JP4233654B2 - Method for producing photocatalyst carrying structure and photocatalyst carrying structure obtained by the method - Google Patents
Method for producing photocatalyst carrying structure and photocatalyst carrying structure obtained by the method Download PDFInfo
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- JP4233654B2 JP4233654B2 JP34815798A JP34815798A JP4233654B2 JP 4233654 B2 JP4233654 B2 JP 4233654B2 JP 34815798 A JP34815798 A JP 34815798A JP 34815798 A JP34815798 A JP 34815798A JP 4233654 B2 JP4233654 B2 JP 4233654B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 109
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Description
【０００１】
【発明の属する技術分野】
本発明は、高分子樹脂製の基材表面に光触媒層を形成してなる光触媒担持構造体の製造技術に関する。
【０００２】
【発明の背景】
光触媒は、紫外線を照射された場合に酸化力を生じ、これにより脱臭、殺菌、防汚などの優れた効果を発揮し得る。従って、基材表面にこのような特性を発揮可能な光触媒層を形成することにより、優れた特性を発揮する高分子樹脂製の素材を得ようとする試みが、様々な分野においてなされている。
【０００３】
例えば、明るい室内空間を得ることが可能であり、また軽く、成形に関する自由度が高いなどの意匠的側面からの優位性を備えるために建材としての利用が近年急激に増大している高分子樹脂製の膜材では、従来、屋外使用の際に雨だれによって発生する黒色の筋模様が悩みの種であった。そこで、かかる不具合を解消するために膜基材の表面に酸化チタンなどの光触媒を塗布する技術が実用化されるに至っている（特開平１０−２３７７６９号参照。）。このような膜基材は、自浄力を備えるものであり、上記の如き意匠的利点に加えて構造物の美観を維持するに必要な手間も小さくて済むという非常に優れた建材となっている。
【０００４】
しかしながら、光触媒層をその表面に形成した樹脂膜材でもその酸化力に基づく脱臭、殺菌、防汚などの機能が十分だとは言えない場合もある。例えば、光触媒層を備えた上記の如き樹脂膜材においては、水との接触角が５０°程度と比較的大きいことから表面の親水性を十分に確保できない場合があり、降雨後一時的に、雨水の流下した部分に汚れが発生することがある。このような不具合を解消するために光触媒性能を更に強化するのが望ましいのが自明であることは、樹脂製の膜基材を用いた光触媒担持構造体に限らず、他の樹脂製基材を用いた光触媒担持構造体についても同様である。
【０００５】
【発明が解決しようとする課題】
そこで、本発明は、高分子樹脂製基材の表面に光触媒層を形成してなる光触媒担持構造体を、その光触媒の機能がより強力になるように改良することをその目的とする。
【０００６】
【課題を解決するための手段】
本発明では、従来の光触媒担持構造体表面に設けられた光触媒層を再加熱することにより、光触媒の機能を強化することにしている。即ち、従来の光触媒担持構造体は、高分子樹脂からなる基材の表面に光触媒塗布液を塗布して光触媒層を形成し、これを加熱乾燥し、基材の表面に光触媒を担持させることによってその製造がなされているが、本発明では、この加熱乾燥を行った後に、乾燥温度以上且つ８００℃以下の温度で、基材の変形が生じないような時間範囲内で、光触媒層を再加熱することにより光触媒担持構造体を製造することとしている。本出願人は、このようにして得た光触媒担持構造体が従来のそれよりも高い触媒活性を示すことを既に確認している。
【０００７】
現時点では詳しい理論は不明であるが、出願人は、以下のような理論により、上記触媒活性の向上が達成された一因を説明できると考えている。即ち、従来の光触媒担持構造体の製造方法では、光触媒層を基材の表面に塗布した後においては、樹脂基材の軟化による変形が発生するのを防止するために、比較的低温での加熱による光触媒層の乾燥が比較的長時間をかけて行われている。具体的には、基材が塩化ビニルの如き熱可塑性の高分子樹脂からなる場合には、光触媒層を乾燥する際の加熱温度は、３０℃以上１６０℃未満であり、それより高温での乾燥が可能な熱硬化性の樹脂などにおいてもこの程度の温度で光触媒層の乾燥が行われている。出願人の考えでは、この乾燥工程において、基材に含まれている可塑剤などの有機物が光触媒層に移動しており、これが光触媒粒子を覆うことで触媒活性の低下を招いている。従って、前記乾燥工程を行った後に、乾燥工程における温度よりも高い温度での光触媒層加熱を行い、そしてその再加熱の過程で前記不純物の除去が生じているとすれば、再加熱温度が基材に変形を生じないような短時間であったとしても、それにより触媒活性の向上が生じることは十分起こりうることであると考えられる。
【０００８】
つまり、本出願による光触媒担持構造体の製造方法では、乾燥温度よりも高い温度で光触媒層を再加熱することが必要であり、これが再加熱温度の下限となっている。一方、再加熱温度が光触媒層の乾燥温度よりも高ければ、本願発明の再加熱温度には本来上限がない。しかしながら、余りにも再加熱温度が高い場合には例えば基材の熱分解が生じるなどの不具合が予想されるし、また出願人が研究を行った範囲では一定以上の高温で再加熱をしたとしても、光触媒自身の活性の向上はそれ以上の変化を見せないことが判明している。逆に、加熱温度が８００℃を超えた場合には、触媒に二酸化チタンを用いた場合においては、アナターゼ型から触媒活性がそれよりも低いルチル型への相転移が生じることにより、触媒活性が低下することも考えられる。従って、これらの点に加えてコスト面も考慮すれば、本発明による光触媒担持構造体の製造方法で行う再加熱の温度は８００℃もあれば十分と言える。
【０００９】
また、ここで１５０℃以上の高温化でも軟化、変形を生じない、例えば熱硬化性の高分子樹脂からなる基材を用いる場合には、１５０℃以上８００℃以下の温度をある程度長い時間かけることが可能なので、光触媒層の乾燥を従来の如く３０℃以上１６０℃以下の温度で行った後に、１５０℃以上８００℃以下の温度（但し、乾燥温度よりは高い温度範囲とする。）で光触媒層の再加熱を行えば、上記のような高い触媒活性を示す光触媒担持構造体を得られることになる。特に、光触媒層の再加熱を、３００℃以上６００℃以下とした場合には、光触媒の活性が非常に高くなると同時に、コスト面からも優れたものとなるため好ましい。
【００１０】
一方、本発明による光触媒担持構造体の製造方法は、基材の軟化点温度が比較的低い場合に応用することも意図している。例えば、光触媒層が表面に形成された基材を加熱したローラなどに接触させて再加熱したり、高温の熱風が出るライスタなどを用い、これを動かしながら光触媒層を再加熱することによって再加熱の時間を短時間とすることが可能であり、そうすることで基材に変形を生じさせることなく、基材の軟化点温度よりも高い温度によって再加熱を行えるようになる。このような短時間の加熱によっても触媒活性の向上が確認されているのは勿論である。尚、この場合の再加熱温度は、比較的高温の高分子樹脂を基材に利用する場合に適している上記の場合と同様の範囲内とすることができる。
【００１１】
また、上記光触媒担持構造体の製造方法においては、光触媒層の再加熱時に、又は光触媒層を再加熱した後に、光触媒層を基材へ押圧するのが好ましい。このようにすることで、光触媒層の基材への結合力が強固になるからである。
【００１２】
本発明における光触媒塗布液としては、シリコン化合物を０．００１％〜５重量％、金属の酸化物及び／又は水酸化物のゾルを、固型分として０．１〜３０重量％、及び光触媒の粉末及び／又はゾルを、固型分として０．１〜３０重量％含有するものを用いることができる。
【００１３】
ここで本発明における光触媒としては、粉末状、ゾル状、溶液状など、光触媒層の乾燥温度で乾燥した時に、樹脂製の基材に固着して光触媒活性を示すものであればどのようなものでも使用可能である。ゾル状の光触媒を使用する場合、粒子径が２０ｎｍ以下、好ましくは１０ｎｍ以下のものを使用する
。
【００１４】
また、本発明における光触媒としては、ＴｉＯ２、ＺｎＯ、ＳｒＴｉＯ３、ＣｄＳ、ＧａＰ、ＩｎＰ、ＧａＡｓ、ＢａＴｉＯ３、ＫＮｂＯ３、Ｆｅ２Ｏ３、Ｔａ２Ｏ５，ＷＯ３、ＳｎＯ２、Ｂｉ２Ｏ３、ＮｉＯ、Ｃｕ２Ｏ、ＳｉＣ、ＳｉＯ２、ＭｏＳ２、ＩｎＰｂ、ＲｕＯ２、ＣｅＯ２など、及びこれらにＰｔ，Ｒｈ，ＲｕＯ２、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅなどの金属又はこれら金属の酸化物を添加したものを利用することができる。また、これらに光触媒還元作用を利用してＰｔ、Ｒｈ、ＲｕＯ２、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅなどの金属を添加したものなどを使用可能である。
【００１５】
また、本発明の光触媒層の塗布液中に添加するシリコン化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、及びそれらの加水分解生成物の１種又は２種以上の混合物を用いることができる
。
【００１６】
光触媒層形成のための塗布液中へシリコン化合物を添加する方法についての制限は特にないが、光触媒粉末若しくはゾルの液中へ添加する方法や、光触媒とともに添加する金属酸化物及び／又は水酸化物のゾル液中へ添加する方法など種々の方法を使用することが出来る。また、部分加水分解されたシリコン化合物をこれに添加されていても良い。
【００１７】
また、上記金属酸化物ゲル若しくは金属水酸化物ゲルは、その比表面積が、１５０℃で乾燥後５０ｍ２／ｇ以上あるのが好ましく、１００ｍ２／ｇ以上あると更に好ましい。このような比表面積を有するのであれば接着性はより強固になり、触媒活性も向上することになる。ここで、金属成分としては、珪素、アルミニウム、チタニウム、ジルコニウム、マグネシウム、ニオビウム、タンタラム、タングステン、錫等の金属の酸化物ゲル若しくは水酸化物ゲルを好ましく例示することができる。
【００１８】
また、実際の使用に当たっては、ゲルを形成させるためのゾルを混合し乾燥して得られるゲルでも、共沈法などの方法で作られる複合酸化物ゲルを使用しても良い。光触媒との複合化には、ゲルとなる前のゾルの状態で均一混合するか、若しくは、ゾルを調製する前の原料段階で混合するのが望ましい。ゲルを調製する方法には、金属塩を加水分解する方法、中和分解する方法、イオン交換する方法、金属アルコキシドを加水分解する方法等があるが、ゲルの中に光触媒粉末が均一に分散された状態で得られるものであれば、いずれの方法も使用可能である。但し、ゲル中に多量の不純物が存在すると、光触媒の接着性や触媒活性に悪影響を与えるので、不純物の少ないゲルの方が好ましい。
【００１９】
また、本発明に使用される光触媒坦持基材では、光触媒層と基材との間に接着層及び／又は中間層を設けることができる。接着層塗布液としては、例えばシリコン含有量２〜６０重量％のシリコン変性樹脂、ポリシロキサンを３〜６０重量％含有する樹脂やコロイダルシリカを５〜４０重量％含有する樹脂を樹脂固形分として１〜５０重量％含む溶液を使用することができる。
【００２０】
接着層樹脂がアクリル−シリコン樹脂やエポキシ−シリコン樹脂等のシリコン変性樹脂とされている場合におけるシリコンの樹脂への導入方法は、エステル交換反応、シリコンマクロマーや反応性シリコンモノマーを用いたグラフト反応、ヒドロシリル化反応、ブロック共重合法等種々あるが、本発明ではどのような方法で作られた物でも使用することができる。シリコンを導入する樹脂としては、成膜性、強靭性、担体との密着性の点で最も優れたアクリル樹脂やエポキシ樹脂を使用するのが好ましいが、アルキッド樹脂、ウレタン樹脂、ポリエステル樹脂等をこれらに代えて使用することもできる。これらの樹脂は、溶剤に溶けたタイプであってもエマルジョンタイプであってもどちらでも使用することができる。また、架橋剤などの添加物が含まれていても何等問題はない。
【００２１】
接着層樹脂として、ポリシロキサンを含有し、そのポリシロキサンが炭素数１〜５のアルコキシ基を有するシリコンアルコキシドの加水分解物或いは該加水分解物からの生成物を用いた場合には、接着性及び耐久性がより向上した担持構造体を得ることができる。また、シリコンアルコキシドのアルコキシ基の炭素数が６以上であると、高価であり、しかも加水分解速度が非常に遅くなるので樹脂中での硬化が困難になり、接着性や耐久性に劣るものとなる。また、部分的に塩素を含んだシリコンアルコキシドを加水分解したポリシロキサンを使用することもできるが、塩素を多量に含有したポリシロキサンを使用すると、不純物の塩素イオンによって、担体の腐食や接着性の劣化が生じる場合もある。
【００２２】
ポリシロキサンを樹脂へ導入する方法としては、シリコンアルコキシドモノマーの状態でポリシロキサンを樹脂溶液へ混合し、接着層形成時に空気中の水分で加水分解させる方法、前もって、シリコンアルコキシドを部分加水分解した物を樹脂と混合し、更に、保護膜形成時に空気中の水分で加水分解する方法等種々あるが、樹脂と均一に混合できる方法ならどのような方法でも良い。また、シリコンアルコキシドの加水分解速度を変えるために、酸や塩基触媒を少量添加しても構わない。ここで、ポリシロキサンを導入する樹脂としては、アクリル樹脂、アクリル−シリコン樹脂、エポキシ−シリコン樹脂、シリコン変性樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、アルキッド樹脂等の使用が可能であるが、耐久性の点から見れば、アクリル−シリコン樹脂やエポキシ−シリコン樹脂を含むシリコン変性樹脂を用いるのが最も優れている。
【００２３】
接着層が、コロイダルシリカを含有する樹脂の場合、そのコロイダルシリカの粒子径は１０ｎｍ以下が好ましい。１０ｎｍ以上になると、接着層中の樹脂は光触媒により劣化し易くなるばかりか、光触媒層と接着層との接着も悪くなる。このコロイダルシリカを樹脂に導入する方法としては、樹脂溶液とコロイダルシリカ溶液とを混合後、これを塗布、乾燥して接着層を形成する方法が最も簡便であるが、コロイダルシリカを分散した状態で、樹脂を重合し、合成したものを塗布、乾燥して使用しても良い。また、コロイダルシリカと樹脂との接着性及び分散性を良くするために、シランカップリング剤でコロイダルシリカを処理して用いることもできる。
【００２４】
コロイダルシリカを導入する樹脂としては、アクリル樹脂、アクリル−シリコン樹脂、エポキシ−シリコン樹脂、シリコン変性樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、アルキッド樹脂等を挙げられるが、アクリル−シリコン樹脂やエポキシ−シリコン樹脂を含むシリコン変性樹脂を用いるのが耐久性の点から最も優れている。また、コロイダルシリカは、珪酸ナトリウム溶液を陽イオン交換することにより作られるシリカゾルであっても、シリコンアルコキシドを加水分解して作られるシリカゾルであっても、どのような物でも使用することができる。
【００２５】
また、光触媒作用による劣化を抑える目的で、上記接着層樹脂に、光安定化剤及び／又は紫外線吸収剤等を混合することにより耐久性を向上させることができる。光安定化剤としては、ヒンダードアミン系のものを用いるのが好ましいが、その他の物を使用することも可能である。紫外線吸収剤としてはトリアゾール系などを使用できる。添加量は、樹脂に対して０．００５ｗｔ％以上１０ｗｔ％以下、好ましくは０．０１ｗｔ％以上５ｗｔ％以下である。尚、接着層の表面をシラン系若しくはチタン系カップリング剤で処理すると光触媒層との接着性が向上することがある。また、接着層の溶液中に界面活性剤を０．００００１重量％〜０．１重量％添加することによっても良好な光触媒担持体とすることができる。
【００２６】
接着層を担体に担持する方法としては、樹脂溶液を、印刷法、シート成形法、スプレー吹き付け法、ディップコーティング法又はスピンコーティング法等でコートしてから乾燥する方法を使用できる。この場合の乾燥温度は、溶媒や樹脂の種類によっても異なるが、一般的に１５０℃以下が好ましい。接着層の厚さを０．１μｍ以上とすれば、光触媒層を強固に接着した耐久性の高い光触媒担持構造体とすることが可能である。尚、光触媒担持構造体の基材を膜材とする場合においてその屈曲性能の確保を考慮するのであれば、接着層の厚さは１０μｍが上限となる。また、グラビア印刷法などの短時間で接着層を乾燥硬化させることが必要な塗布法の場合は、シリコン系などの硬化剤を接着層固形分に対し、必要な硬化速度に応じて０．１〜１０重量％添加することも好ましく採用される。
【００２７】
光触媒層を基材又は接着層上へ形成するには、金属酸化物ゾル若しくは金属水酸化物ゾル液中に光触媒を分散した懸濁液を、接着層形成の場合と同様のコート法を用いてコートすることができる。金属酸化物ゾル若しくは金属水酸化物ゾルの前駆体溶液の状態で光触媒を分散し、コート時に加水分解や中和分解してゾル化若しくはゲル化させても良い。ゾルを使用する場合には、安定化のために、酸やアルカリの解膠剤等が添加されていても良い。また、ゾル懸濁液中に光触媒に対し、５重量％以下の界面活性剤やシランカップリング剤などを添加して、接着性や操作性を良くすることもできる。光触媒層形成時の乾燥温度としては、担体材質及び接着層中の樹脂材質によっても異なるが、３０℃以上１６０℃未満が好ましい。
【００２８】
光触媒層は、厚さを増した方が高活性を得られるが、厚さが５μｍ以上になると活性がほとんど変わらなくなる。一方、厚さ５μｍ以下でも実用的に足りる十分に高い触媒活性を得ることが可能であり、しかも光触媒槽の厚さを減少させた場合には、透光性に優れ、且つ触媒層が目立たなくなるという利点が生じる。しかし、厚さが、０．１μｍ未満になると透光性には非常に優れたものになるものの、光触媒が利用している紫外線をも透過するものとなってしてしまうため、高い触媒活性は望めなくなる。ここで、光触媒層の厚さを０．１μｍ以上５μｍ以下にし、且つ結晶粒子径が４０ｎｍ以下の光触媒粒子及び比表面積１００ｍ２／ｇ以上の金属酸化物ゲルもしくは金属水酸化物ゲルを用いると、光触媒層と接着層の合計の波長５５０ｎｍの全光線透過率は７０％以上になる。波長５５０ｎｍの全光線透過率が、７０％以上になるように担持した構造体は、基材が透明な場合、透過した可視光線を照明として利用でき、また基材が不透明な場合でも、基材上の柄を損なうことがないので装飾性の上でも有用となる。
【００２９】
ここで、中間層塗布液としては光触媒機能及び光触媒坦持基材全体の密着性等を損なわなければその組成について特に制限はなく、例えば、前記した光触媒塗布液又は接着層塗布液をそのまま又は組成を変更して用いることができる。また、前記した条件を満たす限り、複数の層が含まれていても構わない。中間層を接着層上に形成するには、接着層や光触媒層を形成する方法と同様なコート方法でコートすることができる。中間層の厚みは、特に制限はされないが、接着層及び光触媒層を合わせた全体の厚みがあまり大きくなりすぎると、基材の加工性及び耐久性等に問題が生じるため通常は０．１μｍ以上１０μｍ以下の範囲が好ましい。
【００３０】
ここで、本発明に用いられる基材は、高分子樹脂製であればその原料について特に制限されることはないが、例えばポリエチレンテレフタレート樹脂、ポリカーボネート樹脂、ポリアクリル酸エステル樹脂、ポリメチルメタクリレート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリフッ化ビニリデン樹脂、フッ化エチレン−プロピレン共重合樹脂、フッ化エチレン−エチレン共重合樹脂等により、上記基材を形成することができる。また、基材として、１重量％以上８０重量％以下の可塑剤、好ましくは５重量％以上８０重量％以下の可塑剤を含むものを用い、これに本発明による光触媒坦持基材の製造方法を適用した場合には、従来の方法により得た光触媒担持基材と比較して顕著に光触媒機能の向上が見られる。また、基材として１０重量％の塩化ビニル樹脂を含むものを用い、これに本発明による光触媒坦持基材の製造方法を適用した場合には、従来の方法により得た光触媒担持基材と比較して顕著に光触媒機能の向上が見られるようになる。
【００３１】
本発明に用いられる高分子基材の形状は、フィルム状、板状、管状、繊維状、網状等どのような形状でもよい。また、その大きさは１０μｍ以上であれば光触媒を強固に担持することができる。高分子樹脂基材と光触媒層、接着層、又は中間層との密着性を良くするために、放電処理やプライマ−処理等をその表面にい施した高分子樹脂基材を用いることもできる。また、施工済の建築資材、家庭電化製品、めがね等用途によっては、製品として存在する加工済の高分子樹脂成形体に本発明の光触媒担持構造体の製造方法による処理を行うことによって、本発明による光触媒担持構造体とすることもできるため、その応用範囲は極めて広いと言える。
【００３２】
特に膜材、その中でもテント地キャンバスに本発明の方法を応用した場合、従来の方法で製造した場合に比較して顕著な効果が現れる。テント地キャンバスとしては、既存のどの様な種類のテント地キャンバスでも用いることができる。ポリエステル等の樹脂からなる繊維を織った基布、該基布に塩化ビニル樹脂をコート含浸塗布により加工した塩ビ含浸基布、該塩ビ含浸基布の表面をアクリル、フッ素樹脂等でコートした表面処理塩ビ含浸基布など、テント地キャンバスとして呼称される全てのものに適用可能であるが、広く使用されているＢ種テント地キャンバス、Ｃ種テント地キャンバス、倉庫用膜材料に対しては特に好ましく使用できる。
【００３３】
また、本発明の光触媒担持テント地キャンバスは、広く一般建築用材料として、例えばテント倉庫の屋根、トラックシートなどの輸送体機器の幌、野積みシート、店舗用装飾テント、商店等の軒だし日除け、各種アーケードの屋根、展示会パビリオン等の屋根や側面の覆い、ガソリンスタンドの屋根や側面の覆い、防水保護シート、防雪シート、エアードーム、プールカバー等、防汚、抗菌、防カビの効果を必要とする多くの場面にその優れた防汚性、抗菌性、防カビ性を生かして長期にわたって表面の美麗な状態を維持するため、特に好ましく使用できるものである。
【００３４】
【発明の実施の形態】
本発明による光触媒担持基材の製造方法の好ましい一実施形態について以下説明する。
【００３５】
実施例
この実施例では、（株）クラレ製Ｃ種テント地キャンバスであるファルコンＫＮ−Ｃ２０００（１０３ｃｍ幅×５０ｍ ２０７ホワイト）を高分子樹脂基材として使用した。尚、このファルコンＫＮ−Ｃ２０００は、塩化ビニル及び可塑材を含んでいる。
【００３６】
この実施例における光触媒担持基材の製造方法を行うには、まずこのファルコンＫＮ−Ｃ２０００をＡ４サイズに切り出し、シリコン含量３重量％のアクリル−シリコン樹脂を１０重量％含有するキシレン−イソプロパノール（５０／５０）溶液に、アクリル−シリコン樹脂に対して３０重量％のポリシロキサン（コルコート（株）製メチルシリケート５１）と、及び界面活性剤とを添加し、混合した溶液を、Ｎｏ．７のバーコーターで塗布し、６０℃で３０分乾燥して接着層とした。尚、接着層の厚さは約０．５μｍである。
【００３７】
室温下放冷後、光触媒層として酸化チタン含有量５重量％の硝酸酸性チタニアゾルを、酸化珪素含有量５重量％の硝酸酸性シリカゾル中に界面活性剤の存在下分散させ、光触媒塗布液とした。この光触媒塗布液を、接着層の場合と同様にＮｏ．７のバーコーターで上記接着層の表面に塗布して光触媒層を形成した。その後、光触媒層を形成の高分子樹脂基材を、６０℃で３０分間乾燥して光触媒担持構造体（光触媒担持Ｃ種テント地キャンバス）とした。尚、光触媒層の厚さは、約０．６μｍである。
【００３８】
その後、加熱温度、再加熱時間を変化させ、上記乾燥させた光触媒層を複数条件下で再加熱した。この実施例における再加熱は、ライスタによる速さ３．０ｍ／分での高温熱風吹き付け、又は恒温槽での１分間の加熱により行った。再加熱の条件及びそれにより得られた光触媒担持基材の触媒性能に関する試験結果を表１に示している。この試験では、従来方法及び本件実施形態で説明した方法で得た光触媒担持基材によるシート材を屋外で暴露し、色差を測定することにより行った。暴露期間は、平成１０年８月２５日〜同１０月８日までである。また、色差測定は、波長範囲３８０ｎｍ〜７８０ｎｍまでで、Ｎ＝１である。
【００３９】
【表１】
また、上記と同様の条件で得た光触媒担持構造体に対する水の接触角を調べ、それを表２にまとめた。
【００４１】
【表２】
上記表１及び表２より、ライスタを用いた再加熱の場合には、再加熱処理を行わない場合上比較して、再加熱温度を上げるにつれて光触媒性能が向上しているのがわかる。特に、再加熱温度が２００℃を超え３００℃に達したときには、極めて優れた光触媒性能が発揮されている。尚、この実施例では、いずれの基材の形態にも特に変化は見られなかった。一方、恒温槽による再加熱の場合には、再加熱温度が１００℃の場合には目立った効果が見られなかったが、１５０℃で１分の再加熱を行うことにより光触媒性能の明かな向上が見られた。
【００４３】
【発明の効果】
本発明に係る光触媒担持基材の製造方法によれば、従来品と比較して遥かに高い脱臭、殺菌、防汚などの触媒性能を発揮する光触媒担持基材を得られるようになる。特に、高分子基材として膜基材を用いた光触媒担持基材は、屋外使用で高い自浄作用を発揮しうる優れた建材となり得る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a technique for producing a photocatalyst-supporting structure in which a photocatalyst layer is formed on the surface of a polymer resin substrate.
[0002]
BACKGROUND OF THE INVENTION
The photocatalyst generates oxidizing power when irradiated with ultraviolet rays, and thereby can exhibit excellent effects such as deodorization, sterilization, and antifouling. Therefore, attempts have been made in various fields to obtain a polymer resin material exhibiting excellent characteristics by forming a photocatalyst layer capable of exhibiting such characteristics on the substrate surface.
[0003]
For example, it is possible to obtain a bright indoor space, and it is light and has a rapid increase in use as a building material in recent years in order to have advantages from a design aspect such as high degree of freedom regarding molding. Conventionally, a black streak pattern generated by raindrops when used outdoors has been a problem in film materials made of the material. Therefore, a technique for applying a photocatalyst such as titanium oxide to the surface of the film substrate has been put into practical use in order to eliminate such problems (see Japanese Patent Application Laid-Open No. 10-237769). Such a membrane base material has a self-cleaning power, and is a very excellent building material that requires less labor to maintain the aesthetics of the structure in addition to the design advantages as described above. .
[0004]
However, even a resin film material having a photocatalyst layer formed on its surface may not have sufficient functions such as deodorization, sterilization, and antifouling based on its oxidizing power. For example, in the resin film material having the photocatalyst layer as described above, since the contact angle with water is relatively large as about 50 °, the hydrophilicity of the surface may not be sufficiently secured, temporarily after the rain, Dirt may occur in the area where rainwater flows. It is obvious that it is desirable to further enhance the photocatalytic performance in order to eliminate such problems, not only in the photocatalyst support structure using a resin film base material, but also in other resin base materials. The same applies to the photocatalyst carrying structure used.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to improve a photocatalyst-supporting structure formed by forming a photocatalyst layer on the surface of a polymer resin substrate so that the function of the photocatalyst becomes stronger.
[0006]
[Means for Solving the Problems]
In the present invention, the function of the photocatalyst is enhanced by reheating the photocatalyst layer provided on the surface of the conventional photocatalyst carrying structure. In other words, the conventional photocatalyst-supporting structure is formed by applying a photocatalyst coating solution on the surface of a base material made of a polymer resin to form a photocatalyst layer, drying it by heating, and supporting the photocatalyst on the surface of the base material. In the present invention, after the heat drying, the photocatalyst layer is reheated at a temperature not lower than the drying temperature and not higher than 800 ° C. within a time range in which the base material is not deformed. By doing so, a photocatalyst carrying structure is manufactured. The present applicant has already confirmed that the photocatalyst carrying structure thus obtained shows higher catalytic activity than that of the conventional structure.
[0007]
Although the detailed theory is unknown at present, the applicant believes that the following theory can explain the cause of the improvement in the catalytic activity. That is, in the conventional method for producing a photocatalyst-supporting structure, after applying the photocatalyst layer to the surface of the substrate, heating at a relatively low temperature is performed in order to prevent deformation due to softening of the resin substrate. The photocatalyst layer is dried by a relatively long time. Specifically, when the substrate is made of a thermoplastic polymer resin such as vinyl chloride, the heating temperature for drying the photocatalyst layer is 30 ° C. or more and less than 160 ° C., and drying at a higher temperature than that is performed. The photocatalyst layer is also dried at such a temperature even in a thermosetting resin that can be used. In the applicant's view, in this drying step, organic substances such as a plasticizer contained in the base material move to the photocatalyst layer, and this causes a decrease in catalytic activity by covering the photocatalyst particles. Accordingly, if the photocatalyst layer is heated at a temperature higher than the temperature in the drying step after the drying step, and the removal of the impurities occurs in the reheating process, the reheating temperature is based on the temperature. Even if it is a short time that does not cause deformation of the material, it is considered that the improvement of the catalytic activity can be sufficiently caused.
[0008]
That is, in the manufacturing method of the photocatalyst carrying structure according to the present application, it is necessary to reheat the photocatalyst layer at a temperature higher than the drying temperature, which is the lower limit of the reheating temperature. On the other hand, if the reheating temperature is higher than the drying temperature of the photocatalyst layer, there is essentially no upper limit to the reheating temperature of the present invention. However, if the reheating temperature is too high, problems such as thermal decomposition of the base material are expected, and even if reheating is performed at a high temperature above a certain level within the scope of the applicant's research, It has been found that the improvement in the activity of the photocatalyst itself does not show any further changes. On the contrary, when the heating temperature exceeds 800 ° C., when titanium dioxide is used as the catalyst, the catalytic activity is increased by the phase transition from the anatase type to the rutile type having a lower catalytic activity. It may be reduced. Therefore, considering the cost in addition to these points, it can be said that the reheating temperature performed in the method for producing a photocatalyst-supporting structure according to the present invention is sufficient if it is 800 ° C.
[0009]
In addition, when using a base material made of a thermosetting polymer resin that does not soften or deform even at a high temperature of 150 ° C. or higher, apply a temperature of 150 ° C. or higher and 800 ° C. or lower for a certain long time. Therefore, after the photocatalyst layer is dried at a temperature of 30 ° C. or higher and 160 ° C. or lower as in the prior art, the photocatalyst layer is set at a temperature of 150 ° C. or higher and 800 ° C. or lower (however, the temperature range is higher than the drying temperature). If reheating is performed, a photocatalyst-supporting structure showing high catalytic activity as described above can be obtained. In particular, when the reheating of the photocatalyst layer is set to 300 ° C. or higher and 600 ° C. or lower, the photocatalytic activity becomes very high, and at the same time, it is preferable from the viewpoint of cost.
[0010]
On the other hand, the method for producing a photocatalyst carrying structure according to the present invention is also intended to be applied when the softening point temperature of the substrate is relatively low. For example, the substrate with the photocatalyst layer formed on the surface is reheated by bringing it into contact with a heated roller, etc., or using a lyser that emits hot hot air, and reheating the photocatalyst layer while moving it. This time can be shortened, and by doing so, reheating can be performed at a temperature higher than the softening point temperature of the base material without causing deformation of the base material. Needless to say, improvement in catalytic activity is confirmed even by such a short heating time. In this case, the reheating temperature can be in the same range as in the above case, which is suitable when a relatively high temperature polymer resin is used as the base material.
[0011]
Moreover, in the manufacturing method of the said photocatalyst carrying structure, it is preferable to press a photocatalyst layer to a base material at the time of reheating of a photocatalyst layer or after reheating a photocatalyst layer. By doing so, the bonding force of the photocatalyst layer to the base material becomes strong.
[0012]
As the photocatalyst coating liquid in the present invention, the silicon compound is 0.001% to 5% by weight, the metal oxide and / or hydroxide sol is 0.1 to 30% by weight, and the photocatalyst What contains 0.1-30 weight% of powder and / or sol as a solid part can be used.
[0013]
Here, the photocatalyst according to the present invention is any powder, sol, solution, or the like as long as it is fixed to a resin substrate and exhibits photocatalytic activity when dried at the drying temperature of the photocatalyst layer. But it can be used. When using a sol-like photocatalyst, one having a particle size of 20 nm or less, preferably 10 nm or less is used.
[0014]
As the photocatalyst in the present invention, TiO 2, ZnO, SrTiO 3 , CdS, GaP, InP, GaAs, BaTiO 3, KNbO 3, Fe 2 O 3, Ta 2 O 5, WO 3, SnO 2, Bi 2 O 3 , NiO, Cu 2 O, SiC, SiO 2 , MoS 2 , InPb, RuO 2 , CeO 2, etc., and metals such as Pt, Rh, RuO 2 , Nb, Cu, Sn, Ni, Fe, or these metals A material to which an oxide of the above is added can be used. It is also these by utilizing photocatalytic reduction action Pt, Rh, RuO 2, Nb , Cu, Sn, Ni, or the like obtained by adding a metal such as Fe available.
[0015]
Moreover, as a silicon compound added to the coating liquid of the photocatalyst layer of the present invention, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and one kind of hydrolysis products thereof or A mixture of two or more can be used.
[0016]
There is no particular limitation on the method of adding the silicon compound into the coating solution for forming the photocatalyst layer, but the method of adding it into the photocatalyst powder or sol solution, and the metal oxide and / or hydroxide added together with the photocatalyst. Various methods such as a method of adding to the sol solution can be used. Further, a partially hydrolyzed silicon compound may be added thereto.
[0017]
The metal oxide gel or metal hydroxide gel preferably has a specific surface area of 50 m 2 / g or more after drying at 150 ° C., more preferably 100 m 2 / g or more. If it has such a specific surface area, adhesiveness will become stronger and catalytic activity will also improve. Here, as a metal component, the oxide gel or hydroxide gel of metals, such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin, can be illustrated preferably.
[0018]
In actual use, a gel obtained by mixing and drying a sol for forming a gel or a complex oxide gel produced by a method such as a coprecipitation method may be used. For compounding with the photocatalyst, it is desirable to mix uniformly in the state of the sol before becoming a gel, or to mix at the raw material stage before preparing the sol. Methods for preparing a gel include a method of hydrolyzing a metal salt, a method of neutralizing and decomposing, a method of ion exchange, a method of hydrolyzing a metal alkoxide, etc., but the photocatalyst powder is uniformly dispersed in the gel. Any method can be used as long as it can be obtained in the same state. However, if a large amount of impurities are present in the gel, the adhesiveness and catalytic activity of the photocatalyst are adversely affected. Therefore, a gel with few impurities is preferred.
[0019]
In the photocatalyst-supporting substrate used in the present invention, an adhesive layer and / or an intermediate layer can be provided between the photocatalyst layer and the substrate. Examples of the adhesive layer coating liquid include a silicon-modified resin having a silicon content of 2 to 60% by weight, a resin containing 3 to 60% by weight of polysiloxane, and a resin containing 5 to 40% by weight of colloidal silica as a resin solid content. A solution containing ˜50% by weight can be used.
[0020]
When the adhesive layer resin is a silicon-modified resin such as an acrylic-silicon resin or an epoxy-silicon resin, the method of introducing silicon into the resin is a transesterification reaction, a graft reaction using a silicon macromer or a reactive silicon monomer, There are various hydrosilylation reactions, block copolymerization methods, and the like, but in the present invention, products prepared by any method can be used. As the resin into which silicon is introduced, it is preferable to use an acrylic resin or an epoxy resin that is most excellent in terms of film formability, toughness, and adhesion to the carrier, but alkyd resin, urethane resin, polyester resin, and the like are preferable. It can replace with and can also be used. These resins can be used either in a solvent-soluble type or an emulsion type. Moreover, there is no problem even if an additive such as a crosslinking agent is contained.
[0021]
When using a hydrolyzate of silicon alkoxide or a product from the hydrolyzate containing polysiloxane as the adhesive layer resin, the polysiloxane having an alkoxy group having 1 to 5 carbon atoms, A supporting structure with improved durability can be obtained. Further, when the number of carbon atoms of the alkoxy group of the silicon alkoxide is 6 or more, it is expensive, and the hydrolysis rate becomes very slow, so that curing in the resin becomes difficult, and the adhesiveness and durability are inferior. Become. Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can also be used. However, when polysiloxane containing a large amount of chlorine is used, the corrosion and adhesion of the carrier are caused by impurity chlorine ions. Degradation may occur.
[0022]
As a method for introducing polysiloxane into a resin, a method in which polysiloxane is mixed into a resin solution in the state of a silicon alkoxide monomer and hydrolyzed with moisture in the air when forming an adhesive layer, or a product obtained by partially hydrolyzing silicon alkoxide in advance. There are various methods such as mixing with a resin and hydrolyzing with moisture in the air when forming the protective film, but any method can be used as long as it can be mixed uniformly with the resin. Moreover, in order to change the hydrolysis rate of silicon alkoxide, a small amount of acid or base catalyst may be added. Here, as the resin for introducing polysiloxane, acrylic resin, acrylic-silicon resin, epoxy-silicon resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, alkyd resin, etc. can be used. From the standpoint of performance, it is most excellent to use a silicon-modified resin including an acrylic-silicon resin or an epoxy-silicon resin.
[0023]
When the adhesive layer is a resin containing colloidal silica, the particle diameter of the colloidal silica is preferably 10 nm or less. If it is 10 nm or more, not only the resin in the adhesive layer is easily deteriorated by the photocatalyst, but also the adhesion between the photocatalyst layer and the adhesive layer is deteriorated. As a method for introducing the colloidal silica into the resin, a method in which the resin solution and the colloidal silica solution are mixed and then applied and dried to form an adhesive layer is the simplest method, but in a state where the colloidal silica is dispersed. Alternatively, a resin synthesized and synthesized may be applied and dried for use. Moreover, in order to improve the adhesiveness and dispersibility between the colloidal silica and the resin, the colloidal silica can be treated with a silane coupling agent.
[0024]
Examples of the resin into which colloidal silica is introduced include acrylic resin, acrylic-silicon resin, epoxy-silicon resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, alkyd resin, etc., but acrylic-silicon resin and epoxy- The use of a silicon-modified resin containing a silicon resin is most excellent from the viewpoint of durability. The colloidal silica can be any silica sol made by cation exchange of a sodium silicate solution or silica sol made by hydrolyzing silicon alkoxide.
[0025]
Further, for the purpose of suppressing deterioration due to photocatalytic action, durability can be improved by mixing a light stabilizer and / or an ultraviolet absorber with the adhesive layer resin. As the light stabilizer, a hindered amine-based one is preferably used, but other substances can also be used. As the ultraviolet absorber, a triazole type or the like can be used. The addition amount is 0.005 wt% or more and 10 wt% or less, preferably 0.01 wt% or more and 5 wt% or less with respect to the resin. If the surface of the adhesive layer is treated with a silane-based or titanium-based coupling agent, the adhesion with the photocatalytic layer may be improved. A good photocatalyst carrier can also be obtained by adding 0.00001% to 0.1% by weight of a surfactant to the adhesive layer solution.
[0026]
As a method for supporting the adhesive layer on the carrier, a method in which the resin solution is coated by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, or the like and then dried can be used. The drying temperature in this case is preferably 150 ° C. or lower, although it varies depending on the type of solvent and resin. When the thickness of the adhesive layer is 0.1 μm or more, a highly durable photocatalyst carrying structure in which the photocatalyst layer is firmly adhered can be obtained. In the case where the base material of the photocatalyst-supporting structure is used as a film material, the upper limit of the thickness of the adhesive layer is 10 μm if securing the bending performance is taken into consideration. In the case of a coating method that requires the adhesive layer to be dried and cured in a short time, such as a gravure printing method, a silicon-based curing agent is added to the adhesive layer solid content in an amount of 0.1 according to the required curing rate. Addition of -10 wt% is also preferably employed.
[0027]
In order to form a photocatalyst layer on a base material or an adhesive layer, a suspension in which a photocatalyst is dispersed in a metal oxide sol or metal hydroxide sol solution is coated using the same coating method as in the case of forming an adhesive layer. Can be coated. The photocatalyst may be dispersed in the state of a metal oxide sol or metal hydroxide sol precursor solution, and may be hydrolyzed or neutralized and decomposed into a sol or gel during coating. When a sol is used, an acid or alkali peptizer may be added for stabilization. In addition, it is possible to improve the adhesiveness and operability by adding 5% by weight or less of a surfactant or a silane coupling agent to the photocatalyst in the sol suspension. The drying temperature when forming the photocatalyst layer varies depending on the carrier material and the resin material in the adhesive layer, but is preferably 30 ° C. or higher and lower than 160 ° C.
[0028]
The photocatalyst layer has higher activity when the thickness is increased, but the activity hardly changes when the thickness is 5 μm or more. On the other hand, even when the thickness is 5 μm or less, it is possible to obtain a sufficiently high catalytic activity that is practically sufficient, and when the thickness of the photocatalyst tank is reduced, it is excellent in translucency and the catalyst layer becomes inconspicuous. This produces the advantage. However, when the thickness is less than 0.1 μm, the translucency is very excellent, but the ultraviolet ray used by the photocatalyst is also transmitted. I can't hope. Here, when the photocatalyst particle having a thickness of the photocatalyst layer of 0.1 μm or more and 5 μm or less and a crystal particle diameter of 40 nm or less and a metal oxide gel or metal hydroxide gel having a specific surface area of 100 m 2 / g or more are used, The total light transmittance at a wavelength of 550 nm of the photocatalyst layer and the adhesive layer is 70% or more. The structure supported so that the total light transmittance at a wavelength of 550 nm is 70% or more can be used as illumination when the substrate is transparent, and even when the substrate is opaque, Since the upper handle is not damaged, it is also useful for decorativeness.
[0029]
Here, the composition of the intermediate layer coating solution is not particularly limited as long as it does not impair the photocatalytic function and the adhesion of the entire photocatalyst-supporting substrate. For example, the photocatalyst coating solution or the adhesive layer coating solution is used as it is or as a composition. Can be used. Moreover, as long as the above-described conditions are satisfied, a plurality of layers may be included. In order to form the intermediate layer on the adhesive layer, it can be coated by a coating method similar to the method for forming the adhesive layer or the photocatalyst layer. The thickness of the intermediate layer is not particularly limited, but if the total thickness of the adhesive layer and the photocatalyst layer is too large, problems such as workability and durability of the base material occur, and usually 0.1 μm or more. A range of 10 μm or less is preferred.
[0030]
Here, if the base material used in the present invention is made of a polymer resin, the raw material is not particularly limited. For example, a polyethylene terephthalate resin, a polycarbonate resin, a polyacrylate resin, a polymethyl methacrylate resin, The base material is formed from polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, polyvinylidene fluoride resin, fluorinated ethylene-propylene copolymer resin, fluorinated ethylene-ethylene copolymer resin, etc. can do. Further, as the substrate, a material containing 1% by weight or more and 80% by weight or less of a plasticizer, preferably 5% by weight or more and 80% by weight or less of a plasticizer is used. When is applied, the photocatalytic function is remarkably improved as compared with the photocatalyst-supporting substrate obtained by the conventional method. In addition, when a method containing a photocatalyst-supporting substrate according to the present invention was used as a substrate containing 10% by weight of vinyl chloride resin, it was compared with the photocatalyst-supporting substrate obtained by the conventional method. As a result, the photocatalytic function is remarkably improved.
[0031]
The shape of the polymer substrate used in the present invention may be any shape such as a film shape, a plate shape, a tubular shape, a fiber shape, and a net shape. Moreover, if the magnitude | size is 10 micrometers or more, a photocatalyst can be carry | supported firmly. In order to improve the adhesion between the polymer resin substrate and the photocatalyst layer, the adhesive layer, or the intermediate layer, a polymer resin substrate that has been subjected to discharge treatment, primer treatment, or the like on its surface can also be used. In addition, depending on the use such as construction materials, home appliances, and glasses that have already been constructed, the processed polymer resin molded body that exists as a product is treated by the method for producing a photocatalyst-supporting structure of the present invention. Therefore, it can be said that the application range is extremely wide.
[0032]
In particular, when the method of the present invention is applied to a film material, in particular, a tented canvas, a remarkable effect appears as compared with the case of manufacturing by a conventional method. As the tent place canvas, any existing kind of tent place canvas can be used. A base fabric woven with a fiber made of resin such as polyester, a vinyl impregnated base fabric processed by coating and impregnating vinyl chloride resin on the base fabric, and a surface treatment in which the surface of the PVC impregnated base fabric is coated with acrylic, fluororesin, etc. It can be applied to everything called as tent canvas, such as PVC-impregnated base fabric, but it is particularly preferable for widely used B-type tent canvas, C-type tent canvas, and warehouse membrane materials. Can be used.
[0033]
In addition, the photocatalyst-supported tent canvas of the present invention is widely used as a general building material, for example, roofs of tent warehouses, hoods of transport equipment such as truck seats, field stacks, decorative tents for shops, and sunshades for shops. , Various arcade roofs, roofs and side covers of exhibition pavilions, etc., gas station roofs and side covers, waterproof protective sheets, snowproof sheets, air domes, pool covers, etc. It can be used particularly preferably in order to maintain a beautiful surface state over a long period of time by utilizing its excellent antifouling property, antibacterial property and antifungal property in many required scenes.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
A preferred embodiment of the method for producing a photocatalyst-supporting substrate according to the present invention will be described below.
[0035]
Example In this example, Falcon KN-C2000 (103 cm width × 50 m 207 white), which is a C-type tent ground canvas manufactured by Kuraray Co., Ltd., was used as a polymer resin substrate. The Falcon KN-C2000 contains vinyl chloride and a plastic material.
[0036]
In order to carry out the method for producing a photocatalyst-supporting substrate in this example, first, this Falcon KN-C2000 was cut into A4 size, and xylene-isopropanol (50/50) containing 10% by weight of an acrylic-silicone resin having a silicon content of 3% by weight. 50) 30% by weight of polysiloxane (Methyl silicate 51 manufactured by Colcoat Co., Ltd.) and a surfactant with respect to the acrylic-silicon resin were added to the solution. 7 was applied with a bar coater and dried at 60 ° C. for 30 minutes to form an adhesive layer. The thickness of the adhesive layer is about 0.5 μm.
[0037]
After cooling at room temperature, a nitric acid acidic titania sol having a titanium oxide content of 5% by weight was dispersed as a photocatalyst layer in a nitric acid acidic silica sol having a silicon oxide content of 5% by weight in the presence of a surfactant to obtain a photocatalyst coating solution. This photocatalyst coating solution was applied in the same manner as in the case of the adhesive layer. The photocatalyst layer was formed by applying to the surface of the adhesive layer with a bar coater No. 7. Thereafter, the polymer resin base material on which the photocatalyst layer was formed was dried at 60 ° C. for 30 minutes to obtain a photocatalyst carrying structure (photocatalyst carrying C type tent canvas). Note that the thickness of the photocatalyst layer is about 0.6 μm.
[0038]
Thereafter, the heating temperature and the reheating time were changed, and the dried photocatalyst layer was reheated under a plurality of conditions. Reheating in this example was performed by spraying high-temperature hot air at a speed of 3.0 m / min with a lystor or heating for 1 minute in a thermostatic bath. Table 1 shows the test results regarding the reheating conditions and the catalyst performance of the photocatalyst-supported substrate obtained thereby. In this test, the sheet material by the photocatalyst carrying base material obtained by the conventional method and the method described in the present embodiment was exposed outdoors, and the color difference was measured. The exposure period is from August 25, 1998 to October 8, 1998. Further, the color difference measurement is N = 1 in the wavelength range from 380 nm to 780 nm.
[0039]
[Table 1]
Further, the contact angle of water with the photocatalyst-supporting structure obtained under the same conditions as described above was examined and is summarized in Table 2.
[0041]
[Table 2]
From Table 1 and Table 2 above, it can be seen that in the case of reheating using a lysator, the photocatalytic performance is improved as the reheating temperature is increased as compared with the case where the reheating treatment is not performed. In particular, when the reheating temperature exceeds 200 ° C. and reaches 300 ° C., extremely excellent photocatalytic performance is exhibited. In this example, no particular change was observed in the form of any of the substrates. On the other hand, in the case of reheating in a thermostatic bath, no noticeable effect was seen when the reheating temperature was 100 ° C, but the photocatalytic performance was clearly improved by performing reheating at 150 ° C for 1 minute. It was observed.
[0043]
【The invention's effect】
According to the method for producing a photocatalyst-supporting substrate according to the present invention, it is possible to obtain a photocatalyst-supporting substrate that exhibits catalytic performance such as deodorization, sterilization, and antifouling that is far higher than conventional products. In particular, a photocatalyst-supporting substrate using a membrane substrate as a polymer substrate can be an excellent building material that can exhibit a high self-cleaning effect when used outdoors.
Claims (13)
加熱乾燥後に、乾燥温度以上且つ３００℃以上６００℃以下の温度で光触媒層を再加熱するとともに、
光触媒層の再加熱を、基材がたとえ熱可塑性の高分子樹脂を含むものであったとしても当該基材に変形を生じさせない時間内で行なう、
ことを特徴とする光触媒担持構造体の製造方法。In the method for producing a photocatalyst-supporting structure in which a photocatalyst coating liquid is applied on a base material made of a polymer resin to form a photocatalyst layer, and the photocatalyst is supported on the surface of the base material by heating and drying it.
After heating and drying, the photocatalyst layer is reheated at a temperature not lower than the drying temperature and not lower than 300 ° C. and not higher than 600 ° C. ,
Reheating the photocatalyst layer is performed within a time period that does not cause deformation of the base material even if the base material contains a thermoplastic polymer resin.
A method for producing a photocatalyst-supporting structure, comprising:
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| CN101716525B (en) * | 2009-12-10 | 2012-08-29 | 南京大学 | Anion resin-based loaded CdS composite material and preparation method thereof |
| CN101708464B (en) * | 2009-12-10 | 2012-08-29 | 南京大学 | Cation resin matrix CdS-loaded composite material and preparation method thereof |
| CN102102198B (en) * | 2011-02-12 | 2013-08-07 | 南京大学 | Method for regulating distribution of metal nano granules in resin carrier |
| CN102268198B (en) * | 2011-05-26 | 2013-02-27 | 上海梅思泰克生态科技有限公司 | Nano precious metal modified tungsten oxide photocatalyst paint and preparation method thereof |
| CN104549395B (en) * | 2014-10-24 | 2017-01-18 | 阜阳师范学院 | Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst |
| CN104817281A (en) * | 2015-04-22 | 2015-08-05 | 陕西科技大学 | Preparation method of orange-yellow photonic crystal structure color thin film with photo-catalytic effect |
| CN109201029B (en) * | 2018-09-17 | 2021-04-06 | 绍兴文理学院 | Preparation method of efficient porous composite photocatalytic material |
| CN110026181B (en) * | 2019-05-13 | 2022-04-05 | 辽宁大学 | Novel Z-shaped photocatalyst CeO2/CeVO4/V2O5And preparation method and application thereof |
| CN113145136A (en) * | 2021-03-31 | 2021-07-23 | 天津城建大学 | WO for photoelectrocatalytic degradation of pollutants3/CdS/MoS2Preparation method of composite film |
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