JP3613084B2 - A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor - Google Patents
A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor Download PDFInfo
- Publication number
- JP3613084B2 JP3613084B2 JP23956799A JP23956799A JP3613084B2 JP 3613084 B2 JP3613084 B2 JP 3613084B2 JP 23956799 A JP23956799 A JP 23956799A JP 23956799 A JP23956799 A JP 23956799A JP 3613084 B2 JP3613084 B2 JP 3613084B2
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- Japan
- Prior art keywords
- sample
- water
- contact angle
- optical semiconductor
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- 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.)
- Expired - Lifetime
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Images
Classifications
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- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
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- 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
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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
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
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Description
【０００１】
【発明の属する技術分野】
本発明は、基材の表面を高度の親水性になし、かつ、維持する技術に関する。より詳しくは、本発明は、鏡、レンズ、板ガラスその他の透明基材の表面を高度に親水化することにより、基材の曇りや水滴形成を防止する防曇技術に関する。本発明は、また、建物や窓ガラスや機械装置や物品の表面を高度に親水化することにより、表面が汚れるのを防止し、又は表面を自己浄化（セルフクリーニング）し若しくは容易に清掃する技術に関する。
【０００２】
【従来の技術】
基材表面が親水化されると、付着水滴が基材表面に一様に拡がるようになるので、ガラス、レンズ、鏡等の透明性部材の曇りを有効に防止でき、湿分による失透防止、雨天時の視界性確保等に役立つ。さらに、都市煤塵、自動車等の排気ガスに含有されるカーボンブラック等の燃焼生成物、油脂、シーラント溶出成分等の疎水性汚染物質が付着しにくく、付着しても降雨や水洗により簡単に落せるようになるので便利である。
【０００３】
このような事情から特に防曇塗料、外装防汚塗料の分野において、従来から親水性樹脂が提案されている（例えば、実開平５−６８００６号や、「高分子」、４４巻、１９９５年５月号、ｐ．３０７）。また、親水化するための表面処理方法も提案されている（例えば、実開平３−１２９３５７号）。
【０００４】
しかしながら、従来提案されている親水性樹脂は水との接触角に換算して３０〜５０゜程度までしか親水化されず、充分な曇り防止効果が発揮できない。また無機粘土質からなる汚染物質の付着及び降雨、水洗による清浄性が充分でない。また従来提案されている親水化するための表面処理方法（エッチング処理、プラズマ処理等）では、一時的に高度に親水化できてもその状態を長期間維持することができない。
【０００５】
本発明者は、ＰＣＴ／ＪＰ９６／００７３３号において、基材表面に光半導体含有層を形成すると、光半導体の光励起に応じて表面が高度に親水化されることを発明し、この技術をガラス、レンズ、鏡、外装材、水回り部材等の種々の複合材に適用すれば、これら複合材に優れた防曇、防汚等の機能を付与できることを提案した。この方法によれば、充分な曇り防止効果が発揮され、疎水性汚染物質及び無機粘土質からなる汚染物質の付着及び降雨、水洗による清浄性が飛躍的に向上する。また光半導体の光励起に応じて親水化された状態が維持、回復される。
【０００６】
【発明が解決しようとする課題】
しかしながら、実質的に耐摩擦性に優れた光半導体のみからなる層を、施釉タイル基材やガラス基材等の平滑な表面を有する基材に直接光半導体ゾル塗布法で塗布し、焼成する場合には、光半導体の光励起に応じて１０゜以下程度まで親水化されない。また、例えば光半導性酸化チタンのみからなる層をガラス基材上に形成するのに、アルコキシド法、スパッタリング法等にて無定型酸化チタン層を形成後、焼成して無定型酸化チタンを結晶化させる方法等ならば、光半導体の光励起に応じて１０゜以下程度まで親水化されるが、この場合もさらに親水化が進めばより高い防曇、防汚等の性能が発揮されると考えられる。そこで、本発明では、光半導体のみからなる層と比較して、光半導体の光励起に応じて、より高度に親水化される部材、より具体的には、より曇り防止性に優れた防曇性部材、より汚染物質が付着しにくく、かつ降雨、水洗による清浄性に優れた防汚性部材、より表面の乾燥しやすい部材を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明では、上記課題を解決すべく、光半導体の光励起に応じて部材表面が親水化される親水性部材、防曇性部材、防汚性部材、易乾燥性部材において、基材表面に、光半導体とそれ以外にリチウム、ナトリウム、カリウム、カルシウム、ストロンチウム、アルミニウム、アルミナ、ジルコニア、イットリアの１群から選ばれた少なくとも１種を含む層が形成されているようにして、太陽光あるいは室内照明光による光半導体の光励起に応じて、水との接触角に換算して２０°以下の親水性を呈するようにした。本発明の好ましい態様においては、上記部材表面は、光半導体の光励起に応じ、水との接触角に換算して１０゜以下、より好ましくは５゜以下まで親水化されるようにする。このようにすることで、特に防曇性、汚染物質の付着防止性及び降雨、水洗による清浄性の飛躍的に優れた部材となる。
【０００８】
【発明の実施の形態】
次に、本発明の構成要素について説明する。ここでいう光半導体とは、価電子帯中の電子の励起によって生成する正孔或いは伝導電子を介する反応により、おそらくは表面に極性を付与して吸着水層を形成することにより、基材表面を親水化できるものをさし、より具体的には、アナターゼ型酸化チタン、ルチル型酸化チタン、酸化錫、酸化亜鉛、三酸化二ビスマス、三酸化タングステン、酸化第二鉄、チタン酸ストロンチウム等が使用できる。
【０００９】
ここでいう親水化とは、水濡れ性が向上する状態の変化をいう。都市煤塵、自動車等の排気ガスに含有されるカーボンブラック等の燃焼生成物、油脂、シーラント溶出成分等の疎水性汚染物質が付着しにくく、付着しても降雨や水洗により簡単に落せるようにするには、基材表面は水との接触角に換算して５０゜以下、より好ましくは３０゜以下程度まで親水化するのがよい。さらに無機粘土質汚染物質が付着しにくく、付着しても降雨や水洗により簡単に落せるようにするには、基材表面は水との接触角に換算して２０゜以下、好ましくは１０゜以下、より好ましくは５゜以下程度まで親水化するのがよい。また透明基材や鏡基材表面に付着した水滴を一様に拡がらせて、ガラス、レンズ、プリズム、鏡の曇りを有効に防止し、湿分による失透防止、雨天時の視界性確保を図るためには基材表面は１０゜以下程度まで親水化するのがよい。
【００１０】
本発明に使用できる基材としては、防曇用途においては、ガラス、透明プラスチック、レンズ、プリズム、鏡等の透明性の基材である。より具体的には、浴室用又は洗面所用鏡、車両用バックミラー、歯科用歯鏡、道路鏡のような鏡；眼鏡レンズ、光学レンズ、写真機レンズ、内視鏡レンズ、照明用レンズ、半導体製造用レンズのようなレンズ；プリズム；建物や監視塔の窓ガラス；自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、ロープウエイのギンドラ、遊園地のゴンドラ、宇宙船のような乗り物の窓ガラス；自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、スノーモービル、オートバイ、ロープウエイのギンドラ、遊園地のゴンドラ、宇宙船のような乗り物の風防ガラス；防護用又はスポーツ用ゴーグル又はマスク（潜水用マスクを含む）のシールド；ヘルメットのシールド；冷凍食品陳列ケースのガラス；計測機器のカバーガラス、及びそれら物品に貼着可能なフィルム等を含む。
【００１１】
本発明に使用できる基材としては、降雨による自己浄化が期待できる屋外用途においては、例えば、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、紙、それらの組合せ、それらの積層体、それらの塗装体等である。より具体的には、外壁や屋根のような建物外装；窓枠；自動車、鉄道車両、航空機、船舶、自転車、オートバイのような乗物の外装及び塗装；窓ガラス；看板、交通標識、防音壁、ビニールハウス、碍子、乗物用カバー、テント材、反射板、雨戸、網戸、太陽電池用カバー、太陽熱温水器等の集熱器用カバー、街灯、舖道、屋外照明、人工滝・人工噴水用石材・タイル、橋、温室、外壁材、壁間や硝子間のシーラー、ガードレール、ベランダ、自動販売機、エアコン室外機、屋外ベンチ、各種表示装置、シャッター、料金所、料金ボックス、屋根樋、車両用ランプ保護カバー、防塵カバー及び塗装、機械装置や物品の塗装、広告塔の外装及び塗装、構造部材、及びそれら物品に貼着可能なフィルム等を含む。
【００１２】
本発明に使用できる基材としては、水洗による清浄化が期待できる用途においては、例えば、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、紙、それらの組合せ、それらの積層体、それらの塗装体等である。より具体的には、上記屋外用途部材が含まれることは勿論、その他に、建物の内装材、窓ガラス、住宅設備、便器、浴槽、洗面台、照明器具、台所用品、食器、食器乾燥器、流し、調理レンジ、キッチンフード、換気扇、窓レール、窓枠、トンネル内壁、トンネル内照明、及びそれら物品に貼着可能なフィルム等を含む。
【００１３】
本発明に使用できる基材としては、乾燥促進が期待できる用途においては、例えば、窓サッシ、熱交換器用放熱フィン、舖道、浴室用洗面所用鏡、洗面化粧台、ビニールハウス天井及びそれら物品に貼着可能なフィルム等を含む。
【００１４】
本発明に使用できる基材は上記以外にも着雪防止、気泡付着防止、生体親和性向上等に利用できる。着雪防止性は特に表面粗さ１μｍ以下の表面層を設けると顕著に優れた特性が得られ、例えば、雪国用屋根材、アンテナ、送電線及びそれら物品に貼着可能なフィルム等を含む基材に適用可能である。
【００１５】
光半導体の光励起は、光半導体結晶の伝導電子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）を有する光を光半導体に照射して行う。より具体的には、光半導体がアナターゼ型酸化チタンの場合には波長３８７ｎｍ以下、ルチル酸化チタンの場合には波長４１３ｎｍ以下、酸化錫の場合には波長３４４ｎｍ以下、酸化亜鉛の場合には波長３８７ｎｍ以下の光を含有する光線を照射する。上記光半導体の場合は、紫外線光源により光励起されるので、光源としては、蛍光灯、白熱電灯、メタルハライドランプ、水銀ランプのような室内照明、太陽光や、それらの光源を低損失のファイバーで誘導した光源等を利用できる。複合材表面の親水化に必要な、光半導体を光励起するために必要な光の照度は、０．００１ｍＷ／ｃｍ２以上、より好ましくは０．０１ｍＷ／ｃｍ２以上である。
【００１６】
本発明において、基材表面に、光半導体以外に添加する物質にアルミナ又はイットリアを選ぶと、０．０１ｍＷ／ｃｍ２未満程度の微弱な励起光照射下、あるいは暗所での親水維持性がよりよく発揮されるようになる。
【００１７】
また、本発明における、さらに好ましい態様においては、光半導体含有層にはさらに、シリカ、及び／又はシリコン原子に結合された有機基の少なくとも一部が水酸基に置換されたシリコーン樹脂が添加されているようにする。こうすることにより光半導体の光励起に応じて生じる複合材表面の親水化はより高度に進むようになると共に、一旦親水化された複合材を暗所に放置した場合でも、長期にわたり親水性が維持されるようになる。
【００１８】
光半導体含有層の膜厚は０．２μｍ以下にするのが好ましい。そうすれば、光の干渉による光半導体含有層の発色を防止することができる。また光半導体含有層の膜厚が薄ければ薄いほど基材の透明度を確保することができる。更に、膜厚を薄くすれば光半導体含有層の耐摩耗性が向上する。光半導体含有層上に、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よい。
【００１９】
光半導体含有層の屈折率は、基材の屈折率より小さいか、あまり大きくないほうがよい。例えば基材がガラス基材（屈折率１．５）である場合は、光半導体含有層の屈折率は２以下であるのが好ましい。そうすれば、複合材表面での可視光の反射を防止でき、透明材における視界確保、意匠性外装又は塗装におけるギラギラ感の防止に役立つ。光半導体含有層の屈折率を２以下にするには、例えば光半導体がアナターゼ型酸化チタン（屈折率２．５）のように屈折率が２をこえる物質の場合には、光半導体以外に屈折率２未満の物質を添加する。屈折率２未満の物質としては、例えば、アルミナ（屈折率１．６）、シリカ（屈折率１．５）、酸化錫（屈折率１．９）、シリコン原子に結合された有機基の少なくとも一部が水酸基に置換されたシリコーン樹脂（屈折率１．４〜１．６）が好適に利用できる。
【００２０】
基材表面に、光半導体と、それ以外に前記基材表面の親水化を促進する作用を持つリチウム、ナトリウム、カリウム、カルシウム、ストロンチウム、アルミニウム、アルミナ、ジルコニア、イットリアの１群から選ばれた少なくとも１種を含む層を形成する方法は以下のような方法がある。（１）基材表面に、光半導体粒子層を形成後、上記金属含有物を塗布し、乾燥固定する。（２）基材表面に、光半導体粒子層を形成後、上記金属含有物を塗布し、さらに光半導体の光励起により金属を還元固定する。（３）基材表面に、光半導体粒子と上記金属含有物を塗布後焼成する。（４）基材表面に、光半導体粒子と上記金属含有物と、光半導体の光励起により親水化しうる硬化性結着剤とを塗布後、硬化性結着剤を硬化させ、さらに光半導体の光励起により結着剤を親水化させる。
【００２１】
光半導体粒子層の形成方法は、例えば、ゾル塗布焼成法、アルコキシド法、スパッタリング法等がある。ゾル塗布焼成法とは、光半導体ゾルを、スプレーコーティング、スピンコーティング、ディップコーティング、ロールコーティング、フローコーティングその他のコーティング法により、基材表面に塗布し、焼成する方法である。アルコキシド法とは、例えば光半導体が結晶性酸化チタンの場合には、チタンのアルコキシド（例えば、テトラエトキシチタン、テトライソプロポキシチタン、テトラｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン）に、塩酸又はエチルアミンのような加水分解抑制剤を添加し、エタノールやプロパノール等の希釈剤で希釈した後、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、スピンコーティング、ディップコーティング、ロールコーティング、フローコーティングその他のコーティング法により、基材表面に塗布し、乾燥させて無定型酸化チタン層を形成し、その後、焼成により無定型酸化チタンを、アナターゼ型酸化チタン或いはルチル型酸化チタンに変換させる方法である。尚、チタンのアルコキシドに代えて、チタンのキレート又はチタンのアセテートのような他の有機チタン化合物を用いてもよい。スパッタリング法とは、例えば光半導体が結晶性酸化チタンの場合には、金属チタン又は酸化チタンをターゲットとし、酸素雰囲気で、基材表面に無定型酸化チタン層を形成し、その後、焼成により無定型酸化チタンを、アナターゼ型酸化チタン或いはルチル型酸化チタンに変換させる方法である。
【００２２】
また金属含有物とは、例えば、前記基材表面の親水化を促進する作用を持つリチウム、ナトリウム、カリウム、カルシウム、ストロンチウム、アルミニウム、アルミナ、ジルコニア、イットリアの１群から選ばれた少なくとも１種を溶質とする溶液等をさす。
【００２３】
光半導体の光励起により親水化しうる硬化性結着剤とは、シリコーン樹脂、脱水縮重合すればシリコーン樹脂になるオルガノシラノール、加水分解・脱水縮重合すればシリコーン樹脂になるオルガノアルコキシシラン等が挙げられる。結着剤の親水化方法は光半導体の光励起により行うことができる。
【００２４】
基材表面に、光半導体と、それ以外に前記基材表面の親水化を促進する作用を持つリチウム、ナトリウム、カリウム、カルシウム、ストロンチウム、アルミニウム、アルミナ、ジルコニア、イットリアの１群から選ばれた少なくとも１種を含む層を形成する方法は以下のような方法がある。（５）基材表面に、光半導体粒子と上記酸化物を塗布後焼成する。（６）基材表面に、光半導体の前駆体と上記酸化物を塗布後、焼成等の方法で光半導体の前駆体を光半導体に変換させる。（７）基材表面に、光半導体粒子と上記酸化物と、光半導体の光励起により親水化しうる硬化性結着剤とを塗布後、硬化性結着剤を硬化させ、さらに光半導体の光励起により結着剤を親水化させる。
【００２５】
光半導体の前駆体とは、例えば光半導体が結晶性酸化チタンの場合には、チタンのアルコキシド（例えば、テトラエトキシチタン、テトライソプロポキシチタン、テトラｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン）、チタンのキレート又はチタンのアセテートのような他の有機チタン化合物を用いてもよい。光半導体の前駆体を光半導体に変換するとは、光半導体が結晶性酸化チタンの場合には、加水分解、脱水縮重合、焼成等の過程により、アナターゼ型酸化チタン或いはルチル型酸化チタンに変換させる方法である。
【００２６】
【実施例】
比較例１
１５ｃｍ角の施釉タイル（東陶機器製、ＡＢ０２Ｅ０１）表面に、アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）をスプレー・コーティング法にて塗布し、８００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。焼成直後の試料表面の水との接触角を接触角測定器（協和界面科学製、形式ＣＡ−Ｘ１５０）により測定した。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。焼成直後の試料表面の水との接触角は８゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２１゜まで上昇した。この上昇は吸着水の試料表面からの離脱や、大気中の汚れ物質の付着によると考えられる。この試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は１５゜までしか親水化しなかった。
【００２７】
実施例１（カルシウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にカルシウム金属濃度５０μｍｏｌ／ｇの硝酸カルシウム水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は３８゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２２゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は５゜まで親水化された。
【００２８】
実施例２（カルシウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、カルシウム金属濃度７７μｍｏｌ／ｇの硝酸カルシウム水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、８００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は２２゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２５゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は８゜まで親水化された。
【００２９】
実施例３（カリウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にカリウム金属濃度５０μｍｏｌ／ｇの塩化カリウム水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は３７゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２７゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は８゜まで親水化された。
【００３０】
実施例４（ナトリウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にナトリウム金属濃度５０μｍｏｌ／ｇの硝酸ナトリウム水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は３７゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２６゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は７゜まで親水化された。
【００３１】
実施例５（ナトリウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、ナトリウム金属濃度７７μｍｏｌ／ｇの硝酸ナトリウム水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、８００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は１７゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２２゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は６゜まで親水化された。
【００３２】
実施例６（マグネシウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にマグネシウム金属濃度５０μｍｏｌ／ｇの塩化マグネシウム二水塩水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は３７゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２２゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は８゜まで親水化された。
【００３３】
実施例７（マグネシウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、ナトリウム金属濃度７７μｍｏｌ／ｇの塩化マグネシウム二水塩水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、８００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は２０゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２５゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は７゜まで親水化された。
【００３４】
実施例８（リチウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にリチウム金属濃度５０μｍｏｌ／ｇの塩化リチウム水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は３６゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２８゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は８゜まで親水化された。
【００３５】
実施例９（亜鉛添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面に亜鉛金属濃度５０μｍｏｌ／ｇの塩化亜鉛水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は４３゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２３゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は８゜まで親水化された。
【００３６】
実施例１０（ストロンチウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にストロンチウム金属濃度５０μｍｏｌ／ｇの塩化ストロンチウム六水塩水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は３３゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２３゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は７゜まで親水化された。
【００３７】
実施例１１（ストロンチウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、ストロンチウム金属濃度７７μｍｏｌ／ｇの塩化ストロンチウム六水塩水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、７００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は８゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、１４゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は５゜まで親水化された。
【００３８】
実施例１２（白金添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面に白金金属濃度５０μｍｏｌ／ｇの塩化白金酸六水塩水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は４２゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、１８゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は６゜まで親水化された。その後、さらにこの試料に紫外線照度０．０１ｍＷ／ｃｍ２の白色灯を９日間照射し、室内照明下での親水維持性を調べた。その結果、試料表面は９゜程度に維持された。
【００３９】
実施例１３（白金添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、白金金属濃度７７μｍｏｌ／ｇの塩化白金酸六水塩水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、７００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は２１゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２２゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は７゜まで親水化された。
【００４０】
実施例１４（パラジウム添加、後添加）
比較例１と同様の方法で、膜厚０．３μｍの酸化チタン層被覆施釉タイル試料を得た。この試料表面にパラジウム金属濃度５０μｍｏｌ／ｇの塩化パラジウム水溶液を０．３ｇ塗布後、０．４ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１０分照射して試料を得た。この試料作製直後の試料表面の水との接触角は４７゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、１８゜になった。さらにこの試料に紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は６゜まで親水化された。
【００４１】
実施例１５（パラジウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、パラジウム金属濃度７７μｍｏｌ／ｇの塩化パラジウム水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、７００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は１５゜であった。この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、２０゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は７゜まで親水化された。
【００４２】
実施例１６（ルテニウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）１８ｇと、ルテニウム金属濃度７７μｍｏｌ／ｇの塩化ルテニウム水和塩水溶液２７ｇとを混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、７００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．３μｍとなるようにした。この試料作製直後の試料表面の水との接触角は１５゜であった。 この試料を暗所に１週間放置し、その後再び試料表面の水との接触角を測定したところ、１８゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を０．２日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は７゜まで親水化された。
【００４３】
実施例１７（アルミニウム添加、混合添加）
アンモニア解膠型の酸化チタンゾル（石原産業製、ＳＴＳ−１１）と、アルミニウム金属濃度５０μｍｏｌ／ｇの塩化アルミニウム水溶液とを、酸化チタンとアルミニウム金属量のモル比が８７：１３となるように混合し、１５ｃｍ角の施釉タイル表面に、スプレー・コーティング法にて塗布し、７００℃で焼成し試料を得た。このときの酸化チタン層の膜厚は０．７μｍとなるようにした。この試料作製直後の試料表面の水との接触角は１１゜であった。この試料を暗所に１日放置し、その後再び試料表面の水との接触角を測定したところ、１３゜になった。さらにこの試料に紫外線照度０．１５ｍＷ／ｃｍ２のＢＬＢ蛍光灯（三共電気製、ブラックライトブルー、ＦＬ２０ＢＬＢ）を１日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は３゜まで親水化された。
【００４４】
実施例１８（イットリア添加）
硝酸解膠型酸化チタンゾル（石原産業製、ＣＳ−Ｎ）と酢酸解膠型酸化イットリウムゾル（多木化学製、溶質濃度１５重量％、平均結晶子径４ｎｍ、ｐＨ７．６）を、酸化チタンと酸化イットリウムとのモル比が８８：１２になるように混合した後、１５ｃｍ角の施釉タイル表面に、スプレーコーティング法にて塗布し、８００℃で１時間焼成し試料を得た。このときの膜厚は０．３μｍになるようにした。焼成直後の試料表面の水との接触角は２１゜であった。得られた試料を、２週間暗所に放置した。その後再び試料表面の水との接触角を測定したところ、２５゜になった。その後、紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１３日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は２゜まで親水化された。その後紫外線照度０．００４ｍＷ／ｃｍ２の白色灯を４日間照射し、室内照明下での親水維持性を調べた。その結果、試料表面は９゜程度に維持された。
【００４５】
実施例１９（アルミナ添加）
硝酸解膠型酸化チタンゾル（石原産業製、ＣＳ−Ｃ）と、酸化アルミニウムゾル（日産化学製、アルミナゾル−１００）を、酸化チタンと酸化アルミニウムとのモル比が８８：１２になるように混合した後、１５ｃｍ角の施釉タイル表面に、スプレーコーティング法にて塗布し、８００℃で１時間焼成し試料を得た。このときの膜厚は０．３μｍになるようにした。焼成直後の試料表面の水との接触角は２゜であった。得られた試料を、２週間暗所に放置した。その後再び試料表面の水との接触角を測定したところ、２０゜になった。その後紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１３日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は再び２゜まで親水化された。その後紫外線照度０．００４ｍＷ／ｃｍ２の白色灯を２日間照射し、室内照明下での親水維持性を調べた。その結果、試料表面は９゜程度に維持された。
【００４６】
実施例２０（ジルコニア添加）
アンモニア解膠型酸化チタンゾル（石原産業製、ＳＴＳ−１１）と、酸化ジルコニウムゾル印産化学製、ＮＺＳ−３０Ｂ）を、酸化チタンと酸化ジルコニウムとのモル比が８８：１２になるように混合した後、１５ｃｍ角の施釉タイル表面に、スプレーコーティング法にて塗布し、８００℃で１時間焼成し試料を得た。このときの膜厚は０．３μｍになるようにした。焼成直後の試料表面の水との接触角は２３゜であった。得られた試料を、１週間暗所に放置した。その後再び試料表面の水との接触角を測定したところ、３５゜になった。その後紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１３日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は４゜まで親水化された。
【００４７】
実施例２１（セリア添加）
アンモニア解膠型酸化チタンゾル（石原産業製、ＳＴＳ−１１）と、酸化セリウムゾル（多木化学製Ｗ−１５）を、酸化チタンと酸化セリウムとのモル比が８８：１２になるように混合した後、１５ｃｍ角の施釉タイル表面に、スプレーコーティング法にて塗布し、８００℃で１時間焼成し試料を得た。このときの膜厚は０．３μｍになるようにした。焼成直後の試料表面の水との接触角は２２゜であった。得られた試料を、１週間暗所に放置した。その後再び試料表面の水との接触角を測定したところ、３８゜になった。その後紫外線照度０．３ｍＷ／ｃｍ２のＢＬＢ蛍光灯を１３日間照射した後、水との接触角を測定したところ、光励起に応じて試料表面は６゜まで親水化された。
【００４８】
実施例２２（水との接触角と防曇性との関係）
エタノールの溶媒８６重量部に、テトラエトキシシラン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製した。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１０ｃｍ角のソーダライムガラス板の表面に塗布し、８０℃の温度で乾燥させた。この間にテトラエトキシシランは加水分解を受けてまずシラノールになり、続いてシラノールの脱水縮重合により無定型シリカの薄膜がガラス板の表面に形成された。次に、テトラエトキシチタン（Ｍｅｒｃｋ社製）１重量部とエタノール９重量部との混合物に加水分解抑制剤として３６％塩酸０．１重量部添加してチタニアコーティング溶液を調製し、この溶液を前記ガラス板の表面に乾燥空気中でフローコーティング法により塗布した。塗布量はチタニアに換算して４５μｇ／ｃｍ２とした。次に、このガラスを１０分間１５０℃の温度に保持することにより、テトラエトキシチタンの加水分解を完了させるとともに、生成した水酸化チタンを脱水縮重合に付し、無定型チタニアを生成させた。こうして無定型シリカの上に無定型チタニアがコーティングされたガラス板を得た。このガラス板を５００℃の温度で焼成し、無定型チタニアをアナターゼ型チタニアに変換した。得られた試料を数日間暗所に放置した。次に、ＢＬＢ蛍光灯を内蔵したデシケータ（温度２４℃、湿度４５〜５０％）内にこのガラス板を配置し、０．５ｍＷ／ｃｍ２の照度で１日間紫外線を照射し、＃１試料を得た。＃１試料の水との接触角を測定したところ０゜であった。次に、＃１試料をデシケータから取出して、６０℃に保持した温浴上に迅速に移し、１５秒後に透過率を測定した。測定された透過率を元の透過率で割り、水蒸気の凝縮により生成した曇りに起因する透過率の変化を求めた。テトラエトキシチタン（Ｍｅｒｃｋ社製）１重量部とエタノール９重量部との混合物に加水分解抑制剤として３６％塩酸０．１重量部添加してチタニアコーティング溶液を調製し、この溶液を１０ｃｍ角のガラス板の表面に乾燥空気中でフローコーティング法により塗布した。塗布量はチタニアに換算して４５μｇ／ｃｍ２とした。次に、このガラスを１０分間１５０℃の温度に保持することにより、テトラエトキシチタンの加水分解を完了させるとともに、生成した水酸化チタンを脱水縮重合に付し、無定型チタニアを生成させた。こうして無定型チタニアがコーティングされたガラス板を得た。このガラス板を５００℃の温度で焼成し、無定型チタニアをアナターゼ型チタニアに変換した。得られた試料を数日間暗所に放置した。次に、ＢＬＢ蛍光灯を内蔵したデシケータ（温度２４℃、湿度４５〜５０％）内にこのガラス板を配置し、０．５ｍＷ／ｃｍ２の照度で水との接触角が３゜になるまで紫外線を照射し、＃２試料を得た。次に、＃２試料を暗所に放置した。異なる時間間隔で、＃２試料を暗所から取出し、水との接触角をその都度測定した。更に、＃２試料を一旦デシケータ（温度２４℃、湿度４５〜５０％）内に移し、温度を平衡させた後、＃１試料と同様に、６０℃に保持した温浴上に迅速に移し、１５秒後に透過率を測定し、水蒸気の凝縮により生成した曇りに起因する透過率の変化を求めた。比較のため、市販の並板ガラス、アクリル樹脂、ポリ塩化ビニル板、ポリカーボネート板について、水との接触角を測定した。更に、これらの板材を同じ条件のデシケータ内に移し、温度を平衡させた後、同様に、６０℃に保持した温浴上に迅速に移し、１５秒後に透過率を測定し、水蒸気の凝縮により生成した曇りに起因する透過率の変化を求めた。得られた結果を表１に示す。表１の結果から、水との接触角が１０゜以下であれば、極めて高い防曇性が実現されることが確認された。上記実施例１〜２１はいずれも光励起に応じて水との接触角が１０゜以下になることから、基材に透明基材を選べば、いずれも優れた防曇性が発揮されると考えられる。
【００４９】
【表１】
実施例２３ （水との接触角と防汚性との関係）
種々の試料を以下に示す汚泥試験に付した。調べた試料は、以下に示す＃１〜＃６試料である。＃１試料：アナターゼ型酸化チタンゾル（石原産業製、ＳＴＳ−１１）とコロイダルシリカゾル（スノーテックス２０）との混合物（固形分におけるシリカの割合が１０重量％）を固形分換算で４．５ｍｇだけ、１５ｃｍ四角の施釉タイル（東陶機器製、ＡＢ０２Ｅ０１）に塗布し、８８０℃の温度で１０分焼成して、＃０試料を得た。この＃０試料に、ＢＬＢ蛍光灯を用いて０．５ｍＷ／ｃｍ２の紫外線照度で３時間紫外線を照射して、＃１試料を得た。＃２試料：＃０試料に、さらに銅濃度５０μｍｏｌ／ｇの酢酸銅一水塩水溶液を０．３ｇ塗布後、ＢＬＢ蛍光灯を用いて０．４ｍＷ／ｃｍ２の紫外線照度で１０分照射することにより銅を固定した。その後、ＢＬＢ蛍光灯を用いて０．５ｍＷ／ｃｍ２の紫外線照度で３時間紫外線を照射して、＃２試料を得た。＃３試料：施釉タイル（東陶機器製、ＡＢ０２Ｅ０１）。＃４試料：アクリル樹脂（ＰＭＭＡ）板。＃５試料：人造大理石板（東陶機器製、ＭＬ０３）。＃６試料：ポリテトラフルオロエチレン（ＰＴＦＥ）板。汚泥試験は以下の要領で行った。まず、汚泥スラリーを以下のようにして調製した。すなわち、イエローオーカー６４．３重量％、焼成関東ローム２１．４重量％、疎水性カーボンブラック４．８重量％、シリカ粉４．８重量％、親水性カーボンブラック４．７重量％を含む粉体混合物を１．０５ｇ／リッターの濃度で水に懸濁させたスラリーを調製した。４５度に傾斜させた＃１〜＃６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と光沢度変化を調べた。色差変化は、試験後の試料表面の色差から試験前の試料表面の色差を引くことにより求めた。色差は日本工業規格（ＪＩＳ）Ｈ０２０１に従い、ΔＥ＊表示を用いた。光沢度の測定は日本工業規格（ＪＩＳ）Ｚ８７４１の規定に従って行い、光沢度変化は試験後の試料表面の光沢度を試験前の試料表面の光沢度で割ることにより求めた。結果を表２に示す。
【００５１】
【表２】
更に＃１試料、＃３試料、＃４試料、＃６試料及び下記に示す＃７試料について、屋外汚れ加速試験を行った。＃７試料：１０ｃｍ角のアルミニウム基板に、シリカゾル（日本合成ゴム製、グラスカＡ液）とトリメトキシシラン（日本合成ゴム製、グラスカＢ液）を、重量比が３：１となるように混合した液状物を塗布し、１５０℃で硬化させ、膜厚３μｍのシリコーン被覆板（＃７試料）を得た。屋外汚れ加速試験は、以下の要領で行った。すなわち、茅ケ崎市所在の建物の屋上に図１（ａ）及び図１（ｂ）に示す屋外汚れ加速試験装置を設置した。図１（ａ）及び図１（ｂ）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に上記＃１試料、＃３試料、＃４試料、＃６試料及び＃７試料を取り付け、１か月間屋外に暴露した。この試験における汚れの付着は雨天の流路である縦筋部に多量の汚れが付着する傾向がある。そこで、試料表面の汚れ具合を、試験後の縦筋汚れ部の色差から試験前の色差を引くことにより評価した。結果を表３に示す。
【００５３】
【表３】
理解を容易にするため、表２と表３に示した水との接触角及び色差変化を図２のグラフにプロットした。図２のグラフにおいて、カーブＡは汚れ加速試験における大気中のカーボンブラックなどの燃焼生成物や都市塵埃のような汚れによる色差変化と水との接触角との関係を示し、カーブＢは汚泥試験における汚泥による色差変化と水との接触角との関係を示す。図２のグラフを参照するに、カーブＡから良く分かるように、基材の水との接触角が増加するにつれて燃焼生成物や都市塵埃による汚れが目立つようになる。これは、燃焼生成物や都市塵埃のような汚染物質は基本的に疎水性であり、従って、疎水性の表面に付着しやすいからである。これに対して、カーブＢは、汚泥による汚れは水との接触角が２０゜から５０゜の範囲でピーク値を呈することを示している。これは、泥や土のような無機物質は、本来、水との接触角が２０゜から５０゜程度の親水性を有し、類似の親水性を有する表面に付着しやすいからである。従って、表面を水との接触角が２０゜以下の親水性にするか、或いは、水との接触角が６０゜以上に疎水化すれば、表面への無機物質の付着を防止することができることが分かる。水との接触角が２０゜以下になると汚泥による汚れが減少するのは、表面が水との接触角で２０゜以下の高度の親水性になると、無機物質に対する親和性よりも水に対する親和性の方が高くなり、表面に優先的に付着する水によって無機物質の付着が阻害されると共に、付着しようとする無機物質が水によって容易に洗い流されるからである。以上から、建物などの表面に疎水性の汚れ物質と親水性の汚れ物質のいずれもが付着しないようにするため、或いは、表面に堆積した汚れが降雨により洗い流されて表面がセルフクリーニングされるようにするには、表面の水との接触角が２０゜以下、好ましくは１０゜以下、更に好ましくは５゜以下にすればよいことが分かる。上記実施例１〜２１はいずれも光励起に応じて水との接触角が１０゜以下になることから、いずれも優れた降雨又は水洗による清浄性が発揮されると考えられる。
【００５５】
【発明の効果】
基材表面に、光半導体以外に前記基材表面の親水化を促進する作用を持つリチウム、ナトリウム、カリウム、カルシウム、ストロンチウム、アルミニウム、アルミナ、ジルコニア、イットリアの１群から選ばれた少なくとも１種を含む層を形成することにより、ゾル塗布焼成法で基材表面に光半導体含有層を形成した場合においても、太陽光、室内照明等の日常よく使用されている光源による光半導体の光励起に応じて１０゜以下まで親水化されるようになる。また、ゾル塗布焼成法以外の、アルコキシド法、スパッタリング法、シリカ、シリコーンなどの結着剤の硬化を利用した方法等で基材表面に光半導体含有層を形成した場合においても、光半導体の光励起に応じた親水性能の向上が期待できる。更に、アルミナまたはイットリアの場合は０．０１ｍＷ／ｃｍ 2 未満程度の微弱な励起光照射下、あるいは暗所での親水維持性がよりよく発揮されるようになる。
【図面の簡単な説明】
【図１】屋外汚れ加速試験装置を示す図で、（ａ）は正面図、（ｂ）は側面図（寸法数値の単位はミリメートル）。
【図２】異なる親水性をもった表面が都市煤塵と汚泥によって汚れる度合いを示す図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a technique for making and maintaining the surface of a substrate highly hydrophilic. More specifically, the present invention relates to an anti-fogging technique for preventing fogging of a substrate and formation of water droplets by highly hydrophilizing the surface of a transparent substrate such as a mirror, lens, plate glass and the like. The present invention also prevents the surface from becoming dirty by highly hydrophilizing the surface of a building, window glass, mechanical device or article, or self-cleans the surface or easily cleans the surface. About.
[0002]
[Prior art]
When the surface of the base material is made hydrophilic, the attached water droplets spread uniformly on the surface of the base material, so that it is possible to effectively prevent fogging of transparent members such as glass, lenses and mirrors, and to prevent devitrification due to moisture It helps to ensure visibility in rainy weather. In addition, combustion pollutants such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oils and sealants are difficult to adhere, and even if they adhere, they can be easily removed by rain or water washing. This is convenient.
[0003]
Under these circumstances, hydrophilic resins have been proposed in the field of anti-fogging paints and exterior anti-fouling paints (for example, Japanese Utility Model Laid-Open No. 5-68006, “Polymer”, Vol. 44, May 1995). Monthly issue, p.307). In addition, a surface treatment method for hydrophilization has also been proposed (for example, Japanese Utility Model Laid-Open No. 3-129357).
[0004]
However, conventionally proposed hydrophilic resins are only hydrophilized up to about 30 to 50 ° in terms of contact angle with water, and a sufficient antifogging effect cannot be exhibited. Moreover, the adherence of contaminants made of inorganic clay and the cleanliness due to rain and washing are not sufficient. Further, in the conventionally proposed surface treatment methods for hydrophilicity (etching treatment, plasma treatment, etc.), the state cannot be maintained for a long time even if it can be temporarily highly hydrophilic.
[0005]
The present inventor invented that, in PCT / JP96 / 00733, when a photo-semiconductor-containing layer is formed on the substrate surface, the surface is highly hydrophilized in response to photoexcitation of the photo-semiconductor. It has been proposed that when applied to various composite materials such as lenses, mirrors, exterior materials, and water-circulating members, these composite materials can be provided with excellent antifogging and antifouling functions. According to this method, a sufficient anti-fogging effect is exhibited, and adhesion of contaminants composed of hydrophobic contaminants and inorganic clays, and cleanliness by rain and washing are greatly improved. Further, the hydrophilic state is maintained and recovered in response to photoexcitation of the optical semiconductor.
[0006]
[Problems to be solved by the invention]
However, when a layer consisting only of a photosemiconductor that is substantially excellent in abrasion resistance is applied directly to a substrate having a smooth surface such as a glazed tile substrate or a glass substrate by a photosemiconductor sol coating method and fired. Is not hydrophilized to about 10 ° or less in response to photoexcitation of the optical semiconductor. In addition, for example, to form a layer composed only of a light semiconductive titanium oxide on a glass substrate, an amorphous titanium oxide layer is formed by an alkoxide method, a sputtering method, etc., and then fired to crystallize the amorphous titanium oxide. If it is a method to make it hydrophilic, it will be hydrophilized to about 10 ° or less in response to photoexcitation of the optical semiconductor, but in this case as well, it is considered that higher antifogging and antifouling performances will be exhibited if the hydrophilization further proceeds. It is done. Therefore, in the present invention, compared with a layer composed only of an optical semiconductor, a member that is made more highly hydrophilic in response to photoexcitation of the optical semiconductor, more specifically, an antifogging property that is more excellent in antifogging property. It is an object of the present invention to provide a member, an antifouling member that hardly adheres to pollutants, and has excellent cleanliness by rain and water washing, and a member that can be easily dried.
[0007]
[Means for Solving the Problems]
In the present invention, in order to solve the above problems, in the hydrophilic member, the antifogging member, the antifouling member, and the easy-drying member in which the member surface is hydrophilized in response to photoexcitation of the optical semiconductor, With optical semiconductorsItother thanAt least one selected from the group consisting of lithium, sodium, potassium, calcium, strontium, aluminum, alumina, zirconia, and yttriaSo that a layer containing is formedIn response to photoexcitation of the optical semiconductor by sunlight or indoor illumination light, the contact angle with water is converted to a hydrophilicity of 20 ° or less.In a preferred embodiment of the present invention, the surface of the member is hydrophilized to 10 ° or less, more preferably 5 ° or less in terms of a contact angle with water in accordance with photoexcitation of the optical semiconductor. By doing in this way, it becomes a member excellent in the anti-fogging property, the adhesion prevention property of a pollutant, and the cleanliness by rain and washing in particular.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Next, components of the present invention will be described. The photo-semiconductor here means that the surface of the substrate is formed by forming an adsorbed water layer, possibly by imparting polarity to the surface by a reaction via holes or conduction electrons generated by excitation of electrons in the valence band. A material that can be made hydrophilic, more specifically, anatase titanium oxide, rutile titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, ferric oxide, strontium titanate, etc. it can.
[0009]
Hydrophilization here refers to a change in the state in which water wettability is improved. Hydrophobic pollutants such as carbon black and other combustion products, fats and oils and sealant elution components contained in exhaust gas from automobile dust, automobiles, etc. are difficult to adhere and can be easily removed by rain or water washing For this purpose, the surface of the substrate should be hydrophilized to 50 ° or less, more preferably about 30 ° or less in terms of the contact angle with water. Furthermore, in order to prevent inorganic clay contaminants from adhering easily and to be able to be easily removed by rain or washing even if they adhere, the surface of the substrate is converted to a contact angle with water of 20 ° or less, preferably 10 °. In the following, it is preferable to hydrophilize to about 5 ° or less. In addition, water droplets adhering to the surface of transparent and mirror substrates are spread evenly to effectively prevent fogging of glass, lenses, prisms, and mirrors, prevent devitrification due to moisture, and ensure visibility in rainy weather In order to achieve this, the surface of the base material should be hydrophilicized to about 10 ° or less.
[0010]
The base material that can be used in the present invention is a transparent base material such as glass, transparent plastic, lens, prism, and mirror in the anti-fogging application. More specifically, bathroom or toilet mirrors, vehicle rearview mirrors, dental tooth mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, semiconductors Lenses such as manufacturing lenses; prisms; windows for buildings and surveillance towers; automobiles, rail vehicles, aircraft, ships, submersibles, snow vehicles, ropeway guindra, amusement park gondola, spacecraft-like vehicle windows Glasses; Windshields for vehicles such as automobiles, rail cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway guindra, amusement park gondola, spacecraft; protective or sports goggles or masks ( Shield (including diving mask); Helmet shield; Frozen food display case glass; Measuring instrument cover glass; Including the film, and the like.
[0011]
As the base material that can be used in the present invention, in outdoor applications where self-purification by rain can be expected, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, paper, combinations thereof, These laminates, their painted bodies, and the like. More specifically, building exteriors such as exterior walls and roofs; window frames; exteriors and paintings of vehicles such as automobiles, rail cars, aircraft, ships, bicycles, motorcycles; window glass; signs, traffic signs, noise barriers, Plastic houses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater and other heat collector covers, street lights, tunnels, outdoor lighting, artificial waterfalls, artificial fountain stones, Tiles, bridges, greenhouses, exterior wall materials, sealers between walls and glass, guardrails, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, price boxes, roof gutters, vehicle lamps Protective cover, dustproof cover and painting, painting of machinery and articles, exterior and painting of advertising towers, structural members, and films that can be attached to these articles.
[0012]
Examples of the base material that can be used in the present invention include metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, paper, combinations thereof, and the like in applications where cleaning with water can be expected. Laminates of these, their painted bodies, and the like. More specifically, in addition to the above-described outdoor use members, in addition to the above, building interior materials, window glass, housing equipment, toilets, bathtubs, wash basins, lighting equipment, kitchenware, tableware, tableware dryers, It includes sinks, cooking ranges, kitchen hoods, ventilation fans, window rails, window frames, tunnel inner walls, tunnel lighting, and films that can be attached to these articles.
[0013]
As a base material that can be used in the present invention, in applications that can be expected to accelerate drying, for example, window sashes, heat-dissipating fins for heat exchangers, corridors, bathroom mirrors, vanity tables, greenhouse ceilings, and articles thereof Includes films that can be attached.
[0014]
In addition to the above, the substrate that can be used in the present invention can be used for preventing snow accretion, preventing bubble adhesion, improving biocompatibility, and the like. In particular, when a surface layer having a surface roughness of 1 μm or less is provided, the ability to prevent snow accretion can be remarkably improved. For example, a base material including a roofing material for snow country, an antenna, a power transmission line, and a film that can be attached to these articles. Applicable to materials.
[0015]
Photoexcitation of the optical semiconductor is performed by irradiating the optical semiconductor with light having an energy (that is, a short wavelength) larger than the energy gap between the conduction electron band and the valence band of the optical semiconductor crystal. More specifically, when the optical semiconductor is anatase-type titanium oxide, the wavelength is 387 nm or less, when it is rutile titanium oxide, the wavelength is 413 nm or less, when it is tin oxide, the wavelength is 344 nm or less, and when it is zinc oxide, the wavelength is 387 nm. Irradiate light containing the following light. In the case of the above-mentioned optical semiconductor, it is excited by an ultraviolet light source. As a light source, indoor lighting such as fluorescent lamps, incandescent lamps, metal halide lamps, mercury lamps, sunlight, and these light sources are guided by low-loss fibers. Can be used. The illuminance of light necessary for photoexcitation of the optical semiconductor necessary for hydrophilization of the composite surface is 0.001 mW / cm.2Or more, more preferably 0.01 mW / cm2That's it.
[0016]
In the present invention, when alumina or yttria is selected as the material to be added to the substrate surface other than the optical semiconductor, 0.01 mW / cm2Under the weak excitation light irradiation of less than about less, the hydrophilicity maintenance property in a dark place comes to be exhibited better.
[0017]
In a further preferred aspect of the present invention, the optical semiconductor-containing layer further contains silica and / or a silicone resin in which at least a part of the organic group bonded to the silicon atom is substituted with a hydroxyl group. Like that. In this way, the hydrophilicity of the composite surface that occurs in response to photoexcitation of the optical semiconductor is advanced to a higher degree, and the hydrophilicity is maintained for a long time even if the hydrophilicized composite material is left in the dark. Will come to be.
[0018]
The film thickness of the optical semiconductor-containing layer is preferably 0.2 μm or less. If it does so, the color development of the optical semiconductor content layer by light interference can be prevented. Moreover, the transparency of a base material is securable, so that the film thickness of an optical semiconductor content layer is thin. Furthermore, if the film thickness is reduced, the wear resistance of the optical semiconductor-containing layer is improved. A wear-resistant or corrosion-resistant protective layer that can be hydrophilized and other functional films may be further provided on the optical semiconductor-containing layer.
[0019]
The refractive index of the optical semiconductor-containing layer should be smaller than or less than the refractive index of the substrate. For example, when the substrate is a glass substrate (refractive index 1.5), the refractive index of the optical semiconductor-containing layer is preferably 2 or less. If it does so, reflection of visible light on the surface of a composite material can be prevented, and it is useful for ensuring the visual field in a transparent material, and preventing the glare feeling in a design exterior or painting. In order to reduce the refractive index of the optical semiconductor-containing layer to 2 or less, for example, when the optical semiconductor is a substance having a refractive index higher than 2, such as anatase titanium oxide (refractive index 2.5), it is refracted in addition to the optical semiconductor. Add material with a rate of less than 2. Examples of the material having a refractive index of less than 2 include at least one of alumina (refractive index 1.6), silica (refractive index 1.5), tin oxide (refractive index 1.9), and an organic group bonded to a silicon atom. A silicone resin (refractive index: 1.4 to 1.6) in which a part is substituted with a hydroxyl group can be suitably used.
[0020]
On the surface of the base material, the optical semiconductor and otherAt least one selected from the group consisting of lithium, sodium, potassium, calcium, strontium, aluminum, alumina, zirconia, and yttria that has the effect of promoting hydrophilicity on the surface of the substrate.There are the following methods for forming the layer containing. (1) After forming an optical semiconductor particle layer on the surface of the substrate, the metal-containing material is applied and dried and fixed. (2) After forming an optical semiconductor particle layer on the substrate surface, the metal-containing material is applied, and the metal is reduced and fixed by photoexcitation of the optical semiconductor. (3) The optical semiconductor particles and the metal-containing material are applied to the surface of the base material and fired. (4) After applying the optical semiconductor particles, the metal-containing material, and a curable binder that can be hydrophilized by photoexcitation of the optical semiconductor on the surface of the substrate, the curable binder is cured, and further, photoexcitation of the optical semiconductor is performed. To make the binder hydrophilic.
[0021]
Examples of the method for forming the optical semiconductor particle layer include a sol coating baking method, an alkoxide method, and a sputtering method. The sol coating firing method is a method in which an optical semiconductor sol is applied to a substrate surface by spray coating, spin coating, dip coating, roll coating, flow coating, or other coating methods, and is fired. For example, when the optical semiconductor is crystalline titanium oxide, the alkoxide method includes titanium alkoxide (for example, tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium) and hydrochloric acid. Alternatively, after adding a hydrolysis inhibitor such as ethylamine and diluting with a diluent such as ethanol or propanol, the mixture is spray-coated, while partially hydrolyzing or completely hydrolyzing, Spin coating, dip coating, roll coating, flow coating, and other coating methods are applied to the substrate surface and dried to form an amorphous titanium oxide layer. After that, the amorphous titanium oxide is baked to form an anatase titanium oxide. Or rutile titanium oxide A method for converted. Instead of the titanium alkoxide, other organic titanium compounds such as titanium chelate or titanium acetate may be used. For example, in the case where the optical semiconductor is crystalline titanium oxide, the sputtering method is a method in which an amorphous titanium oxide layer is formed on the surface of a base material in an oxygen atmosphere using a metal titanium or titanium oxide as a target, and then amorphous by firing. In this method, titanium oxide is converted into anatase type titanium oxide or rutile type titanium oxide.
[0022]
The metal-containing material is, for example,At least one selected from the group consisting of lithium, sodium, potassium, calcium, strontium, aluminum, alumina, zirconia, and yttria that has the effect of promoting hydrophilicity on the surface of the substrate.This refers to solutions that contain
[0023]
Examples of the curable binder that can be hydrophilized by photoexcitation of an optical semiconductor include a silicone resin, an organosilanol that becomes a silicone resin by dehydration condensation polymerization, and an organoalkoxysilane that becomes a silicone resin by hydrolysis and dehydration condensation polymerization. . The method for hydrophilizing the binder can be performed by photoexcitation of an optical semiconductor.
[0024]
On the surface of the base material, the optical semiconductor and otherAt least one selected from the group consisting of lithium, sodium, potassium, calcium, strontium, aluminum, alumina, zirconia, and yttria that has the effect of promoting hydrophilicity on the surface of the substrate.There are the following methods for forming the layer containing. (5) The optical semiconductor particles and the oxide are applied to the surface of the base material and fired. (6) After applying the optical semiconductor precursor and the oxide on the surface of the substrate, the optical semiconductor precursor is converted into an optical semiconductor by a method such as firing. (7) After applying the photo-semiconductor particles, the oxide, and a curable binder that can be hydrophilized by photo-excitation of the photo-semiconductor on the surface of the substrate, the curable binder is cured, and further, by photo-excitation of the photo-semiconductor Make the binder hydrophilic.
[0025]
The precursor of the optical semiconductor is, for example, an alkoxide of titanium (for example, tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium, tetrabutoxy titanium, tetramethoxy titanium) when the optical semiconductor is crystalline titanium oxide. Other organotitanium compounds such as titanium chelates or titanium acetates may also be used. The conversion of a photo-semiconductor precursor into a photo-semiconductor means that when the photo-semiconductor is crystalline titanium oxide, it is converted into anatase-type titanium oxide or rutile-type titanium oxide by a process such as hydrolysis, dehydration condensation polymerization, or firing. Is the method.
[0026]
【Example】
Comparative Example 1
Ammonia peptized titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) is applied to the surface of a 15cm square glazed tile (manufactured by Totoki Kikai, AB02E01) and fired at 800 ° C to obtain a sample. It was. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was measured with a contact angle measuring device (manufactured by Kyowa Interface Science, model CA-X150). The contact angle was measured 30 seconds after a water droplet was dropped from the microsyringe onto the sample surface. The contact angle of the sample surface with water immediately after firing was 8 °. The sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again. This rise is thought to be due to the separation of adsorbed water from the sample surface and the adhesion of dirt substances in the atmosphere. This sample has UV illumination of 0.3 mW / cm2The BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) was irradiated for 2 days, and then the contact angle with water was measured. As a result, the sample surface was only hydrophilized up to 15 ° in response to photoexcitation.
[0027]
Example 1 (calcium addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After 0.3 g of a calcium nitrate aqueous solution having a calcium metal concentration of 50 μmol / g is applied to the sample surface, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 38 °. The sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 5 ° in response to photoexcitation.
[0028]
Example 2 (calcium added, mixed added)
18 g of ammonia peptization type titanium oxide sol (manufactured by Ishihara Sangyo Co., Ltd., STS-11) and 27 g of calcium nitrate aqueous solution with a calcium metal concentration of 77 μmol / g are mixed and applied to the surface of a 15 cm square glazed tile by spray coating. And calcined at 800 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 22 °. This sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again to find 25 °. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 8 ° in response to photoexcitation.
[0029]
Example 3 (potassium addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After applying 0.3 g of potassium chloride aqueous solution having a potassium metal concentration of 50 μmol / g to the surface of this sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 37 °. This sample was allowed to stand in the dark for one week, and then the contact angle with water on the sample surface was again measured and found to be 27 °. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the surface of the sample was hydrophilized to 8 ° in response to photoexcitation.
[0030]
Example 4 (sodium addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After 0.3 g of a sodium nitrate aqueous solution having a sodium metal concentration of 50 μmol / g was applied to the sample surface, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 37 °. This sample was allowed to stand in the dark for one week, and then the contact angle with water on the sample surface was again measured and found to be 26 °. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the sample surface was hydrophilized to 7 ° in response to photoexcitation.
[0031]
Example 5 (sodium addition, mixed addition)
Ammonia peptization type titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) 18g and sodium nitrate concentration 77gmol / g sodium nitrate aqueous solution 27g were mixed and applied to the surface of 15cm square glazed tile by spray coating method. And calcined at 800 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 17 °. The sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 6 ° in response to photoexcitation.
[0032]
Example 6 (magnesium added, post-added)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After 0.3 g of magnesium chloride dihydrate aqueous solution having a magnesium metal concentration of 50 μmol / g was applied to the surface of this sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 37 °. The sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the surface of the sample was hydrophilized to 8 ° in response to photoexcitation.
[0033]
Example 7 (magnesium addition, mixed addition)
Ammonia peptization type titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) 18g and sodium chloride concentration 77μmol / g magnesium chloride dihydrate aqueous solution 27g are mixed, spray coating method on the surface of 15cm square glazed tile And then baked at 800 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 20 °. This sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again to find 25 °. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 7 ° in response to photoexcitation.
[0034]
Example 8 (lithium addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After 0.3 g of lithium chloride aqueous solution having a lithium metal concentration of 50 μmol / g was applied to the surface of this sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 36 °. This sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the surface of the sample was hydrophilized to 8 ° in response to photoexcitation.
[0035]
Example 9 (zinc addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After coating 0.3 g of zinc chloride aqueous solution with a zinc metal concentration of 50 μmol / g on the surface of this sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 43 °. This sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again to find 23 °. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the surface of the sample was hydrophilized to 8 ° in response to photoexcitation.
[0036]
Example 10 (strontium addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After applying 0.3 g of a strontium chloride hexahydrate aqueous solution having a strontium metal concentration of 50 μmol / g to the surface of the sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 33 °. This sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again to find 23 °. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the sample surface was hydrophilized to 7 ° in response to photoexcitation.
[0037]
Example 11 (strontium addition, mixed addition)
Ammonia peptization-type titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) 18g and strontium metal concentration 77μmol / g strontium chloride hexahydrate aqueous solution 27g are mixed and spray coating method on the surface of 15cm square glazed tile And then baked at 700 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 8 °. The sample was left in the dark for one week, and then the contact angle with the water on the sample surface was measured again. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 5 ° in response to photoexcitation.
[0038]
Example 12 (platinum addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After applying 0.3 g of a chloroplatinic acid hexahydrate aqueous solution having a platinum metal concentration of 50 μmol / g to the surface of the sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after the preparation of the sample was 42 °. The sample was left in the dark for one week, and then the contact angle with the water on the sample surface was measured again. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the sample surface was hydrophilized to 6 ° in response to photoexcitation. Thereafter, this sample was further irradiated with ultraviolet light of 0.01 mW / cm.2Were irradiated with a white light for 9 days, and the hydrophilicity maintenance under indoor lighting was examined. As a result, the sample surface was maintained at about 9 °.
[0039]
Example 13 (platinum addition, mixed addition)
18 g of ammonia peptization type titanium oxide sol (manufactured by Ishihara Sangyo Co., Ltd., STS-11) and 27 g of chloroplatinic acid hexahydrate aqueous solution with a platinum metal concentration of 77 μmol / g are mixed and spray coated on the surface of a 15 cm square glazed tile. The sample was applied by the method and baked at 700 ° C. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 21 °. The sample was left in the dark for one week, and then the contact angle with water on the sample surface was measured again. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 7 ° in response to photoexcitation.
[0040]
Example 14 (palladium addition, post-addition)
A titanium oxide layer-coated glazed tile sample having a film thickness of 0.3 μm was obtained in the same manner as in Comparative Example 1. After applying 0.3 g of palladium chloride aqueous solution having a palladium metal concentration of 50 μmol / g to the surface of the sample, 0.4 mW / cm2A sample was obtained by irradiating with a BLB fluorescent lamp for 10 minutes. The contact angle of the sample surface with water immediately after preparation of this sample was 47 °. The sample was left in the dark for one week, and then the contact angle with the water on the sample surface was measured again. Furthermore, this sample was irradiated with UV light of 0.3 mW / cm.2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 0.2 days, the sample surface was hydrophilized to 6 ° in response to photoexcitation.
[0041]
Example 15 (palladium addition, mixed addition)
18g of ammonia peptization type titanium oxide sol (STS-11, manufactured by Ishihara Sangyo) and 27g of palladium chloride aqueous solution with a palladium metal concentration of 77μmol / g were mixed and applied to the surface of 15cm square glazed tiles by spray coating method. And calcined at 700 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 15 °. This sample was left in a dark place for 1 week, and then the contact angle with water on the sample surface was measured again. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 7 ° in response to photoexcitation.
[0042]
Example 16 (ruthenium addition, mixed addition)
Ammonia peptization type titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) 18g and ruthenium metal concentration of 77μmol / g ruthenium chloride hydrate aqueous solution 27g are mixed, spray coating method on 15cm square glazed tile surface And then baked at 700 ° C. to obtain a sample. At this time, the thickness of the titanium oxide layer was set to 0.3 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 15 °. The sample was left in the dark for one week, and then the contact angle with the water on the sample surface was measured again. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2When the contact angle with water was measured after irradiation with a BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) for 0.2 days, the sample surface was hydrophilized to 7 ° in response to photoexcitation.
[0043]
Example 17 (aluminum addition, mixed addition)
Ammonia peptization type titanium oxide sol (Ishihara Sangyo Co., Ltd., STS-11) and an aluminum chloride aqueous solution with an aluminum metal concentration of 50 μmol / g were mixed so that the molar ratio of titanium oxide to the amount of aluminum metal was 87:13. The sample was applied to the surface of a 15 cm square glazed tile by a spray coating method and baked at 700 ° C. At this time, the thickness of the titanium oxide layer was set to 0.7 μm. The contact angle of the sample surface with water immediately after the preparation of the sample was 11 °. This sample was left in the dark for one day, and then the contact angle with water on the surface of the sample was again measured and found to be 13 °. Furthermore, this sample was irradiated with ultraviolet light of 0.15 mW / cm.2The BLB fluorescent lamp (Sankyo Electric, Black Light Blue, FL20BLB) was irradiated for 1 day, and the contact angle with water was measured. As a result, the sample surface was hydrophilized to 3 ° in response to photoexcitation.
[0044]
Example 18 (yttria addition)
Nitric acid peptization type titanium oxide sol (manufactured by Ishihara Sangyo Co., Ltd., CS-N) and acetic acid peptization type yttrium oxide sol (manufactured by Taki Chemical Co., Ltd., solute concentration 15% by weight, average crystallite diameter 4 nm, pH 7.6) After mixing so that the molar ratio with yttrium oxide was 88:12, it was applied to the surface of a 15 cm square glazed tile by a spray coating method and fired at 800 ° C. for 1 hour to obtain a sample. The film thickness at this time was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was 21 °. The obtained sample was left in the dark for 2 weeks. Thereafter, when the contact angle of the sample surface with water was measured again, it was 25 °. Then, UV illuminance 0.3mW / cm2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 13 days, the sample surface was hydrophilized to 2 ° in response to photoexcitation. Then UV illuminance 0.004mW / cm2The white light was irradiated for 4 days, and the hydrophilicity maintenance under indoor lighting was examined. As a result, the sample surface was maintained at about 9 °.
[0045]
Example 19 (alumina added)
Nitric acid peptized titanium oxide sol (Ishihara Sangyo, CS-C) and aluminum oxide sol (Nissan Chemical, alumina sol-100) were mixed so that the molar ratio of titanium oxide to aluminum oxide was 88:12. Thereafter, the sample was applied to the surface of a 15 cm square glazed tile by a spray coating method and fired at 800 ° C. for 1 hour to obtain a sample. The film thickness at this time was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was 2 °. The obtained sample was left in the dark for 2 weeks. Thereafter, when the contact angle of the sample surface with water was measured again, it was 20 °. Then UV illumination intensity 0.3mW / cm2When the contact angle with water was measured after irradiating the BLB fluorescent lamp for 13 days, the surface of the sample was again made hydrophilic by 2 ° in response to photoexcitation. Then UV illuminance 0.004mW / cm2Were irradiated with white light for 2 days, and the hydrophilicity maintenance under indoor lighting was examined. As a result, the sample surface was maintained at about 9 °.
[0046]
Example 20 (Zirconia added)
Ammonia peptization type titanium oxide sol (manufactured by Ishihara Sangyo Co., Ltd., STS-11) and zirconium oxide sol Indian Chemical Co., Ltd., NZS-30B) were mixed so that the molar ratio of titanium oxide and zirconium oxide was 88:12. Thereafter, the sample was applied to the surface of a 15 cm square glazed tile by a spray coating method and fired at 800 ° C. for 1 hour to obtain a sample. The film thickness at this time was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was 23 °. The obtained sample was left in the dark for one week. Thereafter, when the contact angle of the sample surface with water was measured again, it was 35 °. Then UV illumination intensity 0.3mW / cm2After the BLB fluorescent lamp was irradiated for 13 days, the contact angle with water was measured. As a result, the sample surface was hydrophilized to 4 ° in response to photoexcitation.
[0047]
Example 21 (ceria addition)
After mixing the ammonia peptization type titanium oxide sol (Ishihara Sangyo, STS-11) and the cerium oxide sol (Taki Chemical W-15) so that the molar ratio of titanium oxide to cerium oxide is 88:12. A 15 cm square glazed tile surface was applied by spray coating, and baked at 800 ° C. for 1 hour to obtain a sample. The film thickness at this time was set to 0.3 μm. The contact angle of the sample surface with water immediately after firing was 22 °. The obtained sample was left in the dark for one week. Thereafter, when the contact angle of the sample surface with water was measured again, it was 38 °. Then UV illumination intensity 0.3mW / cm2After the BLB fluorescent lamp was irradiated for 13 days, the contact angle with water was measured, and the sample surface was hydrophilized to 6 ° in response to photoexcitation.
[0048]
Example 22 (Relationship between contact angle with water and anti-fogging property)
A silica coating solution was prepared by adding 6 parts by weight of tetraethoxysilane, 6 parts by weight of pure water, and 2 parts by weight of 36% hydrochloric acid as a hydrolysis inhibitor for tetraethoxysilane to 86 parts by weight of ethanol. 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 10 cm square soda lime glass plate by a flow coating method and dried at a temperature of 80 ° C. During this time, tetraethoxysilane was first hydrolyzed to become silanol, and then a thin film of amorphous silica was formed on the surface of the glass plate by dehydration condensation polymerization of silanol. Next, a titania coating solution was prepared by adding 0.1 part by weight of 36% hydrochloric acid as a hydrolysis inhibitor to a mixture of 1 part by weight of tetraethoxytitanium (Merck) and 9 parts by weight of ethanol. The surface of the glass plate was applied in a dry air by a flow coating method. The coating amount is 45 μg / cm in terms of titania2It was. Next, this glass was kept at a temperature of 150 ° C. for 10 minutes to complete the hydrolysis of tetraethoxytitanium, and the produced titanium hydroxide was subjected to dehydration condensation polymerization to produce amorphous titania. Thus, a glass plate in which amorphous titania was coated on amorphous silica was obtained. This glass plate was baked at a temperature of 500 ° C. to convert amorphous titania into anatase titania. The obtained sample was left in the dark for several days. Next, this glass plate is placed in a desiccator (
[0049]
[Table 1]
Example 23 (Relationship between contact angle with water and antifouling property)
Various samples were subjected to the sludge test shown below. The examined samples are the following # 1 to # 6 samples. # 1 sample: a mixture of anatase-type titanium oxide sol (manufactured by Ishihara Sangyo Co., Ltd., STS-11) and colloidal silica sol (Snowtex 20) (silica content of 10% by weight) in terms of solid content is only 4.5 mg, It was applied to a 15 cm square glazed tile (manufactured by Totoki Equipment, AB02E01) and baked at a temperature of 880 ° C. for 10 minutes to obtain a # 0 sample. This # 0 sample was irradiated with ultraviolet rays at 0.5 mW /
[0051]
[Table 2]
Furthermore, an outdoor dirt acceleration test was conducted on the # 1, # 3, # 4, # 6, and # 7 samples shown below. # 7 Sample: Silica sol (manufactured by Nippon Synthetic Rubber, Glassca A solution) and trimethoxysilane (manufactured by Nippon Synthetic Rubber, Glassca B solution) were mixed in a 10 cm square aluminum substrate so that the weight ratio was 3: 1. The liquid material was applied and cured at 150 ° C. to obtain a silicone-coated plate (# 7 sample) having a film thickness of 3 μm. The outdoor dirt acceleration test was conducted as follows. That is, the outdoor dirt acceleration test apparatus shown in FIGS. 1A and 1B was installed on the roof of the building in Chigasaki City. Referring to FIGS. 1 (a) and 1 (b), the apparatus includes an inclined
[0053]
[Table 3]
In order to facilitate understanding, the contact angles with water and the color difference changes shown in Tables 2 and 3 were plotted in the graph of FIG. In the graph of FIG. 2, curve A shows the relationship between the color difference change caused by combustion products such as carbon black in the atmosphere and dirt such as urban dust in the dirt acceleration test and the contact angle with water, and curve B shows the sludge test. Shows the relationship between the change in color difference due to sludge and the contact angle with water. Referring to the graph of FIG. 2, as can be clearly seen from the curve A, as the contact angle of the substrate with water increases, the contamination due to the combustion products and urban dust becomes conspicuous. This is because pollutants such as combustion products and urban dust are basically hydrophobic and therefore tend to adhere to hydrophobic surfaces. On the other hand, curve B shows that dirt due to sludge exhibits a peak value when the contact angle with water is in the range of 20 ° to 50 °. This is because an inorganic substance such as mud and soil has a hydrophilicity with a contact angle with water of about 20 ° to 50 °, and tends to adhere to a surface having a similar hydrophilicity. Therefore, if the surface is made hydrophilic with a contact angle with water of 20 ° or less, or if the contact angle with water is hydrophobized to 60 ° or more, adhesion of inorganic substances to the surface can be prevented. I understand. When the contact angle with water is 20 ° or less, the dirt due to sludge decreases. When the surface becomes highly hydrophilic with a contact angle with water of 20 ° or less, the affinity for water is higher than the affinity for inorganic substances. This is because the adhesion of the inorganic substance is inhibited by the water preferentially adhering to the surface, and the inorganic substance to be adhered is easily washed away by the water. From the above, in order to prevent both hydrophobic dirt and hydrophilic dirt substances from adhering to the surface of buildings, etc., or dirt accumulated on the surface is washed away by rain and the surface is self-cleaned. It can be seen that the contact angle with water on the surface should be 20 ° or less, preferably 10 ° or less, and more preferably 5 ° or less. In any of the above Examples 1 to 21, the contact angle with water becomes 10 ° or less in response to photoexcitation, and thus it is considered that all of them exhibit excellent cleanliness by rain or washing.
[0055]
【The invention's effect】
In addition to optical semiconductors on the substrate surfaceAt least one selected from the group consisting of lithium, sodium, potassium, calcium, strontium, aluminum, alumina, zirconia, and yttria that has the effect of promoting hydrophilicity on the surface of the substrate.Even when the optical semiconductor-containing layer is formed on the surface of the substrate by the sol coating and baking method, the photo-semiconductor is photoexcited by a light source that is commonly used such as sunlight or indoor lighting. Until 10 ° or less. In addition, even when an optical semiconductor-containing layer is formed on the substrate surface by an alkoxide method, a sputtering method, or a method using curing of a binder such as silica or silicone other than the sol coating baking method, photoexcitation of the optical semiconductor is performed. Improvement in hydrophilic performance can be expected according to the conditions.Furthermore, in the case of alumina or yttria, 0.01 mW / cm 2 Under the weak excitation light irradiation of less than about less, the hydrophilicity maintenance property in a dark place comes to be exhibited better.
[Brief description of the drawings]
1A and 1B are diagrams showing an outdoor dirt acceleration test apparatus, in which FIG. 1A is a front view, and FIG. 1B is a side view (units of dimensional numerical values are millimeters).
FIG. 2 is a diagram showing the degree of contamination of a surface having different hydrophilicity by urban dust and sludge.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23956799A JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
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| Application Number | Priority Date | Filing Date | Title |
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| JP35464995 | 1995-12-22 | ||
| JP7-354649 | 1995-12-22 | ||
| JP23956799A JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
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| Application Number | Title | Priority Date | Filing Date |
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| JP8195184A Division JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2000227055A Division 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 |
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| JP2000136370A JP2000136370A (en) | 2000-05-16 |
| JP3613084B2 true JP3613084B2 (en) | 2005-01-26 |
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| 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 |
| 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 |
| JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
| 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 |
| JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
| JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
| 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 |
| JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
| JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
| JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
| JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
| JP2002020533A Expired - Fee Related JP3882625B2 (en) | 1995-12-22 | 2002-01-29 | Sound insulation wall and cleaning method for sound insulation wall |
| JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Family Applications Before (59)
| 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 |
| JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
| JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
| 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 |
| 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 |
| 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 |
| JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
| JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
| JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
| JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
| JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel 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 |
| JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
| JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
| 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 |
| JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
| 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 |
| JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
| JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
| 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 |
| JP28579796A Expired - Lifetime JP3697795B2 (en) | 1995-12-22 | 1996-09-20 | Display and cleaning method thereof |
| 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 |
| JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
| 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 |
| 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 |
| JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
| 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 |
| JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
| JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
| JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
| JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
Family Applications After (11)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
| JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
| JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
| JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
| JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
| JP2002020533A Expired - Fee Related JP3882625B2 (en) | 1995-12-22 | 2002-01-29 | Sound insulation wall and cleaning method for sound insulation wall |
| JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (71) | JPH09231821A (en) |
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| JP3499585B2 (en) * | 1993-09-21 | 2004-02-23 | 日揮ユニバーサル株式会社 | Ethylene decomposition photocatalyst |
| JP2517874B2 (en) * | 1993-09-30 | 1996-07-24 | 工業技術院長 | Method for producing titanium oxide thin film photocatalyst |
| JP3334767B2 (en) * | 1993-10-20 | 2002-10-15 | 日新製鋼株式会社 | Building materials with moisture absorption and release functions |
| JP2602022Y2 (en) * | 1993-11-25 | 1999-12-20 | 旭光学工業株式会社 | Dew condensation removal device in camera |
| JPH07149520A (en) * | 1993-11-29 | 1995-06-13 | Hoya Corp | Coating composition |
| JPH07164607A (en) * | 1993-12-13 | 1995-06-27 | Mitsubishi Chem Corp | Agricultural film |
| JPH07168001A (en) * | 1993-12-15 | 1995-07-04 | Nikon Corp | Mildew-proofing optical equipment |
| JP3488496B2 (en) * | 1993-12-21 | 2004-01-19 | 日揮ユニバーサル株式会社 | Poison-resistant deodorizing photocatalyst |
| JP3391543B2 (en) * | 1993-12-27 | 2003-03-31 | 花王株式会社 | Hydrophilizing agent and hydrophilizing method |
| JP2883000B2 (en) * | 1994-03-29 | 1999-04-19 | 三菱重工業株式会社 | Automobile sound insulation wall cleaning device |
| JP3693363B2 (en) * | 1994-03-30 | 2005-09-07 | 松下エコシステムズ株式会社 | Supporting method for forming a photocatalyst layer |
| JPH07331120A (en) * | 1994-06-10 | 1995-12-19 | Hitachi Ltd | Coating for removing nitrogen oxide and its use |
| JP2832239B2 (en) * | 1994-06-21 | 1998-12-09 | 三井金属鉱業株式会社 | Lighting equipment with photocatalytic function |
| JPH0810576A (en) * | 1994-07-05 | 1996-01-16 | Ebara Res Co Ltd | Removing method of harmful gas and device therefor |
| JPH08119673A (en) * | 1994-10-21 | 1996-05-14 | Kansai Paint Co Ltd | Hydrophilization treatment of glass |
| JPH08277147A (en) * | 1995-03-31 | 1996-10-22 | Nippon Muki Co Ltd | Plate glass |
| JPH09129012A (en) * | 1995-03-31 | 1997-05-16 | Toshiba Lighting & Technol Corp | Photocatalyst, fluorescent lamp and luminaire |
| JP3101537B2 (en) * | 1995-05-10 | 2000-10-23 | ワイケイケイ株式会社 | Antifouling building material and exterior building material unit |
| JPH0929103A (en) * | 1995-05-17 | 1997-02-04 | Toshiba Lighting & Technol Corp | Photocatalytic body, photocatalytic device, light source and lightening equipment |
| JPH08313705A (en) * | 1995-05-22 | 1996-11-29 | Seiko Epson Corp | Anti-clouding article and its production |
| JP3127827B2 (en) * | 1995-06-14 | 2001-01-29 | 東陶機器株式会社 | Anti-fog seal |
| EP1955768A1 (en) * | 1995-06-19 | 2008-08-13 | Nippon Soda Co., Ltd. | Photocatalyst-carrying structure and photocatalyst coating material |
| JPH0990889A (en) * | 1995-09-27 | 1997-04-04 | Toshiba Lighting & Technol Corp | Sign body and externally illuminated sign device |
| JPH09173783A (en) * | 1995-10-27 | 1997-07-08 | Matsushita Electric Ind Co Ltd | Sheet glass and resin plate and their production and method for removing contaminant |
| JP4237830B2 (en) * | 1995-12-20 | 2009-03-11 | 日本曹達株式会社 | Photocatalyst-carrying lighting fixture |
| JPH09231821A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
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1996
- 1996-04-05 JP JP8083499A patent/JPH09231821A/en active Pending
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