharge treatment was carried out under the condition of a sample feeding speed of 4.2 m / min to obtain a # 1 sample. On the other hand, 56 parts by weight of anatase-type titanium oxide sol (TA-15, average particle size 1
2 nm) and 33 parts by weight of silica sol (Japan Synthetic Rubber, Glasca A liquid) are mixed, diluted with ethanol, and then 11 parts by weight of methyltrimethoxysilane (Japan Synthetic Rubber, Glasca B liquid) are added, and a titanium oxide-containing paint is added. The composition was adjusted. The above coating composition was applied to the # 1 sample by the flow coating method, and heat-treated at 90 ° C. for 3 hours to cure,
A # 2 sample was obtained. This # 2 sample was exposed to an ultraviolet light source (Sankyo Denki, Black Light Blue (BLB) fluorescent lamp) on the surface of the sample at an ultraviolet illuminance of 0.6 mW / cm 2 for about 48 hours.
It was irradiated with ultraviolet rays for an hour to obtain a sample # 3. 1 for comparison
A 0 cm square aluminum coated plate sample was also prepared. First,
A water drop was dropped on the # 3 sample and the aluminum coated plate sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water is a contact angle measuring device (Kyowa Interface Science, CA
-X150) was used to evaluate the contact angle with water 30 seconds after the dropping. As a result, when a water drop was dropped on the sample surface from the microsyringe in the # 3 sample, it was observed that the water droplet spread uniformly on the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the aluminum coated plate 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 70 °.

【００２４】次に、＃３試料とアルミニウム塗装板試料
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、アルミニウム塗装板試料では、オレイン
酸は試料の表面に付着したままであり、軽くこするとオ
レイン酸は試料表面を伸びるだけであった。それに対
し、＃３試料では、オレイン酸は丸くなり、軽くこする
と試料の表面から離脱した。Next, oleic acid was applied to the surfaces of the # 3 sample and the aluminum coated plate 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 aluminum coated plate sample, oleic acid remained attached to the surface of the sample, and when lightly rubbed, oleic acid only extended the sample surface. On the other hand, in the # 3 sample, the oleic acid became round, and when it was lightly rubbed, it separated from the surface of the sample.

【００２５】[0025]

【発明の効果】本発明では、ブラインド基材の表面に、
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、ブラインド表面は、光触媒の光励起に応じて高度
の親水性を呈し、散水や水濯ぎ、又は軽い水拭き程度で
清掃可能になる。According to the present invention, the surface of the blind substrate is
By providing a surface layer containing photocatalyst particles, the blind surface exhibits a high degree of hydrophilicity in response to photoexcitation of the photocatalyst and can be cleaned with a water spray, a water rinse, or a light water wipe.

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

【図１】 本発明に係るブラインドの表面構造を示す
図。FIG. 1 is a diagram showing a surface structure of a blind according to the present invention.

【図２】 本発明に係るブラインドの他の表面構造を示
す図。FIG. 2 is a diagram showing another surface structure of the blind according to the present invention.

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 ブラインド基材の表面に、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、以てブラインドの前記層
表面を水で洗浄するのが容易になる易清掃性ブライン
ド。1. A surface layer containing photocatalyst particles is provided on the surface of a blind substrate, and in response to photoexcitation of the photocatalyst,
The easily-cleanable blind in which the surface of the layer exhibits hydrophilicity, and thus the surface of the layer of the blind can be easily washed with water. 【請求項２】 ブラインド基材の表面に、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、以てブラインドの前記層
が降雨にさらされるようにしたときに付着堆積物及び／
又は汚染物が雨滴により洗い流されるのを可能にする易
清掃性ブラインド。2. The surface of the blind substrate is provided with a surface layer containing photocatalyst particles, and in response to photoexcitation of the photocatalyst,
The surface of the layer is hydrophilic so that when the layer of blinds is exposed to rainfall, deposits and / or
Or an easy-to-clean blind that allows contaminants to be washed away by raindrops. 【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に記載のブライ
ンド。3. The blind 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に記載のブライ
ンド。4. The blind 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に記載のブ
ラインド。5. The blind 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に記載のブラ
インド。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. blind. 【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に記載のブライ
ンド。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. blind. 【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に記載のブラインド。8. A hydrophilic protective layer is further provided on the surface of the surface layer.
The blind according to 7. 【請求項９】 請求項１〜８に記載のブラインドを準備
する工程と；前記ブラインド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；前記ブラインドを水で濯ぐ又は軽く水拭きす
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；
からなるブラインドの清掃方法。9. A step of preparing the blind according to claim 1; a step of rendering the surface of the layer hydrophilic by photoexciting a photocatalyst contained in a surface layer of the blind; Deposits and / or contaminants adhering to the surface of the layer by rinsing with water or wiping with water, and rinsing with water.
How to clean blinds. 【請求項１０】 請求項１〜８に記載のブラインドを準
備する工程と；前記ブラインドを屋外に配置する工程
と；前記ブラインド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；前記ブラインドを降雨にさらして、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；からなるブラインドの清掃方法。10. A step of preparing the blind according to claim 1; a step of arranging the blind outdoors; a surface of the layer by photoexciting a photocatalyst contained in a surface layer of the blind. And a step of exposing the blind to rainfall to wash away deposits and / or contaminants adhering to the surface of the layer with raindrops.
JP8282808A 1995-12-22 1996-09-18 Blind and manufacture thereof Pending JPH09228765A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8282808A JPH09228765A (en) 1995-12-22 1996-09-18 Blind and manufacture thereof

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP7-354649 1995-12-22
JP35464995 1995-12-22
JP8282808A JPH09228765A (en) 1995-12-22 1996-09-18 Blind and manufacture thereof

Publications (1)

Publication Number Publication Date
JPH09228765A true JPH09228765A (en) 1997-09-02

Family

ID=18438979

Family Applications (71)

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Family Applications Before (35)

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
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JP8281220A Expired - Lifetime JP3003593B2 (en) 1995-12-22 1996-09-17 Photocatalytic hydrophilic member
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
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
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JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8246180A Pending JPH09230493A (en) 1995-12-22 1996-09-18 Camera
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Family Applications After (35)

Application Number Title Priority Date Filing Date
JP8284532A Pending JPH09227805A (en) 1995-12-22 1996-09-19 Photocatalytic hydrophilic coating composition
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP28453496A Expired - Lifetime JP3173391B2 (en) 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
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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
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JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
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JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
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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
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
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
JP2000181284A Pending JP2001048679A (en) 1995-12-22 2000-06-16 Photocatalytic hydrophilic tile and its production
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

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JP (71) JPH09231821A (en)

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JP3697795B2 (en) 2005-09-21
JPH09225389A (en) 1997-09-02
JP3760509B2 (en) 2006-03-29
JPH09225021A (en) 1997-09-02
JP2000127289A (en) 2000-05-09
JP3173391B2 (en) 2001-06-04
JPH09226042A (en) 1997-09-02
JPH09230108A (en) 1997-09-05
JPH09224874A (en) 1997-09-02
JP2000141537A (en) 2000-05-23
JP2000136370A (en) 2000-05-16
JP3414367B2 (en) 2003-06-09
JPH09229724A (en) 1997-09-05
JP3414365B2 (en) 2003-06-09
JP3339304B2 (en) 2002-10-28
JP3348613B2 (en) 2002-11-20
JP2001049829A (en) 2001-02-20
JP3740736B2 (en) 2006-02-01
JPH09230107A (en) 1997-09-05
JPH09227832A (en) 1997-09-02
JPH09224793A (en) 1997-09-02
JPH09225054A (en) 1997-09-02
JPH09224960A (en) 1997-09-02
JPH09227156A (en) 1997-09-02
JP2002030258A (en) 2002-01-31
JPH09241038A (en) 1997-09-16
JP2001129916A (en) 2001-05-15
JPH09230810A (en) 1997-09-05
JPH09228022A (en) 1997-09-02
JP3003593B2 (en) 2000-01-31
JPH09227805A (en) 1997-09-02
JP2001081948A (en) 2001-03-27
JPH09228332A (en) 1997-09-02
JPH09231499A (en) 1997-09-05
JPH09230119A (en) 1997-09-05
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JPH09228134A (en) 1997-09-02
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JP2001122679A (en) 2001-05-08
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