JPH09228331A - Self-cleaning guard fens, and cleaning method of guard fens - Google Patents

Self-cleaning guard fens, and cleaning method of guard fens

Info

Publication number
JPH09228331A
JPH09228331A JP8288954A JP28895496A JPH09228331A JP H09228331 A JPH09228331 A JP H09228331A JP 8288954 A JP8288954 A JP 8288954A JP 28895496 A JP28895496 A JP 28895496A JP H09228331 A JPH09228331 A JP H09228331A
Authority
JP
Japan
Prior art keywords
surface layer
guard fence
guard
self
cleaning
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.)
Granted
Application number
JP8288954A
Other languages
Japanese (ja)
Other versions
JP3588205B2 (en
Inventor
Atsushi Kitamura
厚 北村
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
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Application filed by Toto Ltd filed Critical Toto Ltd
Priority to JP28895496A priority Critical patent/JP3588205B2/en
Publication of JPH09228331A publication Critical patent/JPH09228331A/en
Application granted granted Critical
Publication of JP3588205B2 publication Critical patent/JP3588205B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related 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

Abstract

PROBLEM TO BE SOLVED: To wash away the sediment or contaminant adhered to a surface layer by rain and self-clean a guard fens base by forming the surface layer containing a photocatalytic oxide particle on the surface of the guard fens base. SOLUTION: A surface layer containing a photocatalytic oxide such as titanium oxide is formed on the surface of a guard fens base for guard rail, guard pipe or the like, and the surface layer is made highly hydrophilic by the optical excitation of the photocatalyst to wash away the sediment or contaminant adhered to the surface layer by rain. When the outermost surface is formed of a general organic oxide, the same effect can be provided by the action of the photocatalyst. When either one of silica, solid acid and silicone is combined with the photocatalytic oxide, hydrophilic property is further improved, and hydrophilic property of 10 deg. or less in terms of contact angle with water can be exhibited. When the guard fens base is formed of a steel plate, an intermediate layer is provided to prevent the reduction in hydrophilic speed by inclusion of either atom of Fe, Ni, and Co to the surface layer.

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、降雨により自己浄
化（セルフクリーニング）可能なガードフェンス、及び
そのセルフクリーニング方法に関する。TECHNICAL FIELD The present invention relates to a guard fence capable of self-cleaning (self-cleaning) by rainfall and a self-cleaning method thereof.

【０００２】[0002]

【従来の技術】走行車の道路、走行車線、橋梁からの離
脱防止や、歩道を歩く歩行者の隣接する車線を走る走行
車からの保護等を目的としてガードフェンスが使用され
ている。ガードフェンスには、ガードレール、ガードケ
ーブル、ガードパイプの３種がある。このうち、ガード
レールが最も汎用性が高いが、歩道用途では市街地を中
心にガードパイプが使用されるようになっている。ガー
ドフェンスには、アルミニウム板、鋼板、ステンレス
板、チタン板等が使用されている。2. Description of the Related Art A guard fence is used for the purpose of preventing a traveling vehicle from leaving a road, a traveling lane or a bridge, and protecting a pedestrian walking on a sidewalk from a traveling vehicle traveling in an adjacent lane. There are three types of guard fences: guard rails, guard cables, and guard pipes. Of these, guardrails have the highest versatility, but guardrails are used mainly for urban areas in sidewalk applications. Aluminum plates, steel plates, stainless steel plates, titanium plates, etc. are used for the guard fence.

【０００３】[0003]

【発明の解決すべき課題】ガードフェンスは、排気ガス
中の煤煙やタイヤの摩耗粉や路面や大地から舞い上がっ
た煤塵によって汚れる。ガードフェンスが薄黒く汚れる
と不快な印象を与え、景観が損なわれる。本発明の目的
は、降雨により自己清浄化可能なガードフェンス及びそ
の降雨によるセルフクリーニング方法を提供することに
ある。The guard fence is contaminated by soot in exhaust gas, tire abrasion powder, and dust soared from the road surface or the ground. If the guard fence becomes dark and dirty, it gives an unpleasant impression and the landscape is damaged. An object of the present invention is to provide a guard fence that can be self-cleaned by rainfall and a method of self-cleaning by rainfall.

【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、ガードフェンス基材の表面
に、実質的に透明な光触媒性酸化物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ードフェンスを提供
する。光触媒性酸化物粒子を含有する表面層を備えるこ
とにより、光触媒の光励起に応じて、表面層の表面は親
水性を呈し、ガードフェンス表面が、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。The present invention provides a self-cleaning guard fence having a surface layer containing substantially transparent photocatalytic oxide particles on the surface of a guard fence substrate. By providing a surface layer containing photocatalytic oxide particles, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, and the guard fence surface, when exposed to rainfall, deposits and / or deposits. The contaminants will be washed away by the raindrops.

【０００６】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.

【０００７】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
ず極端に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 the surface layer contains a solid acid, the polarity of the surface is extremely large regardless of the presence or absence of light, so that water molecules, which are polar molecules, are selectively adsorbed over hydrophobic molecules. Easy to make. Therefore, a stable physically adsorbed water layer is easily formed, and even if the layer is kept in a dark place, the hydrophilicity of the surface can be maintained at a high level for a considerably long period.

【０００８】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.

【０００９】[0009]

【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。本発明におけるガードフェンス表面に
は、図１又は図２に示すように、基材の表面に光触媒
（結晶）性酸化物等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、ガードフェンスの表面は、
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、降雨により前記表面層の表面に付着する堆
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. On the surface of the guard fence in the present invention, as shown in FIG. 1 or 2, a layer containing a photocatalytic (crystalline) oxide or the like is formed on the surface of the base material. By taking such a surface structure, the surface of the guard fence is
It becomes highly hydrophilic in response to photoexcitation of the photocatalyst.
As a result, the deposits and / or contaminants attached to the surface of the surface layer due to rainfall are washed away by the raindrops.

【００１０】図１においては、表面層が光触媒性酸化物
粒子のみからなる。この場合、光触媒が酸化物からなる
ことにより、酸化物は環境中の汚染物質が吸着していな
い状態では親水性を示すので、光励起作用によりその汚
染物質を排斥させ、吸着水層を形成させることで、親水
性を呈しやすく、一様な水膜が形成できる。図２におい
て、Ｍは金属元素を示す。従って、図２の場合、最表面
は一般の無機酸化物からなる。この場合も、酸化物は環
境中の汚染物質が吸着していない状態では親水性を示す
ので、上記無機酸化物以外に表面層に混入する光触媒性
酸化物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, the surface layer consists only of photocatalytic oxide particles. In this case, since the photocatalyst is made of an oxide, the oxide shows hydrophilicity in a state where the pollutant in the environment is not adsorbed, so that the photoexcited action is to eliminate the pollutant to form an adsorbed water layer. Thus, it is easy to exhibit hydrophilicity and 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. Also in this case, since the oxide shows hydrophilicity in the state where the pollutant in the environment is not adsorbed, the pollutant is excluded by the photoexcitation action of the photocatalytic oxide mixed in the surface layer in addition to the above inorganic oxide. By forming the adsorbed water layer, a uniform water film can be formed.

【００１１】本発明が利用できるガードフェンス基材に
は、アルミニウム板、鋼板、ステンレス板、チタン板等
が使用できる。ここでガードフェンス基材が鋼板、ステ
ンレス板等のＦｅ、Ｎｉ、Ｃｏのいずれかの原子を含有
する基材である場合に、基材上に上記表面層を形成する
には基材と表面層の間に中間層を設けたほうがよい。Ｆ
ｅ、Ｎｉ、Ｃｏのいずれかの原子が表面層に混入する
と、親水化速度が低下するからである。As the guard fence base material to which the present invention can be applied, an aluminum plate, a steel plate, a stainless plate, a titanium plate or the like can be used. Here, when the guard fence base material is a base material containing any atom of Fe, Ni, Co such as a steel plate or a stainless steel plate, the base material and the surface layer are used to form the surface layer on the base material. It is better to provide an intermediate layer between them. F
This is because if one of the atoms e, Ni, or Co is mixed in the surface layer, the hydrophilization rate will decrease.

【００１２】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、光触媒性酸化チタ
ンとは、例えば、アナターゼ型酸化チタン、ルチル型酸
化チタン等の結晶性酸化チタンをいう。ここで光触媒の
光励起に用いる光源は、日中は太陽の照射に晒されるの
で、太陽光が利用できる。また、夜間は道路照明や走行
車の照明灯を光源として利用できる。光触媒の光励起に
より、基材表面が高度に親水化されるためには、励起光
の照度は、０．００１ｍＷ／ｃｍ２以上あればよいが、
０．０１ｍＷ／ｃｍ２以上だと好ましく、０． １ｍＷ
／ｃｍ２以上だとより好ましい。A photocatalyst is a photocatalyst of an electron in the valence band when it is 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. Excitation (photoexcitation) refers to a substance capable of generating conduction electrons and holes, and the photocatalytic titanium oxide refers to crystalline titanium oxide such as anatase type titanium oxide and rutile type titanium oxide. Here, the light source used for photoexcitation of the photocatalyst is exposed to the sun during the day, so sunlight can be used. Also, at night, road lighting or running vehicle lighting can be used as a light source. In order for the surface of the base material to be highly hydrophilic by the photoexcitation of the photocatalyst, the illuminance of the excitation light may be 0.001 mW / cm 2 or more,
It is preferably 0.01 mW / cm 2 or more, and 0. 1 mW
/ Cm 2 or more is more preferable.

【００１３】光触媒性酸化チタンを含有する表面層の膜
厚は、０．４μｍ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、光触媒性酸化チタン
を含有する表面層の膜厚を０．２μｍ以下にすると一層
好ましい。そうすれば、光の干渉による表面層の発色を
防止することができる。また、表面層が薄ければ薄いほ
どその透明度は向上する。更に、膜厚を薄くすれば、表
面層の耐摩耗性が向上する。上記表面層の表面に、更
に、親水化可能な耐摩耗性又は耐食性の保護層や他の機
能膜を設けても良い。The thickness of the surface layer containing the photocatalytic titanium oxide is preferably 0.4 μm or less. Then, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, it is more preferable that the thickness of the surface layer containing the photocatalytic titanium oxide be 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. 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.

【００１４】上記表面層には、Ａｇ、Ｃｕ、Ｚｎのよう
な金属を添加することができる。前記金属を添加した表
面層は、表面に付着した細菌や黴を暗所でも死滅させる
ことができる。A metal such as Ag, Cu, or Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.

【００１５】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。この場合にも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。The surface layer has 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, since the acidity of the solid acid is improved by the addition, the hydrophilicity-maintaining property is also improved, and the formation of a water film of the attached water is further promoted, and the hydrophilicity-maintaining property when the photocatalyst is not irradiated with the excitation light for a certain period of time. Also improves.

【００１６】親水性とは、表面に水を滴下したときにな
じみやすい性質をいい、一般に水濡れ角が９０゜未満の
状態をいう。本発明における高度の親水性とは、表面に
水を滴下したときに非常になじみやすい性質をいい、よ
り具体的には水濡れ角が１０゜以下程度になる状態をい
う。特に、防曇性にはＰＣＴ／ＪＰ９６／００７３４に
開示したように、水濡れ角が１０゜以下であると好まし
く、５゜以下ではより好ましい。The term "hydrophilic" refers to the property of being easily conformed when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The term “high hydrophilicity” in the present invention refers to a property that is highly compatible when water is dropped on the surface, and more specifically, a state where the water wetting angle is about 10 ° or less. In particular, as disclosed in PCT / JP96 / 00734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less, as disclosed in PCT / JP96 / 00734.

【００１７】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 in the present invention includes sulfuric acid carrying 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.

【００１８】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性酸化物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 photocatalytic oxide 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.

【００１９】次に、表面層が光触媒性酸化物とシリカか
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 photocatalytic oxide 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 a sol coating and firing method, the other is an organic titanate method, and the other is a tetrafunctional 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.

【００２０】次に、表面層が光触媒性酸化物と固体酸か
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
ン被膜を形成後、タングステン酸を塗布し、その後、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 photocatalytic oxide 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, a method of mixing an ammonia solution of tungstic acid and an anatase-type titanium oxide sol and, if necessary, diluting the mixture with a diluting liquid (water, ethanol, etc.) on the surface of the base material by spray coating, dip coating, or the like. It is applied by a method such as a flow coating method, a spin coating method, and a roll coating method, and is 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 form an amorphous titanium oxide film, and then tungstic acid is applied, and then amorphous. Heat treatment is performed at a temperature at which titanium oxide is crystallized and a TiO 2 / WO 3 composite oxide is formed.

【００２１】次に、表面層が光触媒性酸化物とシリコー
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 photocatalytic oxide 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. Is applied to the surface of the substrate 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 the hydrolyzate of the silicone precursor is dehydrated and polycondensed by a method such as heating. Then, a surface layer composed of anatase type titanium oxide particles and silicone is formed. In the formed surface layer, at least a part of the organic group bonded to the silicon atom in the silicone molecule is replaced with a hydroxyl group by photoexcitation of the anatase type titanium oxide by irradiation with light including ultraviolet rays, and further thereon. A physisorbed water layer is formed and 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, diethyldi Propoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, and their hydrolysates and their mixtures are preferably used. it can.

【００２２】[0022]

【実施例】【Example】

実施例１．１０ｃｍ角のアルミニウム板の表面にシリカ
ゾル（日本合成ゴム、グラスカＡ液、固形分２０重量
％、ｐＨ＝４）３重量部を混合後、メチルトリメトキシ
シラン（日本合成ゴム、グラスカＢ液）１重量部とエタ
ノールを添加し、さらに２時間撹拌し、メチルトリメト
キシシランを部分的に加水分解反応と脱水縮重合反応に
付することにより、コーティング液を調製した。このコ
ーティング液をフローコーティング法により塗布した
後、１５０℃で３０分間加熱し、アルミニウム板の表面
にベースコート層を形成した。次に、アナターゼ型酸化
チタンゾル（日産化学、ＴＡ−１５、固形分１５重量
％、硝酸解膠型、ｐＨ＝１）５６重量部と、シリカゾル
（日本合成ゴム、グラスカＡ液、固形分２０重量％、ｐ
Ｈ＝４）３３重量部を混合後、メチルトリメトキシシラ
ン（日本合成ゴム、グラスカＢ液）１１重量部とエタノ
ールを添加し、さらに２時間撹拌し、メチルトリメトキ
シシランを部分的に加水分解反応と脱水縮重合反応に付
することにより、コーティング液を調製した。このコー
ティング液をフローコーティング法により、ベースコー
ト層の表面に塗布した後、１５０℃で３０分間加熱し
て、表面層を形成した。次に、コーティング液を塗布し
た面に、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０．５ｍＷ／ｃｍ２の紫
外線照度で約３日紫外線を照射し、＃１試料を得た。比
較のため、アルミニウム板＃２試料も準備した。＃１試
料と＃２試料に水滴を滴下し、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、＃２試料では水との接触
角が５０゜と高い値を示したのに対し、＃１試料では水
との接触角が０゜と高度の親水性を示した。Example 1 3 parts by weight of silica sol (Nippon Synthetic Rubber, Glasca A liquid, solid content 20% by weight, pH = 4) was mixed on the surface of a 10 cm square aluminum plate, and then methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B was added. Liquid) 1 part by weight and ethanol were added, and the mixture was further stirred for 2 hours, and a coating liquid was prepared by partially subjecting methyltrimethoxysilane to a hydrolysis reaction and a dehydration polycondensation reaction. After applying this coating liquid by a flow coating method, it was heated at 150 ° C. for 30 minutes to form a base coat layer on the surface of the aluminum plate. Next, 56 parts by weight of anatase-type titanium oxide sol (Nissan Chemical Co., Ltd., TA-15, solid content 15% by weight, nitric acid deflocculation type, pH = 1) and silica sol (Nippon Synthetic Rubber, Glasca A liquid, solid content 20% by weight). , P
H = 4) After mixing 33 parts by weight, 11 parts by weight of methyltrimethoxysilane (Nippon Synthetic Rubber, Liquid Glasco B) and ethanol were added, and the mixture was further stirred for 2 hours to partially hydrolyze methyltrimethoxysilane. And a dehydration polycondensation reaction to prepare a coating liquid. This coating liquid was applied to the surface of the base coat layer by a flow coating method, and then heated at 150 ° C. for 30 minutes to form a surface layer. Next, the surface coated with the coating liquid was irradiated with ultraviolet rays for about 3 days at an ultraviolet illuminance of 0.5 mW / cm 2 using an ultraviolet light source ((Sankyo Denki, Black Light Blue (BLB) fluorescent lamp), and then # 1. A sample was obtained.For comparison, an aluminum plate # 2 sample was also prepared. Water droplets were dropped on the # 1 sample and the # 2 sample, and the contact angle with water was measured. Using a contact angle measuring device (Kyowa Interface Science, CA-X150), the contact angle with water 30 seconds after dropping was evaluated, and as a result, the contact angle with water of the # 2 sample was as high as 50 °. In contrast, the # 1 sample showed a high degree of hydrophilicity with a contact angle with water of 0 °.

【００２３】次に、＃１試料、＃２試料を屋外に設置し
て、降雨によるセルフクリーニング性について調べた。
降雨によるセルフクリーニング性は以下のようにして試
験した。すなわち、茅ケ崎市所在の建物の屋上に３図及
び４図に示す屋外汚れ加速試験装置を設置した。３図及
び４図を参照するに、この装置は、フレーム２０に支持
された傾斜した試料支持面２２を備え、試料２４を取り
付けるようになっている。フレームの頂部には前方に傾
斜した屋根２６が固定してある。この屋根は波形プラス
チック板からなり、集まった雨が試料支持面２２に取り
付けた試料２４の表面に筋を成して流下するようになっ
ている。この装置の試料支持面２２に＃１試料を取り付
け、１９９５年６月１２日から１か月間天候条件に暴露
した。この間梅雨時のため、頻繁に雨が降った。１か月
後に観察したところ、汚れは観察されなかった。その様
子を加速試験装置取り付け前後に最も顕著に汚れた部分
の色差変化で調べた。ここで色差は色差計（東京電色）
を用い、日本工業規格（ＪＩＳ）Ｈ０２０１に従い、Δ
Ｅ＊表示を用いて調べた。その結果、色差変化は０．８
と非常に小さかった。Next, the # 1 sample and the # 2 sample were installed outdoors and examined for self-cleaning property by rainfall.
The self-cleaning property by rainfall was tested as follows. That is, the outdoor stain acceleration test device shown in FIGS. 3 and 4 was installed on the roof of a building located in Chigasaki City. With reference to FIGS. 3 and 4, the apparatus includes an inclined sample support surface 22 supported by a frame 20 for mounting a sample 24. A roof 26 inclined forward is fixed to the top of the frame. The roof is made of a corrugated plastic plate, and the collected rain flows down in a streak on the surface of the sample 24 attached to the sample support surface 22. The # 1 sample was attached to the sample support surface 22 of this device and exposed to weather conditions for one month from June 12, 1995. During the rainy season, it rained frequently. When observed one month later, no stain was observed. The state was examined by the change in color difference of the most contaminated part before and after mounting the acceleration test device. Here, the color difference is a color difference meter (Tokyo Denshoku)
According to Japanese Industrial Standards (JIS) H0201, Δ
Checked using the E * designation. As a result, the color difference change is 0.8
And was very small.

【００２４】実施例２．１０ｃｍ角のステンレス板の表
面にシリカゾル（日本合成ゴム、グラスカＡ液、固形分
２０重量％、ｐＨ＝４）３重量部を混合後、メチルトリ
メトキシシラン（日本合成ゴム、グラスカＢ液）１重量
部とエタノールを添加し、さらに２時間撹拌し、メチル
トリメトキシシランを部分的に加水分解反応と脱水縮重
合反応に付することにより、コーティング液を調製し
た。このコーティング液をフローコーティング法により
塗布した後、１５０℃で３０分間加熱し、ステンレス板
の表面にベースコート層を形成した。次に、アナターゼ
型酸化チタンゾル（日産化学、ＴＡ−１５、固形分１５
重量％、硝酸解膠型、ｐＨ＝１）５６重量部と、シリカ
ゾル（日本合成ゴム、グラスカＡ液、固形分２０重量
％、ｐＨ＝４）３３重量部を混合後、メチルトリメトキ
シシラン（日本合成ゴム、グラスカＢ液）１１重量部と
エタノールを添加し、さらに２時間撹拌し、メチルトリ
メトキシシランを部分的に加水分解反応と脱水縮重合反
応に付することにより、コーティング液を調製した。こ
のコーティング液をフローコーティング法により、ベー
スコート層の表面に塗布した後、１５０℃で３０分間加
熱して、表面層を形成した。次に、コーティング液を塗
布した面に、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０．５ｍＷ／ｃｍ２
の紫外線照度で約３日紫外線を照射し、＃３試料を得
た。比較のため、ステンレス板＃４試料も準備した。＃
３試料と＃４試料に水滴を滴下し、水との接触角の測定
を行った。その結果、＃４試料では水との接触角が６０
゜と高い値を示したのに対し、＃３試料では水との接触
角が０゜と高度の親水性を示した。Example 2 3 parts by weight of silica sol (Nippon Synthetic Rubber, Glasca A liquid, solid content 20% by weight, pH = 4) was mixed on the surface of a 10 cm square stainless plate, and then methyltrimethoxysilane (Nippon Synthetic Rubber) , Glasca B solution) and ethanol were added, and the mixture was further stirred for 2 hours, and methyltrimethoxysilane was partially subjected to a hydrolysis reaction and a dehydration polycondensation reaction to prepare a coating solution. After applying this coating liquid by a flow coating method, it was heated at 150 ° C. for 30 minutes to form a base coat layer on the surface of the stainless steel plate. Next, anatase type titanium oxide sol (NISSAN CHEMICAL, TA-15, solid content 15
% By weight, nitric acid peptization type, pH = 1) 56 parts by weight, and silica sol (Japan Synthetic Rubber, Glask A liquid, solid content 20% by weight, pH = 4) 33 parts by weight are mixed, and then methyltrimethoxysilane (Japan 11 parts by weight of synthetic rubber (Glasca solution B) and ethanol were added, and the mixture was further stirred for 2 hours, and methyltrimethoxysilane was partially subjected to a hydrolysis reaction and a dehydration polycondensation reaction to prepare a coating solution. This coating liquid was applied to the surface of the base coat layer by a flow coating method, and then heated at 150 ° C. for 30 minutes to form a surface layer. Next, 0.5 mW / cm 2 was applied to the surface coated with the coating liquid by using an ultraviolet light source ((Sankyo Denki, Black Light Blue (BLB) fluorescent lamp).
The sample was irradiated with ultraviolet rays at a UV illuminance of 3 days for about 3 days to obtain a # 3 sample. A stainless plate # 4 sample was also prepared for comparison. #
Water droplets were dropped on the 3 samples and the # 4 sample, and the contact angle with water was measured. As a result, the contact angle with water of the # 4 sample was 60.
While the contact angle with water was 0 °, the sample # 3 showed a high degree of hydrophilicity.

【００２５】次に、＃３試料を屋外に設置して、降雨に
よるセルフクリーニング性について調べた。降雨による
セルフクリーニング性は以下のようにして試験した。す
なわち、茅ケ崎市所在の建物の屋上に３図及び４図に示
す屋外汚れ加速試験装置を設置した。３図及び４図を参
照するに、この装置は、フレーム２０に支持された傾斜
した試料支持面２２を備え、試料２４を取り付けるよう
になっている。フレームの頂部には前方に傾斜した屋根
２６が固定してある。この屋根は波形プラスチック板か
らなり、集まった雨が試料支持面２２に取り付けた試料
２４の表面に筋を成して流下するようになっている。こ
の装置の試料支持面２２に＃３試料を取り付け、１９９
５年６月１２日から１か月間天候条件に暴露した。この
間梅雨時のため、頻繁に雨が降った。１か月後に観察し
たところ、汚れは観察されなかった。その様子を加速試
験装置取り付け前後に最も顕著に汚れた部分の色差変化
で調べた。ここで色差は色差計（東京電色）を用い、日
本工業規格（ＪＩＳ）Ｈ０２０１に従い、ΔＥ＊表示を
用いて調べた。その結果、色差変化は０．９と非常に小
さかった。Next, the # 3 sample was placed outdoors and examined for self-cleaning property by rainfall. The self-cleaning property by rainfall was tested as follows. That is, the outdoor stain acceleration test device shown in FIGS. 3 and 4 was installed on the roof of a building located in Chigasaki City. With reference to FIGS. 3 and 4, the apparatus includes an inclined sample support surface 22 supported by a frame 20 for mounting a sample 24. A roof 26 inclined forward is fixed to the top of the frame. The roof is made of a corrugated plastic plate, and the collected rain flows down in a streak on the surface of the sample 24 attached to the sample support surface 22. Attach the # 3 sample to the sample support surface 22 of this device, 199
It was exposed to weather conditions for one month from June 12, 1993. During the rainy season, it rained frequently. When observed one month later, no stain was observed. The state was examined by the change in color difference of the most contaminated part before and after mounting the acceleration test device. Here, the color difference was examined using a color difference meter (Tokyo Denshoku) according to the Japanese Industrial Standards (JIS) H0201 and using ΔE * display. As a result, the change in color difference was 0.9, which was very small.

【００２６】実施例３．１０ｃｍ角のステンレス板を濃
度３．５重量％のテトラエトキシシラン溶液（希釈剤：
エタノール、加水分解触媒：塩酸）に浸漬後、毎分２４
ｃｍの速度で引き上げて、溶液をディップコーティング
法により、ステンレス板の表面に塗布し、乾燥させた。
ここまでの工程により、テトラエトキシシランは加水分
解を受けてシラノール基が生成し、続いてシラノール基
が脱水縮重合して、無定型シリカを主要成分とする薄膜
が表面に形成された。次に、濃度３．５重量％のテトラ
エトキシチタン溶液（希釈剤：エタノール、加水分解触
媒：塩酸）に浸漬後、毎分２４ｃｍの速度で引き上げ
て、溶液をディップコーティング法により、ステンレス
板の表面に塗布し、乾燥させて、＃５試料を得た。ここ
までの工程により、テトラエトキシチタンは加水分解を
受けて水酸基が生成し、続いて水酸基が脱水縮重合し
て、無定型酸化チタンを主要成分とする薄膜が表面に形
成された。次に、＃５試料表面を、コロナ放電処理（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
波コロナ放電処理することにより脱アルキル処理した。
次に、＃５試料表面を、１重量％のタングステン酸溶液
（溶媒：アンモニア水）に浸漬後、毎分２４ｃｍの速度
で引き上げて、溶液をディップコーティング法により、
表面に塗布し、５００℃で焼成して＃６試料を得た。焼
成により、無定型酸化チタンが結晶化してアナターゼ型
酸化チタンが生成した。次に、この＃６試料を数日間暗
所に放置した後、ＢＬＢ蛍光灯を用いて試料の表面に
０．５ｍＷ／ｃｍ２の紫外線照度で約１時間紫外線を照
射し、＃７試料を得た。比較のため、１０ｃｍ角のステ
ンレス板を数日間暗所に放置した＃８試料も準備した。
まず、＃７試料と＃８試料に水滴を滴下し、滴下後の様
子の観察及び水との接触角の測定を行った。その結果＃
７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、＃８試料ではマ
イクロシリンジから試料表面に水滴を滴下されると、水
滴は表面になじんでいくものの、一様に水膜状になるま
でには至らなかった。また３０秒後の水との接触角は６
０゜であった。さらに、＃８試料を、その後２日間暗所
に放置し、＃９試料を得た。そして＃９試料について、
同様に水との接触角を接触角測定器により測定した。そ
の結果、＃９試料にマイクロシリンジから試料表面に水
滴を滴下されると、＃７試料と同様に、水滴が一様に水
膜状に試料表面を拡がる様子が観察された。また水との
接触角は約１゜に維持された。Example 3 A 10 cm square stainless steel plate was used to prepare a 3.5 wt% tetraethoxysilane solution (diluent:
24 minutes per minute after immersion in ethanol and hydrolysis catalyst: hydrochloric acid
It was pulled up at a speed of cm, and the solution was applied to the surface of the stainless plate by the dip coating method and dried.
Through the steps so far, tetraethoxysilane was hydrolyzed to generate silanol groups, and then the silanol groups were subjected to dehydration polycondensation to form a thin film containing amorphous silica as a main component on the surface. Next, after dipping in a tetraethoxy titanium solution (diluent: ethanol, hydrolysis catalyst: hydrochloric acid) with a concentration of 3.5% by weight, the solution is pulled up at a rate of 24 cm / min, and the solution is dip-coated to the surface of the stainless steel plate. And then dried to obtain # 5 sample. Through the steps up to this point, tetraethoxy titanium was hydrolyzed to generate a hydroxyl group, and then the hydroxyl group was dehydrated and polycondensed to form a thin film containing amorphous titanium oxide as a main component on the surface. Next, the # 5 sample surface was subjected to corona discharge treatment (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, the frequency was 39 kHz, and the sample feed rate was 4.2 m / min. Under the conditions, dealkylation treatment was performed by high-frequency corona discharge treatment.
Next, after dipping the # 5 sample surface in a 1 wt% tungstic acid solution (solvent: ammonia water), the sample was pulled up at a rate of 24 cm / min, and the solution was dip-coated.
It was applied on the surface and baked at 500 ° C. to obtain a # 6 sample. By firing, the amorphous titanium oxide was crystallized to produce anatase titanium oxide. Next, after leaving this # 6 sample in a dark place for several days, the surface of the sample was irradiated with ultraviolet rays at a UV illuminance of 0.5 mW / cm 2 for about 1 hour using a BLB fluorescent lamp to obtain a # 7 sample. It was For comparison, a # 8 sample in which a 10 cm square stainless plate was left in the dark for several days was also prepared.
First, water drops were dropped on the # 7 sample and the # 8 sample, and the state after the drop was observed and the contact angle with water was measured. as a result#
When water droplets were dropped on the surface of the 7 samples from the microsyringe, it was observed that the water droplets spread uniformly on the surface of the sample 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 # 8 sample, when a water droplet was dropped from the microsyringe on the surface of the sample, the water droplet adapted to the surface but did not reach a uniform water film shape. The contact angle with water after 30 seconds is 6
It was 0 °. Further, the # 8 sample was left in the dark for 2 days thereafter to obtain a # 9 sample. And for # 9 sample,
Similarly, the contact angle with water was measured by a contact angle measuring device. As a result, when water droplets were dropped onto the sample surface from the microsyringe on the # 9 sample, it was observed that the water droplets spread uniformly on the sample surface in the form of a water film, similarly to the # 7 sample. The contact angle with water was maintained at about 1 °.

【００２７】次に＃７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、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 # 7 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, the oleic acid became round and separated from the surface by light rubbing.

【００２８】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＃７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＊表示を用いて評価
した。その結果、＃７試料の試験前後の色差変化は０．
４とほとんど変化しなかった。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 # 7 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 change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standards (JIS) H0201 using ΔE * notation. As a result, the change in color difference of the # 7 sample before and after the test was 0.
There was almost no change from 4.

【００２９】[0029]

【発明の効果】本発明では、ガードフェンス基材の表面
に、光触媒性酸化物粒子を含有する表面層を備えること
により、光触媒の光励起に応じて、表面層の表面は親水
性を呈する。それにより、降雨により前記表面層の表面
はセルフクリーニングされるようになる。According to the present invention, the surface of the guard fence substrate is provided with a surface layer containing photocatalytic oxide particles, whereby the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst. As a result, the surface of the surface layer is self-cleaned by the rainfall.

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

【図１】 本発明に係るガードフェンスの表面構造を示
す図。FIG. 1 is a diagram showing a surface structure of a guard fence according to the present invention.

【図２】 本発明に係るガードフェンスの他の表面構造
を示す図。FIG. 2 is a diagram showing another surface structure of the guard fence according to the present invention.

【図３】 本発明の実施例に係る屋外汚れ加速試験装置
の正面図。FIG. 3 is a front view of an outdoor dirt acceleration test apparatus according to an embodiment of the present invention.

【図４】 本発明の実施例に係る屋外汚れ加速試験装置
の側面図。FIG. 4 is a side view of an outdoor dirt acceleration test device according to an embodiment of the present invention.

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 ガードフェンス基材の表面に、光触媒性
酸化物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、前記ガード
フェンス表面が、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せるのを可能にす
るセルフクリーニング性ガードフェンス。1. A surface of a guard fence substrate is provided with a surface layer containing photocatalytic oxide particles, the surface of the layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, and the surface of the guard fence is A self-cleaning guard fence that allows deposited deposits and / or contaminants to be washed away by raindrops when exposed to rainfall. 【請求項２】 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に記載のセルフクリ
ーニング性ガードフェンス。2. The self-cleaning guard fence according to claim 1, wherein the surface layer further contains silica. 【請求項３】 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に記載のセルフクリ
ーニング性ガードフェンス。3. The self-cleaning guard fence according to claim 1, wherein the surface layer further contains a solid acid. 【請求項４】 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に記載のセルフ
クリーニング性ガードフェンス。4. The self-cleaning guard fence according to claim 1, wherein the surface layer further contains silicone. 【請求項５】 前記表面層の表面は、前記光触媒性酸化
物が光励起されることに応じて、水との接触角に換算し
て１０゜以下の親水性を呈することを特徴とする請求項
１〜４に記載のセルフクリーニング性ガードフェンス。5. 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 photocatalytic oxide. The self-cleaning guard fence described in 1 to 4. 【請求項６】 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〜
５に記載のセルフクリーニング性ガードフェンス。6. The method according to claim 1, wherein a protective layer capable of being made hydrophilic is further provided on the surface of the surface layer.
The self-cleaning guard fence according to item 5. 【請求項７】 前記ガードフェンス基材は、鋼材又はス
テンレスからなり、前記ガードフェンス基材と前記表面
層の間には中間層が設けられていることを特徴とする請
求項１〜６に記載のセルフクリーニング性ガードフェン
ス。7. The guard fence base material is made of steel or stainless steel, and an intermediate layer is provided between the guard fence base material and the surface layer. Self-cleaning guard fence. 【請求項８】 前記ガードフェンス基材は、ガードレー
ル基材である請求項１〜７に記載のセルフクリーニング
性ガードフェンス。8. The self-cleaning guard fence according to claim 1, wherein the guard fence base material is a guard rail base material. 【請求項９】 前記ガードフェンス基材は、ガードパイ
プ基材である請求項１〜７に記載のセルフクリーニング
性ガードフェンス。9. The self-cleaning guard fence according to claim 1, wherein the guard fence base material is a guard pipe base material. 【請求項１０】 請求項１〜９のガードフェンスを準備
する工程、前記ガードフェンスを屋外に配置する工程、
前記表面層に含有される光触媒を光励起することによ
り、前記表面層の表面を親水性になす工程、前記基材を
降雨にさらして、前記表面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
るガードフェンスのセルフクリーニング方法。10. A step of preparing the guard fence according to claim 1, a step of arranging the guard fence outdoors,
Photoexciting a photocatalyst contained in the surface layer to make the surface of the surface layer hydrophilic, deposits and / or contaminants attached to the surface of the surface layer by exposing the substrate to rainfall A method of self-cleaning the guard fence, which comprises the step of rinsing off with raindrops.
JP28895496A 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence Expired - Fee Related JP3588205B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28895496A JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP35464995 1995-12-22
JP7-354649 1995-12-22
JP28895496A JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence

Publications (2)

Publication Number Publication Date
JPH09228331A true JPH09228331A (en) 1997-09-02
JP3588205B2 JP3588205B2 (en) 2004-11-10

Family

ID=18438979

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JP13408196A Expired - Lifetime JP3385850B2 (en) 1995-12-22 1996-04-19 Composite material with hydrophilicity
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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
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JP8168643A Pending JPH09232096A (en) 1995-12-22 1996-06-06 Electrification preventing method, and electrification preventive composite material
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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
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JP8195184A Expired - Lifetime JP3003581B2 (en) 1995-12-22 1996-06-20 A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor
JP8272814A Pending JPH09226041A (en) 1995-12-22 1996-09-06 Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member
JP8272815A Pending JPH09224957A (en) 1995-12-22 1996-09-06 Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop
JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
JP8272808A Pending JPH09229724A (en) 1995-12-22 1996-09-07 Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover
JP8238927A Pending JPH09227159A (en) 1995-12-22 1996-09-10 Front and rear window glass of vehicle
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
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
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
JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
JP8281225A Pending JPH09230107A (en) 1995-12-22 1996-09-17 Anti-fogging glass lens and its anti-fogging method
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
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
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
JP8282810A Pending JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method
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
JP8282806A Pending JPH09228057A (en) 1995-12-22 1996-09-18 Wheel and its cleaning method
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method
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
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
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
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
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
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
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
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 (40)

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
JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
JP8272808A Pending JPH09229724A (en) 1995-12-22 1996-09-07 Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover
JP8238927A Pending JPH09227159A (en) 1995-12-22 1996-09-10 Front and rear window glass of vehicle
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
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
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
JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
JP8281225A Pending JPH09230107A (en) 1995-12-22 1996-09-17 Anti-fogging glass lens and its anti-fogging method
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
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
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
JP8282810A Pending JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method
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
JP8282806A Pending JPH09228057A (en) 1995-12-22 1996-09-18 Wheel and its cleaning method
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method
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
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

Family Applications After (30)

Application Number Title Priority Date Filing Date
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
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
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
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
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
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)

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JP (71) JPH09231821A (en)

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JPH09224490A (en) 1997-09-02
JPH09232096A (en) 1997-09-05
JP3141802B2 (en) 2001-03-07
JP3612896B2 (en) 2005-01-19
JP3613085B2 (en) 2005-01-26
JP3063968B2 (en) 2000-07-12
JPH09226060A (en) 1997-09-02
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JP3348613B2 (en) 2002-11-20
JPH09230106A (en) 1997-09-05
JP3277983B2 (en) 2002-04-22
JP3075195B2 (en) 2000-08-07
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JP3774955B2 (en) 2006-05-17
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JPH09225021A (en) 1997-09-02
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