JP3760509B2 - Greenhouse ceiling and its condensation prevention method - Google Patents

Greenhouse ceiling and its condensation prevention method Download PDF

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JP3760509B2
JP3760509B2 JP15017196A JP15017196A JP3760509B2 JP 3760509 B2 JP3760509 B2 JP 3760509B2 JP 15017196 A JP15017196 A JP 15017196A JP 15017196 A JP15017196 A JP 15017196A JP 3760509 B2 JP3760509 B2 JP 3760509B2
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photocatalyst
layer
greenhouse
ceiling
water
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JPH09224490A (en
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信 早川
俊也 渡部
厚 北村
真 千国
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東陶機器株式会社
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    • 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

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  • Surface Treatment Of Glass (AREA)
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  • 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)
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  • Refuge Islands, Traffic Blockers, Or Guard Fence (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
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  • Rear-View Mirror Devices That Are Mounted On The Exterior Of The Vehicle (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Panels For Use In Building Construction (AREA)
  • Bridges Or Land Bridges (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Greenhouses (AREA)
  • Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
  • Physical Vapour Deposition (AREA)
  • Optical Radar Systems And Details Thereof (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は、ビニールハウスの天井の結露集中防止構造および方法に関する。
【０００２】
【従来の技術】
農業の分野ではビニールシートで形成されたビニールハウスが簡便な温室として利用されている。
【０００３】
【発明が解決しようとする課題】
ビニールハウスの内面が露点以下の温度になるとビニールハウス内の空気中の湿分が凝縮し、ビニールハウスの内面に結露が生じる。ビニールハウスの天井に結露した凝縮水は互いに融合して次第に大きな水滴に成長し、充分に大きくなると天井から離れて自重により落下する。凝縮水滴の落下点は天井の特定の決まって箇所に集中する傾向にある。このため、落下点直下の農作物に根腐れが生じるという問題が指摘されている。
【０００４】
本発明の目的は、凝縮水滴の落下点が天井の特定の位置に集中することのないビニールハウス天井構造を提供することにある。
本発明の他の目的は、凝縮水滴の落下点が天井の特定の位置に集中するのを防止する方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者は、光触媒を光励起すると光触媒の表面が高度に親水化されることを発見した。驚ろくべきことに、光触媒性チタニアを紫外線で光励起したところ、水との接触角が１０゜以下、より詳しくは５゜以下、特に約０゜になる程度に表面が高度に親水化されることが発見された。
【０００６】
本発明は斯る発見に基づくもので、本発明によれば、ビニールハウスの天井の内面は半導体光触媒を含む透明層で被覆されている。
ビニールハウスを圃場に設置すると、ビニールハウスは日中は太陽の照射を受け、太陽光はビニールシートを透過して天井内面の光触媒含有層の光触媒を光励起する。光励起に伴い、光触媒含有層の表面は水との接触角が１０゜以下、好ましくは５゜以下、より好ましくは約０゜になる程度に親水化される。
一旦親水化されると、光触媒含有層の表面の親水性は夜間でも維持される。夜間に作物を照射するべくビニールハウスに蛍光灯などの人工光源が設けてある場合には、光触媒は夜間にも光励起される。
【０００７】
このように天井内面の光触媒含有層の表面は高度に親水化されているので、寒冷時や夜間に結露が生じたときには、凝縮水は光触媒含有層の表面に一様に広がり、一様な水膜を形成する。結露の進行に伴い水膜の厚さが増すと、凝縮水は、天井から垂れ下がった水滴を形成することなく、水膜を形成したままビニールハウスの側壁に沿って流下する。従って、ビニールハウスの天井の特定の位置から凝縮水滴が落下することがない。
【０００８】
光触媒としては、アナターゼ型チタニア（TiO2）が最も好ましい。チタニアは、無害であり、化学的に安定であり、かつ、安価に入手可能である。ルチル型チタニアも使用可能である。光触媒性チタニアを紫外線によって光励起すると、光触媒作用によって水が水酸基（OH-）の形で表面に化学吸着され、その結果、表面が超親水性になると考えられる。使用可能な他の光触媒としては、ZnO、SnO2、SrTiO3、WO3、Bi2O3、Fe2O3のような金属酸化物がある。これらの金属酸化物は、チタニアと同様に、表面に金属元素と酸素が存在するので、表面水酸基（OH-）を吸着しすいと考えられる。光触媒含有層の膜厚は０.２μｍ以下にするのが好ましい。このようにすれば、充分な透明性を確保することができる。
【０００９】
光触媒含有層は光触媒の粒子を無定形シリカによってビニールシートに結着することにより形成することができる。このため、結晶性チタニアゾルと無定形シリカの前駆体（例えば、テトラエトキシシラン、テトライソプロポキシシラン、テトラｎ−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、等のテトラアルコキシシラン；それらの加水分解物であるシラノール； 又は平均分子量3000以下のポリシロキサン）との混合物をビニールシートの表面に塗布し、必要に応じて加水分解させてシラノールを形成した後、約100℃以上の温度で加熱してシラノールを脱水縮重合に付すことにより、チタニアが無定形シリカで結着された光触媒含有層を形成する。
【００１０】
水との接触角が０゜になる程度の超親水性を呈する光触媒層を形成する他の好ましいやり方は、未硬化の若しくは部分的に硬化したシリコーン（ケイ素樹脂）又はシリコーンの前駆体からなる塗膜形成要素に光触媒の粒子を分散させてなる塗料用組成物を用いることである。この塗料用組成物をビニールシートの表面に塗布し、塗膜形成要素を硬化させた後、光触媒を光励起すると、シリコーン分子のケイ素原子に結合した有機基は光触媒の光触媒作用により水酸基に置換され、光触媒層の表面は超親水化される。
【００１１】
このやり方には、幾つかの利点がある。シリコーン塗料は常温又は比較的低温で硬化させることができるので、ビニールシートのような非耐熱性の材料で形成されている基材にも適用することができる。光触媒を含有したこの塗料用組成物は、刷毛塗り、スプレーコーティング、ロールコーティングなどにより塗布することができる。シリコーン塗料はシロキサン結合を有するので、光触媒の光酸化作用に対する充分な対抗性を有する。光触媒含有シリコーン塗料からなる光触媒性コーティングの更に他の利点は、表面が一旦超親水化された後には、暗所に保持しても長期間超親水性を維持し、かつ、蛍光灯のような室内照明灯の光でも超親水性を回復することである。
【００１２】
この塗料用組成物の塗膜形成要素としては、メチルトリクロルシラン、メチルトリブロムシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリｔ−ブトキシシラン；エチルトリクロルシラン、エチルトリブロムシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、エチルトリｔ−ブトキシシラン；ｎ−プロピルトリクロルシラン、ｎ−プロピルトリブロムシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、ｎ−プロピルトリイソプロポキシシラン、ｎ−プロピルトリｔ−ブトキシシラン；ｎ−ヘキシルトリクロルシラン、ｎ−ヘキシルトリブロムシラン、ｎ−ヘキシルトリメトキシシラン、ｎ−ヘキシルトリエトキシシラン、ｎ−ヘキシルトリイソプロポキシシラン、ｎ−ヘキシルトリｔ−ブトキシシラン；ｎ−デシルトリクロルシラン、ｎ−デシルトリブロムシラン、ｎ−デシルトリメトキシシラン、ｎ−デシルトリエトキシシラン、ｎ−デシルトリイソプロポキシシラン、ｎ−デシルトリｔ−ブトキシシラン；ｎ−オクタデシルトリクロルシラン、ｎ−オクタデシルトリブロムシラン、ｎ−オクタデシルトリメトキシシラン、ｎ−オクタデシルトリエトキシシラン、ｎ−オクタデシルトリイソプロポキシシラン、ｎ−オクタデシルトリｔ−ブトキシシラン；フェニルトリクロルシラン、フェニルトリブロムシラン、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、フェニルトリイソプロポキシシラン、フェニルトリｔ−ブトキシシラン；テトラクロルシラン、テトラブロムシラン、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、ジメトキシジエトキシシラン；ジメチルジクロルシラン、ジメチルジブロムシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン；ジフェニルジクロルシラン、ジフェニルジブロムシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン；フェニルメチルジクロルシラン、フェニルメチルジブロムシラン、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；トリクロルヒドロシラン、トリブロムヒドロシラン、トリメトキシヒドロシラン、トリエトキシヒドロシラン、トリイソプロポキシヒドロシラン、トリｔ−ブトキシヒドロシラン；ビニルトリクロルシラン、ビニルトリブロムシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリｔ−ブトキシシラン；トリフルオロプロピルトリクロルシラン、トリフルオロプロピルトリブロムシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、トリフルオロプロピルトリイソプロポキシシラン、トリフルオロプロピルトリｔ−ブトキシシラン；γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリイソプロポキシシラン、γ−グリシドキシプロピルトリｔ−ブトキシシラン；γ−メタアクリロキシプロピルメチルジメトキシシラン、γ−メタアクリロキシプロピルメチルジエトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリエトキシシラン、γ−メタアクリロキシプロピルトリイソプロポキシシラン、γ−メタアクリロキシプロピルトリｔ−ブトキシシラン；γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノプロピルトリｔ−ブトキシシラン；γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルトリイソプロポキシシラン、γ−メルカプトプロピルトリｔ−ブトキシシラン；β−(３、４−エポキシシクロヘキシル)エチルトリメトキシシラン、β−(３、４−エポキシシクロヘキシル)エチルトリエトキシシラン；および、それらの部分加水分解物；およびそれらの混合物を使用することができる。
【００１３】
光触媒の光酸化作用によりビニールシートが劣化するのを防止するため、ビニールシートと光触媒層との間には光酸化対抗性の中間層を配置するのが好ましい。この中間層はシリコーン（ケイ素樹脂）、フッ素樹脂、又はシリカで形成することができる。
【００１４】
光触媒による超親水化現象は、光触媒による光酸化作用よりも弱い光触媒作用によって実現することができる。従って、ビニールシートの劣化を防止するための他のやり方は、光触媒の光酸化作用を抑制することである。このためには、光触媒含有層の膜厚を０.１μｍ以下にするか、光触媒含有層にアルカリ金属、アルカリ土類金属、アルミナ、シリカ、ジルコニア、酸化アンチモン、無定形チタニア、含水チタニアの１種又は２種以上を添加することができる。
【００１５】
【実施例】
実施例１
１０cm四角のビニールシートを予めシリコーン層で被覆した。このため、日本合成ゴムの塗料用組成物“グラスカ”のＡ液（シリカゾル）とＢ液（トリメトキシメチルシラン）をＡ液とＢ液との重量比が３：１になるように混合し、この混合液をビニールシートに塗布し、60℃の温度で硬化させ、膜厚３μｍのシリコーンのベースコートで被覆された試料を得た。
次に、アナターゼ型チタニアゾル（日産化学、TA-15）と前記“グラスカ”のＡ液を混合し、エタノールで希釈後、更に“グラスカ”の上記Ｂ液を添加し、チタニア含有塗料用組成物を調整した。この塗料用組成物の組成は、シリカ３重量部、トリメトキシメチルシラン１重量部、チタニア４重量部であった。この塗料用組成物を試料の表面に塗布し、150℃の温度で硬化させ、アナターゼ型チタニア粒子がシリコーン塗膜中に分散されたトップコートを形成した。
【００１６】
この試料の表面に20Wのブラックライトブルー蛍光灯（三共電気、FL20BLB）を用いて０.５mW／cm2の紫外線照度（アナターゼ型チタニアのバンドギャップエネルギより高いエネルギの紫外線の照度）で１週間紫外線を照射した後、表面の水との接触角を接触角測定器（協和界面科学社製、形式CA-X150）により測定した。この接触角測定器の低角度側検出限界は１゜であった。接触角は、マイクロシリンジから試料表面に水滴を滴下した後30秒後に測定した。測定器の読みは０゜であり、超親水性を示した。
次に、密閉容器中にこの試料の両端をテープで固定し、湯の入ったビーカを試料の下方に配置し、凝縮水の状態を観察した。凝縮水は一様な水膜になり、水滴の成長は認められなかった。
【００１７】
実施例２
１０cm四角のビニールシートを予め無定形シリカ層で被覆した。このため、エタノールの溶媒86重量部に、テトラエトキシシランSi(OC2H5)4（和光純薬）６重量部と純水６重量部とテトラエトキシシランの加水分解抑制剤として36％塩酸２重量部を加えて混合し、シリカコーティング溶液を調整した。混合により溶液は発熱するので、混合液を約１時間放置冷却した。この溶液をフローコーティング法によりビニールシートの表面に塗布し、50℃の温度で乾燥させた。乾燥に伴い、テトラエトキシシランは加水分解を受けて先ずシラノールSi(OH)4になり、続いてシラノールの脱水縮重合により無定形シリカの薄膜がビニールシートの表面に形成された。
次に、テトラエトキシシラン（和光純薬）0.69ｇとアナターゼ型チタニアゾル（日産化学、TA-15、平均粒径0.01μｍ）1.07ｇとエタノール29.88ｇと純水0.36ｇを混合し、コーティング溶液を調整した。このコーティング溶液をスプレーコーティング法によりビニールシートの表面に塗布した。このビニールシートを約20分間約150℃の温度に保持することにより、テトラエトキシシランを加水分解と脱水縮重合に付し、アナターゼ型チタニア粒子が無定形シリカのバインダーで結着されたコーティングをビニールシートの表面に形成した。チタニアとシリカの重量比は１であった。
【００１８】
この試料を実施例１と同様の条件で紫外線照射した後、表面の水との接触角を測定したところ、接触角は０゜であった。更に、実施例１と同様に湯の入ったビーカの上方に試料を配置したところ、水滴の成長は認められなかった。
【００１９】
比較例
比較のため、実施例で用いたのと同一のビニールシートに実施例１と同様の条件で紫外線を照射した後、表面の水との接触角を接触角測定器で測定したところ、水との接触角は７０゜であった。湯の入ったビーカの上方に試料を配置したところ、水滴の成長が確認された。
【００２０】
【発明の効果】
以上の試験から分かるように、本発明によれば、ビニールハウスの天井に結露が生じても、凝縮水は光触媒層の表面に一様に広がり、一様な水膜を形成するので、凝縮水滴が天井の決まった箇所から落下することがない。従って、作物の根腐れを防止することができる。また、天井の決まった箇所の直下の圃場に根腐れが生じないので、作付け面積を確保し、収穫量を向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a structure and method for preventing condensation on a ceiling of a greenhouse.
[0002]
[Prior art]
In the agricultural field, a plastic house made of plastic sheets is used as a simple greenhouse.
[0003]
[Problems to be solved by the invention]
When the inner surface of the greenhouse becomes below the dew point, moisture in the air in the greenhouse condenses and condensation occurs on the inner surface of the greenhouse. Condensed water condensed on the ceiling of the greenhouse merges and grows into large drops of water, and when it becomes large enough, it falls off the ceiling and falls under its own weight. The falling point of condensed water drops tends to concentrate on a specific fixed point on the ceiling. For this reason, it has been pointed out that root rot occurs in crops just below the drop point.
[0004]
An object of the present invention is to provide a greenhouse ceiling structure in which the falling points of condensed water droplets do not concentrate at a specific position on the ceiling.
Another object of the present invention is to provide a method for preventing the falling points of condensed water droplets from being concentrated at a specific position on the ceiling.
[0005]
[Means for Solving the Problems]
The inventor has discovered that photoexcitation of the photocatalyst results in a highly hydrophilic surface of the photocatalyst. Surprisingly, when photocatalytic titania is photoexcited with ultraviolet rays, the surface becomes highly hydrophilic so that the contact angle with water is 10 ° or less, more specifically 5 ° or less, especially about 0 °. Was discovered.
[0006]
The present invention is based on such discovery, and according to the present invention, the inner surface of the ceiling of the greenhouse is coated with a transparent layer containing a semiconductor photocatalyst.
When the greenhouse is installed in a farm, the greenhouse is exposed to the sun during the day, and sunlight passes through the vinyl sheet to photoexcite the photocatalyst of the photocatalyst containing layer on the inner surface of the ceiling. With photoexcitation, the surface of the photocatalyst-containing layer is hydrophilized so that the contact angle with water is 10 ° or less, preferably 5 ° or less, more preferably about 0 °.
Once hydrophilic, the surface hydrophilicity of the photocatalyst containing layer is maintained at night. When an artificial light source such as a fluorescent lamp is provided in a greenhouse to irradiate crops at night, the photocatalyst is photoexcited at night.
[0007]
Since the surface of the photocatalyst-containing layer on the inner surface of the ceiling is highly hydrophilic in this way, when condensation occurs during cold weather or at night, the condensed water spreads uniformly on the surface of the photocatalyst-containing layer, and the uniform water A film is formed. When the thickness of the water film increases with the progress of dew condensation, the condensed water flows down along the side wall of the greenhouse without forming a water drop hanging from the ceiling. Therefore, the condensed water droplet does not fall from a specific position on the ceiling of the greenhouse.
[0008]
As the photocatalyst, anatase type titania (TiO 2 ) is most preferable. Titania is harmless, chemically stable, and available at low cost. Rutile type titania can also be used. It is considered that when photocatalytic titania is photoexcited by ultraviolet rays, water is chemically adsorbed on the surface in the form of hydroxyl groups (OH − ) by photocatalysis, and as a result, the surface becomes superhydrophilic. Other photocatalysts which can be used include metal oxides such as ZnO, SnO 2, SrTiO 3, WO 3, Bi 2 O 3, Fe 2 O 3. Since these metal oxides, like titania, contain metal elements and oxygen on the surface, it is thought that surface hydroxyl groups (OH − ) should be adsorbed. The film thickness of the photocatalyst containing layer is preferably 0.2 μm or less. In this way, sufficient transparency can be ensured.
[0009]
The photocatalyst-containing layer can be formed by binding photocatalyst particles to a vinyl sheet with amorphous silica. Therefore, a precursor of crystalline titania sol and amorphous silica (for example, tetraalkoxysilane such as tetraethoxysilane, tetraisopropoxysilane, tetra n-propoxysilane, tetrabutoxysilane, tetramethoxysilane, etc .; hydrolyzate thereof Or a polysiloxane having an average molecular weight of 3000 or less) is applied to the surface of the vinyl sheet, hydrolyzed as necessary to form silanol, and then heated at a temperature of about 100 ° C. or higher. Is subjected to dehydration condensation polymerization to form a photocatalyst-containing layer in which titania is bound with amorphous silica.
[0010]
Another preferred way of forming a photocatalytic layer exhibiting superhydrophilicity with a contact angle with water of 0 ° is a coating comprising an uncured or partially cured silicone (silicone resin) or a silicone precursor. A coating composition in which photocatalyst particles are dispersed in a film forming element is used. After coating the coating composition on the surface of the vinyl sheet and curing the coating film forming element, photoexcitation of the photocatalyst, the organic group bonded to the silicon atom of the silicone molecule is replaced with a hydroxyl group by the photocatalytic action of the photocatalyst, The surface of the photocatalyst layer is superhydrophilic.
[0011]
This approach has several advantages. Since the silicone paint can be cured at room temperature or at a relatively low temperature, it can be applied to a substrate formed of a non-heat resistant material such as a vinyl sheet. This coating composition containing a photocatalyst can be applied by brush coating, spray coating, roll coating or the like. Since the silicone paint has a siloxane bond, it has sufficient resistance to the photooxidation action of the photocatalyst. Still another advantage of a photocatalytic coating comprising a photocatalyst-containing silicone paint is that once the surface is made superhydrophilic, it remains superhydrophilic for a long period of time even in a dark place, and is It is to recover the super hydrophilicity even with the light of the interior lighting.
[0012]
The coating film forming element of this coating composition includes methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltrichlorosilane. Bromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxy Silane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyl Riethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyl Triisopropoxysilane, n-decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n- Octadecyltri-t-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxy Silane: Tetrachlorosilane, Tetrabromosilane, Tetramethoxysilane, Tetraethoxysilane, Tetrabutoxysilane, Dimethoxydiethoxysilane; Dimethyldichlorosilane, Dimethyldibromosilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane; Diphenyldichlorosilane , Diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, trimethyl Ethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyl Tribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltri Ethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; Liloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ -Methacryloxypropyltri-t-butoxysilane; gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltriisosilane Propoxysilane, γ-aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane; and partial hydrolysates thereof; and mixtures thereof.
[0013]
In order to prevent the vinyl sheet from being deteriorated by the photooxidation action of the photocatalyst, it is preferable to dispose a photooxidation-resistant intermediate layer between the vinyl sheet and the photocatalyst layer. This intermediate layer can be formed of silicone (silicon resin), fluororesin, or silica.
[0014]
The superhydrophilic phenomenon by the photocatalyst can be realized by a photocatalytic action weaker than the photooxidation action by the photocatalyst. Therefore, another way to prevent the deterioration of the vinyl sheet is to suppress the photooxidation action of the photocatalyst. For this purpose, the film thickness of the photocatalyst containing layer is 0.1 μm or less, or the photocatalyst containing layer is one of alkali metal, alkaline earth metal, alumina, silica, zirconia, antimony oxide, amorphous titania, and hydrous titania. Or 2 or more types can be added.
[0015]
【Example】
Example 1
A 10 cm square vinyl sheet was previously coated with a silicone layer. For this purpose, the A liquid (silica sol) and B liquid (trimethoxymethylsilane) of the Japanese synthetic rubber coating composition “Glaska” are mixed so that the weight ratio of the A liquid and the B liquid is 3: 1. This mixed solution was applied to a vinyl sheet and cured at a temperature of 60 ° C. to obtain a sample coated with a 3 μm-thick silicone base coat.
Next, anatase-type titania sol (Nissan Chemical, TA-15) and “Glaska” solution A were mixed, diluted with ethanol, and then added with “Glaska” solution B, to obtain a titania-containing coating composition. It was adjusted. The composition of the coating composition was 3 parts by weight of silica, 1 part by weight of trimethoxymethylsilane, and 4 parts by weight of titania. This coating composition was applied to the surface of a sample and cured at a temperature of 150 ° C. to form a top coat in which anatase-type titania particles were dispersed in a silicone coating film.
[0016]
Using a 20 W black light blue fluorescent lamp (Sankyo Electric, FL20BLB) on the surface of this sample, ultraviolet light was irradiated for 0.5 week at an ultraviolet illuminance of 0.5 mW / cm 2 (an ultraviolet illuminance with an energy higher than the band gap energy of anatase type titania). Then, the contact angle of the surface with water was measured with a contact angle measuring device (Kyowa Interface Science Co., Ltd., model CA-X150). The detection limit of the low angle side of this contact angle measuring device was 1 °. The contact angle was measured 30 seconds after a water droplet was dropped from the microsyringe onto the sample surface. The measuring instrument reading was 0 °, indicating super hydrophilicity.
Next, both ends of this sample were fixed with tape in a sealed container, a beaker containing hot water was placed below the sample, and the state of condensed water was observed. The condensed water became a uniform water film, and no water droplet growth was observed.
[0017]
Example 2
A 10 cm square vinyl sheet was previously coated with an amorphous silica layer. Therefore, 86 parts by weight of ethanol solvent, 6 parts by weight of tetraethoxysilane Si (OC 2 H 5 ) 4 (Wako Pure Chemical), 6 parts by weight of pure water, and 36% hydrochloric acid 2 as a hydrolysis inhibitor of tetraethoxysilane Part by weight was added and mixed to prepare a silica coating solution. Since the solution generated heat by mixing, the mixture was allowed to cool for about 1 hour. This solution was applied to the surface of a vinyl sheet by a flow coating method and dried at a temperature of 50 ° C. With drying, tetraethoxysilane was first hydrolyzed to silanol Si (OH) 4 , and then an amorphous silica thin film was formed on the surface of the vinyl sheet by dehydration condensation polymerization of silanol.
Next, 0.69 g of tetraethoxysilane (Wako Pure Chemical Industries), 1.07 g of anatase-type titania sol (Nissan Chemical, TA-15, average particle size 0.01 μm), 29.88 g of ethanol and 0.36 g of pure water are mixed to prepare a coating solution. did. This coating solution was applied to the surface of the vinyl sheet by spray coating. By holding this vinyl sheet at a temperature of about 150 ° C. for about 20 minutes, tetraethoxysilane is subjected to hydrolysis and dehydration condensation polymerization, and a coating in which anatase-type titania particles are bound with an amorphous silica binder is vinyl. Formed on the surface of the sheet. The weight ratio of titania and silica was 1.
[0018]
This sample was irradiated with ultraviolet light under the same conditions as in Example 1, and the contact angle with water on the surface was measured. The contact angle was 0 °. Further, when a sample was placed above a beaker containing hot water in the same manner as in Example 1, no growth of water droplets was observed.
[0019]
Comparative example For comparison, the same vinyl sheet used in the example was irradiated with ultraviolet rays under the same conditions as in Example 1, and then the contact angle with water on the surface was measured with a contact angle measuring device. As a result, the contact angle with water was 70 °. When a sample was placed above a beaker containing hot water, growth of water droplets was confirmed.
[0020]
【The invention's effect】
As can be seen from the above test, according to the present invention, even if condensation occurs on the ceiling of the greenhouse, the condensed water spreads uniformly on the surface of the photocatalyst layer and forms a uniform water film. Will not fall from a fixed point on the ceiling. Therefore, crop root rot can be prevented. Moreover, since root rot does not occur in the field directly under the fixed place of the ceiling, it is possible to secure a planting area and improve the yield.

Claims (8)

半導体光触媒を含む透明層によって内面が被覆された天井を備え、太陽光による光触媒の光励起に伴い前記層の表面が親水化され、もって、天井内面に凝縮水が結露したときに凝縮水が一様な水膜を形成するビニールハウス。The ceiling is covered with a transparent layer containing a semiconductor photocatalyst, and the surface of the layer is hydrophilized with photoexcitation of the photocatalyst by sunlight , so that the condensed water is uniform when condensed water condenses on the ceiling inner surface. A greenhouse that forms a water film. 前記層は光触媒の粒子を無定形シリカによって結着してなる請求項１に記載のビニールハウス。   2. The greenhouse according to claim 1, wherein the layer is formed by binding photocatalyst particles with amorphous silica. 前記層は光触媒の粒子が分散されたシリコーンによって形成されており、前記層の表面はシリコーン分子のケイ素原子に結合した有機基が光触媒の作用により少なくとも部分的に水酸基に置換されたシリコーン誘導体で形成されていることを特徴とする請求項１に記載のビニールハウス。   The layer is formed of silicone in which photocatalyst particles are dispersed, and the surface of the layer is formed of a silicone derivative in which an organic group bonded to a silicon atom of a silicone molecule is at least partially substituted with a hydroxyl group by the action of the photocatalyst. The greenhouse according to claim 1, wherein 光触媒の作用により天井素材が劣化するのを防止するため、前記層と天井素材との間には光酸化対抗性の中間層を配置したことを特徴とする請求項１から３のいずれか一項に記載のビニールハウス。  The photo-oxidation-resistant intermediate layer is disposed between the layer and the ceiling material in order to prevent the ceiling material from deteriorating due to the action of the photocatalyst. The greenhouse described in. 前記光触媒の光励起に伴い、前記層の表面は水との接触角が１０°以下に親水化される、請求項１から４のいずれか一項に記載のビニールハウス。With the excitation of the previous SL photocatalyst, the surface of said layer in contact angle with water is hydrophilized to 10 ° or less, greenhouses according to any one of claims 1 to 4. 半導体光触媒を含む透明層によって天井内面が被覆されたビニールハウスを屋外に設置して太陽の照射にさらし、太陽光によって光触媒を光励起させることにより前記層の表面を親水化させ、もって、天井内面に凝縮水が結露したときに凝縮水を一様な水膜に広がらせることを特徴とするビニールハウス天井の結露集中防止方法。  A greenhouse covered with a transparent layer containing a semiconductor photocatalyst is installed outdoors, exposed to the sun, and the photocatalyst is photoexcited by sunlight to hydrophilize the surface of the layer, thereby A method for preventing condensation on the ceiling of a greenhouse, characterized by spreading the condensed water into a uniform water film when the condensed water is condensed. 前記層は光触媒の粒子が分散されたシリコーンからなり、前記層の表面のシリコーン分子のケイ素原子に結合した有機基は光触媒が太陽光によって光励起されるに伴い少なくとも部分的に水酸基に置換されることを特徴とする請求項６に記載の方法。  The layer is made of silicone in which photocatalyst particles are dispersed, and the organic group bonded to the silicon atom of the silicone molecule on the surface of the layer is at least partially substituted with a hydroxyl group as the photocatalyst is photoexcited by sunlight. The method according to claim 6. 前記光触媒の光励起に伴い、前記層の表面は水との接触角が１０°以下に親水化される、請求項６または７に記載のビニールハウス天井の結露集中防止方法。With the excitation of the previous SL photocatalyst, the surface of said layer in contact angle with water is hydrophilized to 10 ° or less, greenhouses ceiling condensation intensive prevention method according to claim 6 or 7.
JP15017196A 1995-12-22 1996-05-22 Greenhouse ceiling and its condensation prevention method Expired - Lifetime JP3760509B2 (en)

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JP28281296A Expired - Lifetime JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them
JP8284532A Pending JPH09227805A (en) 1995-12-22 1996-09-19 Photocatalytic hydrophilic coating composition
JP28453496A Expired - Lifetime JP3173391B2 (en) 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
JP28895496A Expired - Fee Related JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence
JP28895696A Expired - Fee Related JP3588206B2 (en) 1995-12-22 1996-09-25 Self-cleaning road decorative panel, and method of cleaning road decorative panel
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
JP8323516A Pending JPH09241038A (en) 1995-12-22 1996-11-19 Photocatalytic hydrophilic member and its production
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
JP2000181284A Pending JP2001048679A (en) 1995-12-22 2000-06-16 Photocatalytic hydrophilic tile and its production
JP2000181287A Expired - Fee Related JP3465664B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

Family Applications Before (3)

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

Family Applications After (67)

Application Number Title Priority Date Filing Date
JP8150410A Pending JPH09225263A (en) 1995-12-22 1996-05-23 Air pollutant removing filter, air pollutant removing fan and ventilator using the fan
JP8156383A Pending JPH09231849A (en) 1995-12-22 1996-05-29 Insulator and dirt preventing method therefore
JP13653596A Expired - Lifetime JP3339304B2 (en) 1995-12-22 1996-05-30 Painted object and painting method
JP8136777A Pending JPH09227178A (en) 1995-12-22 1996-05-30 Laminated glass and its production
JP13782996A Ceased JP3189682B2 (en) 1995-12-22 1996-05-31 Antifouling material
JP8168643A Pending JPH09232096A (en) 1995-12-22 1996-06-06 Electrification preventing method, and electrification preventive composite material
JP8145265A Pending JPH09225276A (en) 1995-12-22 1996-06-07 Separating membrane and formation of surface layer to separating membrane
JP8168662A Pending JPH09225389A (en) 1995-12-22 1996-06-10 Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture
JP8158518A Pending JPH09225021A (en) 1995-12-22 1996-06-19 Medical material
JP8195184A Expired - Lifetime JP3003581B2 (en) 1995-12-22 1996-06-20 A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor
JP8272814A Pending JPH09226041A (en) 1995-12-22 1996-09-06 Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member
JP8272815A Pending JPH09224957A (en) 1995-12-22 1996-09-06 Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop
JP8272808A Pending JPH09229724A (en) 1995-12-22 1996-09-07 Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover
JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
JP27519096A Expired - Lifetime JP3277983B2 (en) 1995-12-22 1996-09-10 Outdoor display panel and its cleaning method
JP8275189A Pending JPH09231807A (en) 1995-12-22 1996-09-10 Vehicle headlight cover, vehicle with it, and its defogging method
JP8238927A Pending JPH09227159A (en) 1995-12-22 1996-09-10 Front and rear window glass of vehicle
JP8281223A Expired - Lifetime JP3063968B2 (en) 1995-12-22 1996-09-17 Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror
JP8281225A Pending JPH09230107A (en) 1995-12-22 1996-09-17 Anti-fogging glass lens and its anti-fogging method
JP8281222A Pending JPH09230106A (en) 1995-12-22 1996-09-17 Anti-fogging camera filter and its anti-fogging method
JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8281220A Expired - Lifetime JP3003593B2 (en) 1995-12-22 1996-09-17 Photocatalytic hydrophilic member
JP8282806A Pending JPH09228057A (en) 1995-12-22 1996-09-18 Wheel and its cleaning method
JP8246180A Pending JPH09230493A (en) 1995-12-22 1996-09-18 Camera
JP8282808A Pending JPH09228765A (en) 1995-12-22 1996-09-18 Blind and manufacture thereof
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
JP8282805A Pending JPH09231499A (en) 1995-12-22 1996-09-18 Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method
JP8282810A Pending JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method
JP08282811A Expired - Fee Related JP3075195B2 (en) 1995-12-22 1996-09-18 Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror
JP28281296A Expired - Lifetime JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them
JP8284532A Pending JPH09227805A (en) 1995-12-22 1996-09-19 Photocatalytic hydrophilic coating composition
JP28453496A Expired - Lifetime JP3173391B2 (en) 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
JP28895496A Expired - Fee Related JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence
JP28895696A Expired - Fee Related JP3588206B2 (en) 1995-12-22 1996-09-25 Self-cleaning road decorative panel, and method of cleaning road decorative panel
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
JP8323516A Pending JPH09241038A (en) 1995-12-22 1996-11-19 Photocatalytic hydrophilic member and its production
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
JP2000181284A Pending JP2001048679A (en) 1995-12-22 2000-06-16 Photocatalytic hydrophilic tile and its production
JP2000181287A Expired - Fee Related JP3465664B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

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JP2001049829A (en) 2001-02-20
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JPH09230810A (en) 1997-09-05
JP3414367B2 (en) 2003-06-09
JPH09229585A (en) 1997-09-05
JPH09230031A (en) 1997-09-05
JPH09231821A (en) 1997-09-05
JPH09227156A (en) 1997-09-02
JP2000136370A (en) 2000-05-16
JP3612896B2 (en) 2005-01-19
JP3882625B2 (en) 2007-02-21
JPH09228320A (en) 1997-09-02
JPH09227169A (en) 1997-09-02
JPH09228765A (en) 1997-09-02
JP3774955B2 (en) 2006-05-17
JPH09225021A (en) 1997-09-02
JPH09231849A (en) 1997-09-05
JPH09227159A (en) 1997-09-02
JP3740736B2 (en) 2006-02-01
JPH09224793A (en) 1997-09-02
JP2001122679A (en) 2001-05-08
JP2001081948A (en) 2001-03-27
JPH09230493A (en) 1997-09-05
JP2002302646A (en) 2002-10-18
JPH09226531A (en) 1997-09-02
JPH09229767A (en) 1997-09-05
JPH09225388A (en) 1997-09-02
JPH09228332A (en) 1997-09-02
JPH09230796A (en) 1997-09-05
JPH09231807A (en) 1997-09-05
JPH09225389A (en) 1997-09-02
JP2000141537A (en) 2000-05-23
JPH09225054A (en) 1997-09-02
JPH09224960A (en) 1997-09-02
JP3141802B2 (en) 2001-03-07
JPH09224800A (en) 1997-09-02
JPH09226042A (en) 1997-09-02
JP3613085B2 (en) 2005-01-26
JPH09230106A (en) 1997-09-05
JPH09226060A (en) 1997-09-02
JPH09227805A (en) 1997-09-02
JPH09225396A (en) 1997-09-02
JPH09228331A (en) 1997-09-02
JP2001089752A (en) 2001-04-03
JPH09229724A (en) 1997-09-05
JP2002030258A (en) 2002-01-31
JPH09227832A (en) 1997-09-02
JP3588205B2 (en) 2004-11-10
JPH09228057A (en) 1997-09-02
JP2001048679A (en) 2001-02-20
JP3189682B2 (en) 2001-07-16
JPH09227831A (en) 1997-09-02
JPH09228545A (en) 1997-09-02
JPH09231499A (en) 1997-09-05
JPH09224957A (en) 1997-09-02
JPH09224490A (en) 1997-09-02
JP3003581B2 (en) 2000-01-31
JPH09225387A (en) 1997-09-02
JP3697795B2 (en) 2005-09-21
JP3339304B2 (en) 2002-10-28
JP2003113345A (en) 2003-04-18
JP3588202B2 (en) 2004-11-10
JPH09226041A (en) 1997-09-02
JPH09232096A (en) 1997-09-05
JPH09230119A (en) 1997-09-05
JPH09228134A (en) 1997-09-02
JP3277983B2 (en) 2002-04-22
JP3303696B2 (en) 2002-07-22
JP3063968B2 (en) 2000-07-12
JPH09230108A (en) 1997-09-05
JP3173391B2 (en) 2001-06-04
JPH09230107A (en) 1997-09-05
JP3588206B2 (en) 2004-11-10
JPH09228602A (en) 1997-09-02
JPH09225263A (en) 1997-09-02
JPH09227161A (en) 1997-09-02
JP3348613B2 (en) 2002-11-20
JP3743075B2 (en) 2006-02-08
JP3465664B2 (en) 2003-11-10
JPH09225276A (en) 1997-09-02
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