JP4046250B2 - A resin structure obtained by laminating a photocatalyst-carrying film - Google Patents
A resin structure obtained by laminating a photocatalyst-carrying film Download PDFInfo
- Publication number
- JP4046250B2 JP4046250B2 JP32224897A JP32224897A JP4046250B2 JP 4046250 B2 JP4046250 B2 JP 4046250B2 JP 32224897 A JP32224897 A JP 32224897A JP 32224897 A JP32224897 A JP 32224897A JP 4046250 B2 JP4046250 B2 JP 4046250B2
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- Prior art keywords
- resin
- photocatalyst
- film
- laminating
- adhesive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229920005989 resin Polymers 0.000 title claims description 161
- 239000011347 resin Substances 0.000 title claims description 161
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- 239000011941 photocatalyst Substances 0.000 claims description 125
- 238000000576 coating method Methods 0.000 claims description 83
- 239000011248 coating agent Substances 0.000 claims description 74
- 239000012790 adhesive layer Substances 0.000 claims description 71
- 239000010410 layer Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 46
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- 239000000758 substrate Substances 0.000 claims description 37
- -1 polysiloxane Polymers 0.000 claims description 36
- 239000002952 polymeric resin Substances 0.000 claims description 24
- 229920003002 synthetic resin Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
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Description
【０００１】
【発明の属する技術分野】
本発明は、消臭、防汚、抗菌、防カビ等の効果を有する光触媒担持フィルムを加熱加圧処理によってラミネート加工することにより得られる樹脂構造体及びその製造方法、並びにその応用製品に関する。
【０００２】
【従来の技術】
紫外線のエネルギーによって、殺菌、有機物の分解等の各種の化学反応を進行させる光触媒として、ｎ型半導体の酸化チタンが知られている。光触媒をガラス、金属、プラスチック、タイル等に担持する方法は種々提案されている（特開昭６２−６６８６１、特開平５−３０９２６７、ＥＰ６３３０６４、ＵＳＰ４８８８１０１）。しかし、光触媒を担持したフィルムをラミネートした樹脂構造体、特に広く使用されているポリカーボネート樹脂や織布強化ポリ塩化ビニル樹脂に、触媒活性を低下させることなく光触媒を担持した光触媒担持フィルムをラミネートした樹脂構造体は知られておらず、また、かかる光触媒担持フィルムをラミネートした樹脂構造体の光触媒作用を有効に利用して消臭、防汚、抗菌、防カビ性を長期にわたって維持する方法についても報告されていない。
【０００３】
従来、屋外設置したポリカーボネート製遮音壁などの樹脂構造体、ポリ塩化ビニルを含浸させた繊維強化樹脂は外気中の埃やばい煙を付着しやすく通常２〜３ケ月で黒く変色し汚染が進むため、美観を損ねるという大きな欠点を有していた。また、ポリ塩化ビニル樹脂に大量に含まれる可塑剤成分などのためにカビが発生しやすく、その対策として表面にフッ素樹脂をコートしたりする方法が取られている。しかしながら、フッ素樹脂のコートは従来から言われているように、表面の撥水性を増加させ親油性を増加させるため、ばい煙等の油分の汚れが付着しやすいものとなる欠点があった。また、酸化チタンは大気中で紫外線を照射されると親水性を発現するという性質を本来有しているが、この効果を利用して屋外設置構造体の表面を親水性にし、付着したオイルミストなどの油分を水（特に雨水）で洗い流し易くする方法も公開されている（特開昭６３−１０００４２号公報、ＷＯ９６／２９３７５）。これらは構造体表面の物性を親水性にすることにより、水が表面に濡れ易くなり、結果として油分が表面から浮き上がって流れ落ちるという現象を利用したものである。しかしながら、公開された技術による方法では表面に付着した油分の光触媒分解作用が乏しいため、ディーゼル車の排気ガス等の汚れが強固に大量に付着するという道路遮音壁では実用化に際して使用範囲の制約を受けるという大きな問題があった。
【０００４】
また、ＷＯ９７−１３４にはディップ法やスプレー法で樹脂基体上に、ポリシロキサンを添加したアクリルシリコン樹脂からなる接着層を介して、金属酸化物ゲルを含む光触媒粒子複合体からなる光触媒層を設けることにより、高い光触媒活性と優れた耐久性を維持した例が開示されている。しかしながら、公開された技術による方法は、光触媒担持フィルムの裏面に粘着剤を塗布したラミネートフィルムとすることは可能であるが、加熱加圧処理によりラミネート加工すると光触媒活性が低下してしまったり、フィルムの高速成膜時に、接着層の硬化が不充分なため光触媒塗布に問題が生じるという欠点があった。
【０００５】
また、ポリエステルフィルム上にポリシロキサンを添加したアクリルシリコン樹脂からなる接着層を介して、金属酸化物ゲルを含む光触媒粒子複合体からなる光触媒層を設けることにより、高い光触媒活性と優れた耐久性を維持した光触媒担持フィルムも上記ＷＯ９７−１３４に公開されているが、ポリエステルフィルムは一般的には加熱加圧によるラミネート加工が非常に困難で、本発明の目的に使用することは不適当であった。
【０００６】
さらに、この公開された塗布液の組成ではフィルムの高速成膜時に乾燥硬化が不十分となり易く塗布面が裏面に張りつき易いという問題があった。特に加熱加圧によりラミネート可能なフィルムは、耐熱温度や熱変形温度が１００℃以下と低いものであるため、ＷＯ９７−１３４に公開されている塗布液と塗布方法では、こうした熱ラミネート加工に適したフィルムへの高速成膜は困難である上に、光触媒活性が熱ラミネート条件によっては失われてしまうという問題点があった。また、ディップ法やスプレー法などの塗布による方法では平板状の大型樹脂基体の場合、生産設備や成膜速度、乾燥速度の制約から実際には適用困難な場合が多いという問題点があった。特に、１ｍ幅以上の樹脂基体では大型乾燥機が必要な上に乾燥時間も熱容量の関係から３０分以上必要なため生産速度も遅くコスト高になるという問題があった。
【０００７】
樹脂板や塗装樹脂板に、防汚、抗菌、消臭を目的として光触媒を担持させる場合、接着層を介して光触媒層を設けた構造を有する光触媒構造体を直接それら樹脂板等の表面に設けることも一つの方法として考えられる。しかしながらこの方法では、塗布後の乾燥処理時間がフィルム成膜の場合と比較して非常に長く必要で、フィルム成膜の場合秒単位の乾燥処理時間であるのに対して樹脂板への直接成膜では熱容量の問題もあり最低でも分単位の処理時間であり、平坦な面であればフィルムをラミネート加工する時間を考慮してもフィルムラミネートの方が生産性が高いこと、接着層や光触媒層の塗布液のｐＨによっては塗布乾燥時に樹脂基体が浸食されてしまうこと、樹脂基体への塗布加工は１ｍ幅以上の大型になると、ディップ塗布にしろスプレー塗布にしろ均一に成膜することは困難で膜の厚みムラが生じやすいことなどの問題があり、適用可能な樹脂基体の種類や大きさに制限を受けるという欠点があった。
【０００８】
【発明が解決すべき課題】
本発明の課題は、優れた消臭、防汚、抗菌、防カビ等の効果を有する光触媒担持フィルムがラミネート加工された樹脂構造体を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために、光触媒を担持した透明なフィルムを効率良く高速で熱ラミネート加工できること、光触媒活性が光触媒を担持したフィルムを熱ラミネート加工することにより低下しないこと、高速ラミネート加工が可能な材質のフィルムに光触媒を生産性良く担持できること、などの検討項目について鋭意研究を重ね、大気中温度２５℃、相対湿度７０％の状態でＵＶ−Ａ領域の紫外線を３ｍＷ／ｃｍ2 照射した時にトリオレインを５μｇ／ｃｍ2 ・ 日以上分解し得る光触媒活性を有する高分子樹脂フィルムを加熱加圧処理によって樹脂基体表面にラミネート加工することにより、上記課題を解決できることを見出し、本発明を完成するに至った。
【００１０】
すなわち、本発明は、硬化剤としてシランカップリング剤を含有する接着層塗布液の塗布により形成された接着層を介して光触媒層が担持された高分子樹脂フィルムからなる光触媒担持フィルムを、加熱加圧処理によって樹脂基体の表面にラミネート加工することにより得られ、かつ大気中温度２５℃、相対湿度７０％の状態でＵＶ−Ａ領域の紫外線を３ｍＷ／ｃｍ２照射した時にトリオレインを５μｇ／ｃｍ２・日以上分解し得る光触媒活性を有することを特徴とする光触媒担持フィルムをラミネート加工した樹脂構造体に関する。
【００１１】
また本発明は、上記高分子樹脂フィルムが２種以上の樹脂フィルムをラミネート加工したフィルムであること、上記高分子樹脂フィルムがポリカーボネート樹脂、２種以上のポリメチルメタクリレート樹脂又はポリアクリレート樹脂の共重合樹脂、ポリ塩化ビニル樹脂、又はセロファン樹脂の中から選ばれた樹脂であること、上記高分子樹脂フィルムの膜厚が５〜２００μｍであること、上記接着層塗布液としてポリシロキサンを１０〜５０重量％含有するシリコン変性樹脂又はコロイダルシリカを５〜３０重量％含有するシリコン変性樹脂を２〜２０重量％含む塗布液に、硬化剤としてシランカップリング剤を塗布液に対して０．１〜５重量％添加した接着層塗布液を用いること、また上記接着層塗布液としてモノアルキルトリメトキシシラン又はその加水分解生成物であるポリシロキサンを１〜１０重量％とシリカゾルを０．１〜５重量％含む塗布液に、硬化剤としてシランカップリング剤を塗布液に対して０．１〜５重量％添加した接着層塗布液を用いること、上記接着層の厚みが０．５〜５μｍであること、上記光触媒層が金属酸化物ゾルを固形分として１〜１０重量％、酸化チタンゾルを固形分として１〜１０重量％含有すること、上記光触媒層がシリカゾルを１〜１０重量％、モノアルキルトリメトキシシラン又はその加水分解生成物を１〜１０重量％、及び酸化チタンゾルを１〜１０重量％含有することを特徴とした、上記光触媒層の厚みが０．１〜５μｍであること、上記樹脂基体がポリ塩化ビニル樹脂、ポリエチレンテレフタレート樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、耐衝撃性変性ポリスチレン樹脂、アクリル−ブタジエン−スチレン共重合樹脂、の中から選ばれた樹脂であること、あるいは樹脂基体の形状が、板状、シート状、織布状、不織布状、樹脂含浸強化織布状、又は管状のものであること、をそれぞれ特徴とする前記の光触媒担持フィルムをラミネート加工した樹脂構造体に関する。
【００１２】
そしてまた本発明は、高分子樹脂フィルムに、硬化剤としてシランカップリング剤が添加された接着層塗布液を塗布・乾燥した後、この接着層に光触媒層塗布液を塗布乾燥して、高分子樹脂フィルム上に接着層を介して光触媒層を担持した光触媒担持フィルムを調製し、この光触媒担持フィルムを加熱加圧処理によって樹脂基体の表面にラミネート加工することを特徴とする光触媒担持フィルムがラミネート加工された樹脂構造体の製造方法に関する。
【００１３】
さらに本発明は、上記記載の光触媒担持フィルムをラミネート加工した樹脂構造体を、少なくとも一部に使用してなる屋外看板及び屋外標示板、電話ボックス、屋外用テント生地、洗面化粧台、ユニットバス、システムキッチン、観賞魚水槽、プラスチックケース、壁紙、食品トレー、又は包装用フィルムに関する。
【００１４】
【発明の実施の形態】
本発明の光触媒担持フィルムがラミネート加工された樹脂構造体は、例えば高分子樹脂フィルムに、硬化剤としてシランカップリング剤が添加された接着層塗布液を塗布・乾燥した後、この接着層に光触媒層塗布液を塗布乾燥して、高分子樹脂フィルム上に接着層を介して光触媒層を担持した光触媒担持フィルムを調製し、この光触媒担持フィルムを加熱加圧処理によって樹脂基体の表面にラミネート加工することにより製造することができる。本発明の光触媒担持フィルムがラミネート加工された樹脂構造体の断面の模式図を図１に示す。
【００１５】
本発明における高分子樹脂フィルムとしては、その材質としてポリカーボネート樹脂、２種以上のポリメチルメタクリレート樹脂又はポリアクリレート樹脂の共重合樹脂、ナイロン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリアクリロニトリル樹脂、ポリウレタン樹脂、ポリ塩化ビニル樹脂、セロファン樹脂、ポリビニルアルコール樹脂、酢酸ビニル−エチレン共重合体樹脂、又はエチレン−ビニルアルコール共重合体樹脂、の中から選ばれた樹脂からなるフィルムを挙げることができ、また、接着層や光触媒層を塗布成膜する際に、フィルムが伸びたりシワがよったりして均一で均質な光触媒担持フィルムが得られない場合は好ましくないことから、塗布加工時の成膜機械のテンションに耐える引張伸度と弾性率を維持できる材質や厚みを有するものが好ましい。
【００１６】
これらの中でも、ポリカーボネート樹脂、２種以上のポリメチルメタクリレート樹脂又はポリアクリレート樹脂の共重合樹脂、ポリ塩化ビニル樹脂、又はセロファン樹脂からなるフィルムが特に好ましく使用でき、これらの樹脂を使用した光触媒担持フィルムは光触媒活性、耐久性、成膜性、ラミネート加工性、価格等の面で優れているといえる。また、これらのフィルムの２種以上をラミネート加工して得られるフィルムを使用することにより、光触媒を担持するフィルムの有すべき特性、特に耐候性、耐熱性、透湿性などを大きく向上させることも可能で、使用する環境に応じて光触媒を担持するフィルムの特性を設計し変更できることは実用化に際して極めて有利である。
【００１７】
使用する高分子樹脂フィルムの膜厚としては、５〜２００μｍであることが好ましく、５μｍ以下の膜厚では本発明の接着層と光触媒層の成膜が困難となり、２００μｍ以上ではラミネート加工が困難になったりコスト増になる場合もあるため好ましくない。
【００１８】
本発明において、樹脂基体にラミネート加工される光触媒担持高分子樹脂フィルムは、図１に示すように、光触媒層とフィルムとの間に接着層を設けた構造を有している。そして、この光触媒層とフィルムとの間に設けられる接着層は、接着層塗布液をフィルム上に塗布・乾燥することにより形成され、光触媒層をフィルムに強固に接着させる作用と、フィルムもしくはフィルムをラミネートした高分子樹脂から拡散する可塑剤成分による光触媒活性の低下を防ぐとともに、光触媒作用によるフィルムの劣化を防ぐ作用を有しており、また接着層自身が光触媒作用による劣化を受けにくいという特徴を有している。
【００１９】
本発明における接着層塗布液としては、硬化剤としてのシランカップリング剤を含むものが特に好ましく、シランカップリング剤を接着層塗布液に含有せしめることにより、フィルム成膜時の接着層の硬化を促進させフィルムが裏面に張り付くことなく巻取ることを可能とし、高速成膜が可能になるばかりか、光触媒担持フィルムを加熱加圧処理によって樹脂基体の表面にラミネート加工する場合における光触媒活性の低下を防止し、ラミネート加工前の光触媒担持フィルムが有する光触媒活性を維持することができる。
【００２０】
本発明における接着層塗布液として、例えば、ポリシロキサンを１０〜５０重量％含有するシリコン変性樹脂、又は、コロイダルシリカを５〜３０重量％含有するシリコン変性樹脂を２〜２０重量％含む塗布液に、硬化剤としてシランカップリング剤を塗布液に対して０．１〜５重量％添加してなる塗布液を例示することができる。
【００２１】
ポリシロキサン含有量が１０重量％未満のアクリルシリコン樹脂やエポキシシリコン樹脂などのシリコン変性樹脂、もしくは、コロイダルシリカ含有量が５重量％未満のシリコン変性樹脂では、光照射時の光触媒層の接着が悪くなり、また、屋外などの紫外線強度が強い場所では接着層が光触媒により劣化し、光触媒層が剥離し易くなる。他方、ポリシロキサン含有量が５０重量％を超えたり、あるいは、コロイダルシリカ含有量が３０重量％を超えるシリコン変性樹脂では、接着層と担体との接着が悪くなったり、接着層が多孔質となったり、基材フィルムと接着層との間の接着性が悪くなったりして、光触媒はフィルムより剥離し易くなる。
【００２２】
また、本発明における接着層塗布液として、モノアルキルトリメトキシシラン又はその加水分解生成物であるポリシロキサンとシリカゾルとの塗布液に、硬化剤としてシランカップリング剤を塗布液に対して０．１〜５重量％添加してなる塗布液を例示することができる。使用できるモノアルキルトリメトキシシランとしては、モノメチルトリメトキシシラン、モノエチルトリメトキシシランが好ましい。また、シリカゾルとしては一次粒子径の細かいものが好ましく、特に透明なフィルムを得る場合には２０ｎｍ以下のものが好ましい。塗布液には、モノアルキルトリメトキシシラン又はその加水分解生成物であるポリシロキサンを１〜１０重量％とシリカゾルを０．１〜５重量％を含有させることが、接着性、触媒活性の面から好ましい。モノアルキルトリメトキシシラン又はその加水分解生成物とシリカゾルとの割合は、重量比で２０／８０〜６０／４０が好ましく、また硬化促進のため鉱酸などの酸触媒を添加することもできる。
【００２３】
そして、接着層塗布液が、ポリシロキサン−シリコン変性樹脂やコロイダルシリカ−シリコン変性樹脂の場合でも、またモノアルキルトリメトキシシラン−シリカゾルの場合でも、硬化剤として添加するシランカップリング剤はこれら塗布液に対して０．１〜５重量％添加することが望ましい。シランカップリング剤の添加量が塗布液に対して０．１重量％未満では、フィルム成膜時に乾燥後巻取りする際に塗布面がフィルム裏面に張りつくブロッキング現象が生じて光触媒層の塗布が困難となるため好ましくない。他方、シランカップリング剤の添加量が塗布液に対して５重量％以上では、硬化が速くなりすぎたり、成膜途中に液がゲル化するなどの現象が生ずるため好ましくない。また、シランカップリング剤を塗布液に対して０．１〜５重量％添加することことにより、光触媒担持フィルムを加熱加圧処理によって樹脂基体の表面にラミネート加工する場合における光触媒活性が低下することなく、ラミネート加工前の光触媒担持フィルムが有する光触媒活性を維持することができる。
【００２４】
シランカップリング剤としては、一般式：ＲＳｉ(Ｘ)3や (Ｒ)2Ｓｉ(Ｘ)2など（但し、Ｒは有機性官能基を、Ｘは塩素原子又はアルコキシ基を示す。）で示されるものが使用可能であり、式中Ｒは、メチル基、エチル基、ビニル基、γ−グリシドキシプロピル基、γ−メタクリロキシプロピル基、γ−（２−アミノエチル）アミノプロピル基、γ−クロロプロピル基、γ−メルカプトプロピル基、γ−アミノプロピル基、γ−アクリロキシプロピル基などを表し、式中Ｘは、塩素原子の他、メトキシ基、エトキシ基、β−メトキシエトキシ基などのＣ1 〜Ｃ5 のアルコキシ基などを表す。
【００２５】
また、接着層に、光触媒作用による劣化を抑える目的で、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、その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が好ましいが、その他の光安定化剤も使用することができる。紫外線吸収剤としてはトリアゾール系などの紫外線吸収剤が使用できる。添加量は、接着層塗布液に対して０．００５重量％以上１０重量％以下、好ましくは０．０１重量％以上５重量％以下である。接着層中に光安定化剤もしくは紫外線吸収剤を添加することにより、光触媒を担持する高分子樹脂フィルムの耐候性を向上させることも可能となり、特に屋外で使用する場合は有利である。接着層塗布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フィルムをラミネートした樹脂構造体とすることができる。
【００２６】
接着層をフィルムに塗布する方法としては、接着層塗布液をグラビア印刷法、マイクログラビア印刷法、コンマコート法、ロールコート法、リバースロールコート法、バーコート法、キスコート法、フローコート法でコートし、乾燥する方法を例示することができる。乾燥温度は、塗布方法や溶媒やフィルムの樹脂の種類やフィルムの厚みによっても異なるが、一般的には１５０℃以下が望ましい。
【００２７】
また、接着層の厚さは、０．５μｍ以上が望ましい。０．５μｍより薄い場合は、光触媒層を強固にフィルムに接着させる効果に乏しく、長期間の使用において光触媒層が剥離したりしやすくなるため好ましくない。また、接着層の厚みが厚い場合は特に問題はないものの、成膜時の乾燥が不十分になるため、成膜のムラが発生しやすくなったり、成膜コストが上昇するため実際的には５μｍ以下が好ましい。
【００２８】
本発明における樹脂基体にラミネート加工する光触媒担持高分子樹脂フィルムは、図１に示すように、接着層の上に光触媒層を設けた構造を有している。光触媒層は、例えば、金属酸化物ゾルを固形分として１〜１０重量％、酸化チタンゾルを固形分として１〜１０重量％含有する光触媒層塗布液を接着層上に塗布乾燥して形成することができる。光触媒層塗布液中の金属酸化物ゾルは、酸化チタンゾルを固着し接着層と強固に接着させるだけでなく、金属酸化物ゾルを乾燥して得られるゲルが多孔質であることから吸着性をもっており、光触媒活性を高める効果も有している。この金属酸化物ゾルと酸化チタンゾルの光触媒塗布液中での比率は、２５／７５〜９５／５が好ましい。金属酸化物ゾルが２５％以下では接着層との接着が不十分となり、他方９５％以上では光触媒活性が不十分となる。また、金属酸化物ゾルを乾燥して得られるゲルの比表面積が１００ｍ2 ／ｇ以上あると、接着性はより強固になり、触媒活性も向上する。材質としては、ケイ素、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、タングステンの金属の酸化物ゾルがよく、また、これらを混合したゾルや、共沈法などの方法で作られる複合酸化物ゾルを使用してもよい。
【００２９】
金属酸化物ゾルを酸化チタンゾルと混合する場合、ゾルの状態で混合するか、あるいはゾルを調製する前の原料の段階で混合するのが望ましい。ゾ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、ゾルの中に酸化チタンゾル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。しかし、ゾ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、不純物の少ないゾルを用いる方が好ましい。特に、ゾルを乾燥したゲルの中に有機物が５％以上存在すると、光触媒活性が低下する。特に、ジルコニウムやアルミニウムの酸化物ゾルを含む光触媒層を使用する場合は、水道水中での１５分間の耐沸騰水性試験後のテープ剥離試験に合格したり、５％炭酸ナトリウム水溶液中への１６８時間浸漬試験後のテープ剥離試験に合格するものが得られるため特に好ましい。
【００３０】
また、光触媒層として、シリカゾルを１〜１０重量％、モノアルキルトリメトキシシラン又はその加水分解生成物を１〜１０重量％、及び、酸化チタンゾルを１〜１０重量％含む混合液からなる光触媒層塗布液を接着層上に塗布乾燥して得られるものも特に好ましく使用できる。モノアルキルトリメトキシシランとしては、メチルトリメトキシシラン、メチルトリエトキシシランが特に好ましく使用できる。シリカゾルと、モノアルキルトリメトキシシラン又はその加水分解生成物との混合比率は、重量比で１００／０〜６０／４０が好ましく、酸化チタンゾルとこれらの珪素化合物成分の比率は、酸化チタン／珪素化合物の重量比で５／９５〜７５／２５が好ましい。珪素化合物の比率が９５％以上では光触媒活性が低下するし、２５％以下では接着層への接着性が低下する。
【００３１】
光触媒層中の光触媒としては、ＴｉＯ2 、ＺｎＯ、ＳｒＴｉＯ3 、ＣｄＳ、ＧａＰ、ＩｎＰ、ＧａＡｓ、ＢａＴｉＯ3 、Ｋ2 ＮｂＯ3 、Ｆｅ2 Ｏ3 、Ｔａ2 Ｏ5 、ＷＯ3 、ＳｎＯ2 、Ｂｉ2 Ｏ3 、ＮｉＯ、Ｃｕ2 Ｏ、ＳｉＣ、ＳｉＯ2 、ＭｏＳ2 、ＩｎＰｂ、ＲｕＯ2 、ＣｅＯ2 などを例示することができ、またこれらの光触媒にＰｔ、Ｒｈ、ＲｕＯ2 、Ｎｂ、Ｃｕ、Ｓｎ、ＮｉＯなどの金属及び金属酸化物を添加した公知のものが全て使用できる。光触媒層中の光触媒の含有量は、多くなるほど触媒活性が高くなるが、接着性の点から７５重量％以下が好ましい。抗菌性や防カビ性をさらに向上させるため、光触媒層中に酸化チタン光触媒に対して０．０５〜５重量％の銀や銅の金属もしくは金属化合物を添加することもできる。添加量が０．０５重量％以下では抗菌／防カビ性の向上効果に乏しく、５重量％以上では光触媒層が変色したりするという現象が生じるためフィルムをラミネートした樹脂の色や柄によっては使用が困難になる場合もある。
【００３２】
光触媒層を接着層上に形成するには、金属酸化物ゾルもしくは金属水酸化物ゾル溶液中に光触媒を分散した懸濁液を用い、前記接着層を形成するのと同様のコート法でコートすることができる。金属酸化物ゾルも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もしくはゲル化させてもよい。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よい。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、接着性や操作性をよくすることもできるが、光触媒層におけるシランカップリング剤の添加では、光触媒担持フィルムを加熱加圧処理によって樹脂基体の表面にラミネート加工する場合における光触媒活性の低下を防止し、ラミネート加工前の光触媒担持フィルムが有する光触媒活性を維持することができない。光触媒層形成時の乾燥温度としては、塗布方法やフィルムの樹脂の材質及び接着層中の樹脂材質によっても異なるが、一般的に１５０℃以下が好ましい。
【００３３】
光触媒層は、その厚みが厚いほど活性が高いが、５μｍ以上になるとほとんど変わらなくなる。５μｍ以下であっても高い触媒活性を示し、透光性を示して触媒層が目立たなくなるが、厚さが０．１μｍ以下になると透光性はよくなるものの、光触媒が利用する紫外線をも透過してしまうために、高い活性は望めなくなる。光触媒層の厚さを０．１μｍ以上５μｍ以下にし、しかも、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、高い光触媒活性を有し、ベースフィルムをラミネートした樹脂基体の風合いを損なうことがないので美観の上でも好ましい。
【００３４】
本発明において光触媒担持フィルムが加熱加圧処理によりラミネート加工される樹脂基体としては、ポリ塩化ビニル樹脂、ポリエチレンテレフタレート樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、変性ポリスチレン樹脂、耐衝撃性ポリスチレン樹脂、アクリル−ブタジエン−スチレン共重合樹脂、の中から選ばれた樹脂からなるものを例示することができる。また、樹脂基体の形状としては、板状、シート状、織布状、不織布状、樹脂含浸強化織布状、管状等光触媒担持フィルムをラミネート加工できるのものであればどのような形状のものでもよい。
【００３５】
光触媒担持高分子樹脂フィルムを各種樹脂基体にラミネートする方法としては、熱ロールなどで加熱加圧しながら樹脂板や塗装樹脂板等の樹脂基体にラミネートする方法や、樹脂板、塗装樹脂板、樹脂被覆樹脂板等の樹脂基体の製造時の加熱処理の熱を利用した加熱加圧処理による光触媒担持高分子樹脂フィルムをラミネートする方法などが工業的に効率よく製造できるため好ましい。すなわち、樹脂基体に光触媒担持フィルムを加熱加圧処理によってラミネート加工するには、ベースフィルムの樹脂の材質や樹脂基体の材質にもよるが、通常６０℃〜２００℃の温度範囲で短時間加熱加圧処理するラミネート方法、樹脂構造体となる樹脂基体の押し出し成型時の余熱を利用してプレスするラミネート方法、熱ロールを通したり熱プレスで処理するラミネート方法などを採用することが好ましい。
【００３６】
また、加熱加圧処理する樹脂基体の表面を、コロナ放電処理や紫外線照射処理を行ったり、アクリル系、ウレタン系、エポキシ系の接着剤をプライマー層として塗布乾燥したりして得られる基体を使用することにより、より一層熱ラミネート加工品のフィルム密着性、耐久性を高めることができる。樹脂板もしくは塗装樹脂板等の樹脂基体の材質と光触媒を担持したフィルムの材質に応じた適正な温度・圧力・時間を選択することで、長期に使用した場合にも耐久性に優れかつ光触媒活性を維持できる樹脂構造体を得ることができる。また、本発明においては、ラミネート加工に加熱加圧処理を採用することから、光触媒層が接着層に非常に強固に固着し、加熱加圧処理前に比較して、耐久性、密着性、耐剥離性が向上するという利点がある。
【００３７】
本発明における光触媒担持フィルムを加熱加圧処理によってラミネート加工した樹脂構造体は、大気中温度２５℃、相対湿度７０％の状態でＵＶ−Ａ領域（４００〜３１５ｎｍ）の紫外線を３ｍＷ／ｃｍ2 照射した時にトリオレインを５μｇ／ｃｍ2 ・ 日 以上分解しうるものとなっている。本発明による光触媒担持フィルムをラミネートした樹脂構造体は、紫外線強度３ｍＷ／ｃｍ2 のブラックライトの光を温度４０℃、相対湿度９０％のもとで１０００時間照射した後でも、ＪＩＳ Ｋ ５４００の碁盤目テープ法で調べた光触媒層の付着性が、評価点数６点以上を維持するような高耐久性を示す物も得られる。
【００３８】
本発明による接着層と光触媒層を設けた光触媒担持フィルムは、生産性も高く毎分数十ｍ以上の速度で成膜できる上に、この光触媒担持フィルムを各種樹脂基体にラミネート加工する際も加工条件を最適化することによって毎分数ｍ以上の高速度で加工できる。したがって、単に樹脂基体に通常のディップ法やスプレー法やロールコート法によって光触媒層を塗布乾燥する方式に比べて格段に速い速度での成膜が可能になり、生産効率や膜厚の均一性などの成膜品質の向上の面で非常に大きな利点を有している。また、本発明によって得られる光触媒フィルムをラミネートした樹脂構造体は、光触媒フィルムをラミネート後に樹脂基体をプレス加工して成形したり、カットして切断することにより、複雑形状の樹脂加工製品とすることができるため、その応用範囲は極めて広い。
【００３９】
本発明の光触媒担持高分子樹脂フィルムをラミネート加工した樹脂構造体は、広く一般建築用材料や屋外設置構造体材料として、例えば屋外広告塔、道路遮音壁、道路脇電話ボックス、道路標識などの道路関連の設備構造体、浴室・トイレや洗面所・台所などの場所における樹脂成形品、例えば洗面化粧台、ユニットバス、システムキッチン、便器、各種シンクなどの家庭用機器の表面建材として使用することができる。
【００４０】
また、本発明の光触媒担持フィルムをラミネートした樹脂構造体は、屋外看板に使用されているポリ塩化ビニル製のマーキングフィルムで製作した看板、電車・バスなどの輸送体の樹脂製の窓、屋外使用のテント生地、野積みシート、テント倉庫、商店等の軒だし日よけ、各種アーケードのテント屋根、展示会パビリオン等のテント屋根や側面のテント覆い、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、プールカバーなどに使用することができる上に、光触媒担持フィルムをラミネートした樹脂構造体を木材やモルタルの表面に設置し、病院・老人保健施設の壁、ドア、天井、備品等に使用することもできる。このように、本発明の光触媒担持フィルムをラミネートした樹脂構造体は、消臭、防汚、抗菌、防カビの作用を必要とする多くの箇所に使用することができ、その優れた消臭性、防汚性、抗菌性、防カビ性により、長期にわたって表面を美麗な状態に維持することができる。
【００４１】
そして、本発明の光触媒を担持したフィルムをラミネートした樹脂構造体を、屋外表示板や屋外看板、屋外用テント生地、電話ボックス等に使用した場合は、このフィルムが有する優れた光触媒分解活性により排気ガス等に含まれるばい煙や油煙が分解されるため、それらの接着作用によって表面に付着している埃や塵、砂、粘土などが取れ易くなり風雨などで落とされてしまい、結果として汚れにくいものとなる。また、アクリル板製水槽に本発明による光触媒担持高分子樹脂フィルムをラミネート加工したものを使用した場合は、蛍光灯から放射される紫外線によって水槽の内面に付着した有機物や菌が分解されて、表面の水垢による汚れが少なくなり汚れが目立たなくなる。本発明による光触媒担持フィルムをラミネートした樹脂板は、厨房、トイレ、浴室で使用されるシステムキッチン、洗面化粧台、ユニットバスの素材としても好適に使用でき、こうした場所における比較的少ない紫外線を利用しても防汚・抗菌機能を発揮させることができるため好ましい。冷蔵庫、洗濯機、パソコン、ラジオ・テレビなどの家庭用電気製品の樹脂製の筐体表面、及び食器カゴや調味料ケースなどの各種プラスチックケースの表面に本発明による光触媒担持高分子樹脂フィルムをラミネート加工したものを使用した場合は、室内環境で照射される紫外線量は少ないものの室内に浮遊するオイルミストや手指の接触による皮脂成分が光触媒分解作用により徐々に分解され、結果的に表面に付着する手垢や黒ずみが減少するという優れた効果が奏される。
【００４２】
【実施例】
以下実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
実施例１ 光触媒担持フィルムの製造
三菱レイヨン（株）製アクリル樹脂フィルム「アクリプレンＨＢＳ−００６」厚み５０μｍのフィルムに、康井精機（株）製マイクログラビア印刷機を使用して接着層塗布液と光触媒層塗布液を塗布した。シリコン含有量３ｍｏｌ％のアクリルシリコン樹脂を固形分として８重量％含むエタノール−酢酸エチル（５０／５０重量比）溶液に、ポリシロキサンとしてコルコート（株）製メチルシリケートＭＳ５１の２０％エタノール溶液をアクリルシリコン樹脂に対して固形分として３５重量％と、シランカップリング剤としてγ−グリシドキシプロピルトリメトキシシランを塗布液中に１重量％とを添加し、接着層の塗布液とした。２０ｍ／分の速度で温度６０℃で接着層を成膜後、室温下放冷した。界面活性剤の存在下、水−エタノール５０／５０の重量比の液に酸化チタン含有量１０重量％になるよう硝酸酸性チタニアゾルを分散させたものに、同じく水−エタノール５０／５０の重量比の液に酸化珪素含有量１０重量％になるよう硝酸酸性シリカゾルを分散させたものを等量加え、光触媒層塗布液を調整した。この液を使用して接着層と同様の条件で成膜し光触媒層を担持させ、光触媒担持フィルム（Ａ）とした。同様な方法で、接着層と光触媒層を成膜温度と乾燥条件を変えて他のフィルム材質に成膜し、鐘淵化学（株）製アクリル系フィルム「サンデュレン ００８ＮＣＴ」５０μｍ厚（Ｂ）、住友ベークライト製硬質塩ビフィルム５０μｍ厚（Ｃ）、を使用して光触媒担持フィルムを作成した。
【００４３】
実施例２ 光触媒担持フィルムをラミネートしたポリカーボネート樹脂
実施例１で得られた光触媒担持フィルム（Ａ）を、東洋精機製作所製の熱板プレス装置を使用して、室温で圧力５０ｋｇ／ｃｍ2 を１０秒間加える操作を５回繰り返してエアー抜きを行った後、１２０℃に昇温して５０ｋｇ／ｃｍ2 で２分、同じ温度で１００ｋｇ／ｃｍ2 で２分、１５０ｋｇ／ｃｍ2 で１分の温度圧力で加熱加圧した後、加圧したまま５０℃以下に冷却して、筒中プラスチック（株）製ポリカーボネート樹脂板ポリカエースＥＣ１００の３ｍｍ厚みを１０×１０ｃｍ角に切り出したものに張りつけ光触媒担持フィルムをラミネートしたポリカーボネート板とした。このサンプルの可視光に対するヘイズ率は０．７％、全光線透過率は９０．２％であり極めて透明性の高いものであった。（サンプル１）
【００４４】
実施例３ 光触媒担持フィルムをラミネートした塩化ビニル樹脂
実施例１で得られた光触媒担持フィルム（Ｃ）を、実施例２と同じ方法と条件で、積水化学（株）製透明硬質ポリ塩化ビニル樹脂板の３ｍｍ厚みを１０×１０ｃｍ角に切り出したものに張りつけ光触媒フィルムをラミネートした硬質塩化ビニル板とした。（サンプル２）
【００４５】
実施例４ 光触媒担持フィルムをラミネートしたアクリル樹脂
実施例１で得られた光触媒担持フィルム（Ａ）を、実施例２と同一の装置により旭化成（株）製アクリル板デラグラスＡ Ｎｏ．９９９の３ｍｍ厚みを１０×１０ｃｍ角に切り出したものに張りつけ、加熱プレス装置を使用して、１４０℃で１０分間１６０ｋｇ／ｃｍ2 の圧力で熱プレスして光触媒フィルムをラミネートしたアクリル樹脂板とした。（サンプル３）
【００４６】
実施例５ 光触媒担持フィルムをラミネートしたＡＢＳ樹脂
実施例１で得られた光触媒担持フィルム（Ｂ）の裏面に、宇部サイコン（株）製ＡＢＳ樹脂サイコラックＥＸ２１５の３ｍｍ厚みの板を１０×１０ｃｍ角に切り出したものに張りつけ加熱プレス装置を使用して、１２０℃で１０分間１６０ｋｇ／ｃｍ2 の圧力で熱プレスして光触媒フィルムをラミネートしたＡＢＳ樹脂板とした。（サンプル４）
【００４７】
実施例６ 光触媒担持フィルムをラミネートしたＨＩＰＳ樹脂
実施例１で得られた光触媒担持フィルム（Ｂ）の裏面に、出光石油化学（株）製ＨＩＰＳ樹脂出光スチロール ＨＴ−５４の３ｍｍ厚みの板を１０×１０ｃｍ角に切り出したものに張りつけ加熱プレス装置を使用して、１００℃で１０分間１６０ｋｇ／ｃｍ2 の圧力で熱プレスして光触媒フィルムをラミネートしたＡＢＳ樹脂板とした。（サンプル５）
【００４８】
実施例７ 銅添加光触媒担持フィルムをラミネートした塩化ビニル樹脂
実施例１において、光触媒層の塗布液中に、酸化チタンに対して０．０１重量％の硝酸銅水和物を添加溶解したものを使用すること以外は実施例１と同様な方法と装置により、三菱レイヨン（株）製アクリル系フィルム「アクリプレンＨＢＳ−００６」の５０μｍ厚みのフィルムをベースフィルムとする光触媒担持フィルムを作成した。この光触媒担持アクリル樹脂系フィルムを、実施例３と同じ方法と条件で積水化学（株）製透明硬質ポリ塩化ビニル樹脂板の３ｍｍ厚みを１０×１０ｃｍ角に切り出したものに張りつけ銅添加光触媒フィルムラミネートした硬質塩化ビニル板とした。（サンプル６）
【００４９】
実施例８ 光触媒フィルムをラミネートしたＡＢＳ樹脂板を使用した洗面化粧台
実施例５で使用したものと同じ光触媒担持フィルムとＡＢＳ樹脂を使用し、熱ロールラミネート装置を使用してニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１３０℃、シート送り速度１０ｍ／分でラミネートしたＡＢＳ樹脂板を使用して、洗面化粧台の下部の観音開き戸を試作した。評価にはこの板から５×５ｃｍに切りだした試料を使用した。（サンプル７）
【００５０】
実施例９ 光触媒フィルムをラミネートしたアクリル板を使用した屋外看板
アクリル樹脂板に住友３Ｍ社製の屋外表示板用の着色塩化ビニル製マーキングフィルムで看板用の文字型に切り抜いたものを貼り付け、その上に実施例１で試作した光触媒担持フィルム（Ｃ）を、実施例８と同様の方法によりニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１２０℃、シート送り速度１０ｍ／分でラミネートしたアクリル樹脂板を使用した屋外看板を試作した。評価にはこの板から５×５ｃｍに切りだした試料を使用した。（サンプル８）
【００５１】
実施例１０ 光触媒フィルムをラミネートしたポリエステル板からなるユニットバス
ポリエステル樹脂板に実施例１で試作した光触媒担持フィルム（Ｃ）を、実施例８と同様の方法によりニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１２０℃、シート送り速度１０ｍ／分でラミネートしたポりエステル樹脂板を使用したユニットバス用樹脂板を試作した。評価にはこの板から５×５ｃｍに切りだした試料を使用した。（サンプル９）
【００５２】
実施例１１ 光触媒フィルムをラミネートしたアクリル板からなる水槽
アクリル樹脂板に、実施例１で試作した光触媒フィルム（Ｃ）を熱ロールラミネート装置を使用して、ニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１２０℃、シート送り速度１０ｍ／分でラミネートしたアクリル樹脂板を製造した。この光触媒担持フィルムをラミネート加工したアクリル樹脂板を使用して水槽を試作した。評価にはこの板から５×５ｃｍに切りだした試料を使用した。（サンプル１０）
【００５３】
実施例１２
光触媒フィルムをラミネートしたＨＩＰＳ板からなるシステムキチン用収納扉
ＨＩＰＳ樹脂板に、実施例１で製造した光触媒フィルム（Ｃ）を熱ロールラミネート装置を使用して、ニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１２０℃、シート送り速度１０ｍ／分でラミネートしたＨＩＰＳ樹脂板を製造した。この光触媒担持フィルムをラミネート加工したＨＩＰＳ樹脂板を使用してシステムキッチン用収納扉を試作した。３０ｃｍ×３０ｃｍのサンプルを既存のシステムキッチンの扉に貼っておいた所、６ケ月経過後で光触媒フィルムをラミネートしたＨＩＰＳ板を張り付けた部分の耐汚染性を分光色差計で測定した変色度で見た評価では、ΔＥの変化値で４．５であったのに対して、光触媒フィルムをラミネートしていない壁紙の部分は、ΔＥの変化値で１６．５であり、汚染がより進行していた。
【００５４】
実施例１３ 光触媒フィルムをラミネートした塩ビシートからなる壁紙
発泡剤を添加した壁紙用塩ビシートに、実施例１で製造した光触媒フィルム（Ｃ）をエンボスロールを取り付けた熱ロールラミネート装置を使用して、ニッブ圧力３ｋｇ／ｃｍ、エンボスロールでのシート表面温度１４０℃、シート送り速度１０ｍ／分でラミネートした発泡塩ビ壁紙を製造した。１ｍ×１ｍのサンプルを室内の壁に貼っておいた所、６ケ月経過後で光触媒フィルムをラミネートした壁紙を張り付けた部分の耐汚染性を分光色差計で測定した変色度で見た評価では、ΔＥの変化値で６．５であったのに対して、光触媒フィルムをラミネートしていない壁紙の部分は、ΔＥの変化値で２６．５であり、汚染がより進行していた。
【００５５】
実施例１４ 光触媒フィルムをラミネートした食品トレー
厚さ０．５ｍｍのポリプロピレンシートの表面をコロナ放電処理した面にウレタン系接着剤を塗布した後、実施例１で試作した光触媒フィルム（Ａ）を熱ロールラミネート装置を使用して、ニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１４０℃、シート送り速度１０ｍ／分で光触媒フィルムをラミネートしたポリプロピレンシートを製造した。このシートを更に加熱プレス加工して、食品販売用のトレーを試作した。このトレー（縦２５ｃｍ×横１０ｃｍ×深さ３ｃｍ）に牛肉２００ｇを入れポリエチレンのラップフィルムで覆い温度２０℃の恒温槽中で１０Ｗの蛍光灯を４本１５ｃｍの距離で照射した中に入れ、光触媒フィルムをラミネートしていないポリプロピレン製のトレーに同様に牛肉を入れたものと一緒に保管した。光触媒フィルムをラミネートしていないトレーのものは、４時間経過後で既に黒く変色し少し腐敗臭がしたのに対して、光触媒フィルムをラミネートしたものでは４時間経過後でも殆ど腐敗臭はなく変色の程度も少なかった。
【００５６】
実施例１５ 光触媒フィルムをラミネートした包装用フィルム
ポリエチレンフィルムの表面を実施例１４と同様にコロナ放電処理しアクリル系接着剤を塗布した後に、実施例１で試作した光触媒フィルム（Ａ）を熱ロールラミネート装置を使用して、ニッブ圧力３ｋｇ／ｃｍ、ラミネーションロールでのシート表面温度１３０℃、シート送り速度１０ｍ／分で光触媒フィルムをラミネートしたポリエチレンシートを製造した。このポリエチレンシートを使用して、ほうれん草を１束つつみ、１５Ｗの蛍光灯３本照射下で、光触媒フィルムをラミネートしていないポリエチレンフィルムでつつんだほうれん草と比較した。４時間経過後では光触媒フィルムでラミネートしたポリエチレンフィルムで包んだほうれん草は殆ど変色がなかったのに対して、光触媒フィルムをラミネートしていないポリエチレンフィルムでつつんだほうれん草は、濃い緑色に変色し萎れていた。ほうれん草から発散されるエチレンガスが分解されたためと考えられる。
【００５７】
比較例１
三菱レイヨン（株）製アクリル系フィルム「アクリプレンＨＢＳ−００６」厚み５０μｍのフィルムを、実施例２と同一の方法と条件により、筒中プラスチック（株）製ポリカーボネート樹脂板ポリカエースＥＣＫ１００の３ｍｍ厚みを５×５ｃｍに切り出したものに張りつけアクリルフィルムをラミネートしたポリカーボネート板とした。
【００５８】
比較例２
鐘淵化学（株）製アクリル系フィルム「サンデュレン ００８ＮＣＰ」の５０μｍ厚みのものを、旭化成（株）製デラグラスＡ Ｎｏ．９９９の３ｍｍ厚みを５×５ｃｍ角に切り出したものに張りつけ加熱プレス装置を使用して、実施例４と同一の条件と方法により熱プレスしてアクリルフィルムをラミネートしたアクリル樹脂板とした。
【００５９】
比較例３
住友ベークライト製硬質塩ビフィルムの５０μｍ厚みのものを、積水化学（株）製透明硬質ポリ塩化ビニル樹脂板の３ｍｍ厚みを５×５ｃｍ角に切り出したものに実施例３と同一の方法と条件により張り付け塩ビフィルムをラミネートした硬質塩化ビニル板とした。
【００６０】
（光触媒活性の評価）
サンプル１〜１０の試料と比較例の試料を用いて、以下に示すような評価を行い、表１に示す結果を得た。
【００６１】
１）耐汚染性（防汚特性）
５ｃｍ×５ｃｍ角に切りだした試料を、一般道路（トラック通行量５００〜１０００台／日程度）に面したフェンスに光触媒を担持していない同種同サイズのブランク試料とともに張りつけ、３ケ月後試料表面の汚染の度合いを冷暗所に保管した比較対照試料を基準として分光色差計により評価した。
２）トリオレイン分解特性（油分解活性）
５ｃｍ角に切り出した試料にキムワイプを使用して、トリオレイン（和光純薬製試薬特級）を０．１ｍｇ／ｃｍ2 になるよう塗布した後、温度２５℃相対湿度７０％の恒温恒湿槽中に入れ市販の１５Ｗブラックライト蛍光灯を照射して、試料面でＵＶ−Ａ領域の紫外線が３ｍＷ／ｃｍ2 の強度になるよう光源と試料面との距離を調節した。光照射時間に対するトリオレインの減少量を精密天秤により定量しトリオレイン分解活性を求めた。
３）抗菌性評価
５ｃｍ角に切りだした試料を８０％エタノールで消毒し１５０℃で乾燥して滅菌後、予め前培養と希釈を行って菌濃度を１０５個／ｍｌに調節しておいた大腸菌の菌液を０. ２ｍｌ試料面に滴下しインキュベーター内にセットした。白色蛍光灯（１５Ｗ×２本、光源との距離１０ｃｍ）の光を照射したもの、及び光照射を全く行わなかったもの、の２種の光照射条件で各々４個の試料をセットした。所定時間後（１、２、３、４時間後）に試料を取り出し、滅菌生理食塩水に浸した滅菌ガーゼで試料上の菌液を拭き取り、拭き取った滅菌ガーゼを１０ｍｌの滅菌生理食塩水に入れ十分攪拌した。この上澄み菌液をオートクレーブ滅菌した９５ｍｍφのシャーレ寒天培地に植え付け、３６℃２４Ｈｒ培養後大腸菌のコロニー数を計数した。インキュベーターに入れるまでの操作を全く同一にした基準菌数測定用試料を同一の方法により調製し、滅菌生理食塩水の上澄み液をシャーレ寒天培地に植え付けて２４Ｈｒ培養後の大腸菌のコロニー数を計数した。その数値を基準にして各試料の所定時間後における大腸菌の生存率を算出した。４時間経過後の蛍光灯の光を照射した試料の大腸菌の残存率により評価し、評価基準は以下の通りとした。
４）防カビ性
耐汚染性の評価に使用した試料表面の緑色のカビの発生の程度を以下の基準で冷暗所に保管した試料と比較対照することにより評価した。
試料表面のカビの発生の度合い 評価
殆ど発生が認められない Ａ
一部僅かに発生が認められる Ｂ
明らかに発生が認められる Ｃ
【００６５】
（付着性の評価）
ＪＩＳ Ｋ ５４００に規定する碁盤目テープ法試験により、付着性の評価を行った。切り傷の間隔を２ｍｍとし、ます目の数を２５コとした。評価点数は、ＪＩＳ Ｋ ５４００に記載の基準で行った。
【００６６】
（耐久性の評価）
担持した試料にブラックライトで紫外線強度３ｍＷ／ｃｍ2 の光を温度４０℃湿度９０％の恒温恒湿槽内で１０００時間照射後、ＪＩＳ Ｋ ５４００に規定の碁盤目テープ法による付着性を測定し、耐久性の評価とした。評価点数は、付着性評価と同じである。
【００６７】
【表１】
比較例４
ＷＯ９７−１３４に記載された実施例４８に準じて、接着層用の塗布液としてシリコン含有量２０％のアクリルシリコン樹脂エマルジョン水溶液に乾燥接着層中のＳｉＯ2 含有量が１０％となるよう触媒化成（株）製カタロイドＳＩ−３５０を添加して全体としての乾燥固形分を２０％に調整した。また光触媒層塗布液として日本エアロジル社の光触媒用酸化チタンＰ−２５を固形分として３０％、触媒化成（株）製シリカゾルカタロイドＳＩ−３０を固形分として２０％、日産化学（株）製アルミナゾル−２００を乾燥固形分として１０％、シリコン含有量２０重量％のアクリルシリコン樹脂エマルジョン水溶液を不揮発残分として３５％、シランカップリング剤として日本ユニカー（株）製トリ（β−メトキシエトキシ）ビニルシランを不揮発残分として５％を全体として１０％の乾燥残分になるよう調製した。これらの塗布液を用いて、康井精機（株）製マイクログラビア印刷機を使用して三菱レイヨン（株）製アクリルフィルム「アクリプレンＨＢＳ−００６」５０μｍ厚のフィルムに塗布したが、接着層の乾燥硬化が不十分で成膜することはできなかった。そこで、卓上型バーコーターで同じ接着層の塗布液と光触媒層の塗布液を使用して三菱レイヨン（株）製の上述のアクリルフィルム上に塗工し、乾燥温度８０℃で乾燥したが、乾燥時間は１時間必要であった。この光触媒担持アクリルフィルムを、筒中プラスチック（株）製ポリカーボネート樹脂板ポリカエースＥＣ１００の３ｍｍ厚みを１０×１０ｃｍ角に切り出したものに張りつけ、実施例２と同様の方法と条件により熱ラミネート加工した。この熱ラミネート加工したポリカーボネート樹脂板の耐汚染性、油分解活性、抗菌性、防カビ性、付着性、耐久性は表１に示した通りである。このサンプルでは光触媒活性及び耐久性に劣っていた。このように、接着層塗布液にシランカップリング剤を含有することなく調製されたこの光触媒担持フィルムの透明ポリカーボネートへの適用は不適切なものであった。
【００６９】
【発明の効果】
本発明の光触媒担持フィルムをラミネート加工した樹脂構造体は、高い光触媒活性を有し、耐久性に優れ、防汚、抗菌、防カビ等を目的とする、各種建築材料用、屋外看板、屋外表示板、道路周辺設備、屋内建材、室内器具、厨房器具、トイレ洗面設備等に使用可能で、かつ価格性能比に優れている。また、本発明による接着層と光触媒層を設けた光触媒担持フィルムは、生産性も高く毎分数十ｍ以上の速度で成膜できる上に、この光触媒担持フィルムを各種樹脂基体にラミネート加工する際も加工条件を最適化することによって毎分数ｍ以上の高速度で加工できる。
【図面の簡単な説明】
【図１】本発明の光触媒担持フィルムをラミネートした樹脂構造体断面の模式図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin structure obtained by laminating a photocatalyst-supporting film having effects such as deodorizing, antifouling, antibacterial, and antifungal by heat and pressure treatment, a production method thereof, and an application product thereof.
[0002]
[Prior art]
An n-type semiconductor titanium oxide is known as a photocatalyst that promotes various chemical reactions such as sterilization and decomposition of organic substances by the energy of ultraviolet rays. Various methods for supporting a photocatalyst on glass, metal, plastic, tile, and the like have been proposed (Japanese Patent Laid-Open Nos. 62-68661, 5-309267, EP 633064, USP 4888101). However, a resin structure obtained by laminating a film carrying a photocatalyst, particularly a resin obtained by laminating a photocatalyst carrying film carrying a photocatalyst without reducing the catalytic activity on a widely used polycarbonate resin or woven cloth reinforced polyvinyl chloride resin. No structure is known, and a method for maintaining the deodorizing, antifouling, antibacterial, and antifungal properties over a long period of time by effectively utilizing the photocatalytic action of the resin structure laminated with such a photocatalyst carrying film is also reported. It has not been.
[0003]
Conventionally, resin structures such as polycarbonate sound insulation walls installed outdoors and fiber reinforced resin impregnated with polyvinyl chloride tend to adhere to dust and soot in the outside air and usually turn black in 2 to 3 months, causing contamination. Had the major drawback of detracting from Further, mold is easily generated due to a plasticizer component contained in a large amount in the polyvinyl chloride resin, and a method of coating the surface with a fluororesin is taken as a countermeasure. However, since the fluororesin coat increases the water repellency of the surface and increases the oleophilicity as has been said, there has been a drawback that oily dirt such as soot smoke is likely to adhere. In addition, titanium oxide originally has the property of developing hydrophilicity when irradiated with ultraviolet rays in the atmosphere. By utilizing this effect, the surface of the outdoor installation structure is made hydrophilic, and the attached oil mist A method for facilitating washing off oils such as water with water (especially rainwater) is also disclosed (Japanese Patent Laid-Open No. 63-100042, WO96 / 29375). These make use of the phenomenon that water is easily wetted on the surface by making the physical properties of the structure surface hydrophilic, and as a result, oil rises from the surface and flows down. However, since the method based on the published technology has a poor photocatalytic decomposition action of oil adhering to the surface, the road sound insulation wall that adheres a large amount of dirt such as exhaust gas from diesel vehicles is subject to restrictions on the range of use in practical use. There was a big problem.
[0004]
In WO97-134, a photocatalyst layer made of a photocatalyst particle composite containing a metal oxide gel is provided on a resin substrate by a dip method or a spray method through an adhesive layer made of an acrylic silicon resin added with polysiloxane. Thus, an example in which high photocatalytic activity and excellent durability are maintained is disclosed. However, the method based on the published technology can be used as a laminated film with a pressure-sensitive adhesive applied to the back side of the photocatalyst-supporting film. When the film is formed at a high speed, the adhesive layer is not sufficiently cured, which causes a problem in photocatalyst coating.
[0005]
In addition, by providing a photocatalyst layer made of a photocatalyst particle composite containing a metal oxide gel through an adhesive layer made of an acrylic silicon resin added with polysiloxane on a polyester film, high photocatalytic activity and excellent durability are achieved. The maintained photocatalyst-supporting film is also disclosed in the above-mentioned WO97-134. However, the polyester film is generally very difficult to laminate by heating and pressurization, and is not suitable for the purpose of the present invention. .
[0006]
Furthermore, this disclosed composition of the coating solution has a problem that the drying and curing tends to be insufficient at the time of high-speed film formation, and the coated surface tends to stick to the back surface. In particular, a film that can be laminated by heating and pressurization has a low heat-resistant temperature and heat deformation temperature of 100 ° C. or lower, and therefore, the coating liquid and coating method disclosed in WO 97-134 are suitable for such thermal lamination. High-speed film formation on a film is difficult, and photocatalytic activity is lost depending on thermal lamination conditions. In addition, in the case of a plate-shaped large resin substrate, a method by coating such as a dip method or a spray method has a problem that it is often difficult to apply in practice because of restrictions on production facilities, film formation speed, and drying speed. In particular, a resin substrate having a width of 1 m or more has a problem that a large dryer is required and a drying time is 30 minutes or more due to the heat capacity, so that the production speed is slow and the cost is high.
[0007]
When a photocatalyst is supported on a resin plate or a coated resin plate for the purpose of antifouling, antibacterial properties, and deodorization, a photocatalyst structure having a structure in which a photocatalyst layer is provided via an adhesive layer is directly provided on the surface of the resin plate, etc. This is also considered as one method. However, in this method, the drying processing time after coating is much longer than that in the case of film formation, and in the case of film formation, the drying processing time is in seconds. The film has a heat capacity problem, and the processing time is at least in minutes. If the surface is flat, the film lamination is more productive even if the time for laminating the film is considered. Depending on the pH of the coating solution, the resin substrate may be eroded during coating and drying, and when the coating process on the resin substrate becomes larger than 1 m wide, it is difficult to form a uniform film, whether it is dip coating or spray coating. However, there is a problem that unevenness of the thickness of the film is likely to occur, and there is a drawback that the type and size of the applicable resin substrate are limited.
[0008]
[Problems to be Solved by the Invention]
An object of the present invention is to provide a resin structure in which a photocatalyst-carrying film having excellent deodorizing, antifouling, antibacterial, and antifungal effects is laminated.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors can efficiently laminate a transparent film carrying a photocatalyst at high speed, and that the photocatalytic activity does not decrease by heat laminating a film carrying a photocatalyst, We have earnestly researched items such as the ability to carry photocatalysts with high productivity on films that can be laminated at high speed, and the UV-A range of ultraviolet rays is 3 mW / mm at an atmospheric temperature of 25 ° C and a relative humidity of 70%. cm 2 5 μg / cm triolein when irradiated 2 The inventors have found that the above-mentioned problems can be solved by laminating a polymer resin film having photocatalytic activity capable of decomposing for more than a day on the surface of a resin substrate by heat and pressure treatment, and have completed the present invention.
[0010]
That is, the present invention Formed by application of an adhesive layer coating solution containing a silane coupling agent as a curing agent It is obtained by laminating a photocatalyst carrying film made of a polymer resin film carrying a photocatalyst layer through an adhesive layer on the surface of a resin substrate by heat and pressure treatment, and has an atmospheric temperature of 25 ° C. and a relative humidity of 70. % UV light in the UV-A region at 3 mW / cm 2 5 μg / cm triolein when irradiated 2 -It is related with the resin structure which laminated the photocatalyst carrying | support film characterized by having photocatalytic activity which can be decomposed | disassembled more than a day.
[0011]
In the present invention, the polymer resin film is a film obtained by laminating two or more resin films, and the polymer resin film is a copolymer of a polycarbonate resin, two or more polymethyl methacrylate resins, or a polyacrylate resin. The resin is selected from resin, polyvinyl chloride resin, or cellophane resin, and the film thickness of the polymer resin film is 5 to 200 μm. , Silane coupling as a curing agent in a coating solution containing 2 to 20% by weight of a silicone-modified resin containing 10 to 50% by weight of polysiloxane or 5 to 30% by weight of colloidal silica as a coating solution for the adhesive layer. An adhesive layer coating solution in which 0.1 to 5% by weight of an agent is added to the coating solution, and monoalkyltrimethoxysilane or polysiloxane which is a hydrolysis product thereof as 1 to 10 as the adhesive layer coating solution. Use of an adhesive layer coating solution obtained by adding 0.1 to 5% by weight of a silane coupling agent as a curing agent to a coating solution containing 0.1% by weight to 5% by weight of silica sol, and the above adhesive layer The photocatalyst layer has a metal oxide sol as a solid content of 1 to 10% by weight and a titanium oxide sol as a solid content of 1 to 10% by weight. The photocatalyst layer contains 1 to 10% by weight of silica sol, 1 to 10% by weight of monoalkyltrimethoxysilane or a hydrolysis product thereof, and 1 to 10% by weight of titanium oxide sol, The photocatalyst layer has a thickness of 0.1 to 5 μm, and the resin substrate is a polyvinyl chloride resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, polyethylene resin, polypropylene resin, impact-modified polystyrene resin, acrylic -Resin selected from butadiene-styrene copolymer resin, or the shape of the resin substrate is plate, sheet, woven fabric, nonwoven fabric, resin-impregnated reinforced fabric, or tubular A resin structure obtained by laminating the photocatalyst-supporting film characterized by Body on.
[0012]
In the present invention, the polymer layer is coated and dried with an adhesive layer coating solution to which a silane coupling agent is added as a curing agent, and then the photocatalyst layer coating solution is coated and dried on the adhesive layer. A photocatalyst-carrying film having a photocatalyst layer carried on an adhesive layer on a resin film is prepared, and the photocatalyst-carrying film is laminated on the surface of a resin substrate by heat and pressure treatment. The present invention relates to a method for producing a resin structure.
[0013]
Furthermore, the present invention provides an outdoor signboard and outdoor signboard, telephone box, outdoor tent fabric, bathroom vanity, unit bath, and a resin structure obtained by laminating the photocatalyst-supporting film described above. The present invention relates to a system kitchen, an aquarium fish tank, a plastic case, wallpaper, a food tray, or a packaging film.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The resin structure in which the photocatalyst-supporting film of the present invention is laminated is obtained by, for example, applying and drying an adhesive layer coating solution to which a silane coupling agent is added as a curing agent on a polymer resin film, and then applying the photocatalyst to the adhesive layer. A layer coating solution is applied and dried to prepare a photocatalyst-carrying film carrying a photocatalyst layer on a polymer resin film via an adhesive layer, and this photocatalyst-carrying film is laminated on the surface of a resin substrate by heat and pressure treatment. Can be manufactured. FIG. 1 shows a schematic diagram of a cross section of a resin structure in which the photocatalyst-supporting film of the present invention is laminated.
[0015]
As the polymer resin film in the present invention, polycarbonate resin, copolymer of two or more kinds of polymethyl methacrylate resin or polyacrylate resin, nylon resin, polyamide resin, polyimide resin, polyacrylonitrile resin, polyurethane resin, Examples thereof include a film made of a resin selected from vinyl chloride resin, cellophane resin, polyvinyl alcohol resin, vinyl acetate-ethylene copolymer resin, or ethylene-vinyl alcohol copolymer resin, and an adhesive layer. When coating and forming a photocatalyst layer, it is not preferable if a uniform and homogeneous photocatalyst-carrying film cannot be obtained due to stretching or wrinkling, so it can withstand the tension of the film forming machine during coating processing. Material and thickness that can maintain tensile elongation and elastic modulus Those with is preferable.
[0016]
Among these, a film made of a polycarbonate resin, a copolymer of two or more polymethyl methacrylate resins or polyacrylate resins, a polyvinyl chloride resin, or a cellophane resin can be particularly preferably used, and a photocatalyst-supporting film using these resins. Can be said to be excellent in terms of photocatalytic activity, durability, film formability, laminate processability, price, and the like. In addition, by using a film obtained by laminating two or more of these films, the properties to be possessed by the film supporting the photocatalyst, particularly weather resistance, heat resistance, moisture permeability, etc., can be greatly improved. It is possible to design and change the characteristics of the film supporting the photocatalyst according to the environment to be used, which is extremely advantageous for practical use.
[0017]
The film thickness of the polymer resin film to be used is preferably 5 to 200 μm, and if the film thickness is 5 μm or less, it becomes difficult to form the adhesive layer and the photocatalyst layer of the present invention, and if it is 200 μm or more, the lamination process is difficult. This is not preferable because the cost may increase or the cost may increase.
[0018]
In the present invention, the photocatalyst-supported polymer resin film laminated on the resin substrate has a structure in which an adhesive layer is provided between the photocatalyst layer and the film, as shown in FIG. The adhesive layer provided between the photocatalyst layer and the film is formed by applying and drying an adhesive layer coating solution on the film, and has a function of firmly adhering the photocatalyst layer to the film. In addition to preventing the decrease in photocatalytic activity due to the plasticizer component diffusing from the laminated polymer resin, it has the effect of preventing film degradation due to photocatalytic action, and the adhesive layer itself is less susceptible to degradation due to photocatalytic action. Have.
[0019]
As the adhesive layer coating solution in the present invention, a solution containing a silane coupling agent as a curing agent is particularly preferable. By including the silane coupling agent in the adhesive layer coating solution, the adhesive layer is cured during film formation. The film can be rolled up without sticking to the back surface, enabling high-speed film formation, and reducing the photocatalytic activity when laminating the photocatalyst-carrying film on the surface of the resin substrate by heat and pressure treatment. It is possible to prevent and maintain the photocatalytic activity of the photocatalyst-supporting film before lamination.
[0020]
As the adhesive layer coating solution in the present invention, for example, a coating solution containing 2 to 20% by weight of a silicon-modified resin containing 10 to 50% by weight of polysiloxane or a silicon-modified resin containing 5 to 30% by weight of colloidal silica. A coating solution obtained by adding 0.1 to 5% by weight of a silane coupling agent as a curing agent to the coating solution can be exemplified.
[0021]
In the case of a silicon-modified resin such as an acrylic silicone resin or an epoxy silicone resin having a polysiloxane content of less than 10% by weight, or a silicon-modified resin having a colloidal silica content of less than 5% by weight, adhesion of the photocatalyst layer during light irradiation is poor. In addition, the adhesive layer is deteriorated by the photocatalyst at a place where the ultraviolet ray intensity is strong such as outdoors, and the photocatalyst layer is easily peeled off. On the other hand, in the case of a silicon-modified resin having a polysiloxane content exceeding 50% by weight or colloidal silica content exceeding 30% by weight, the adhesion between the adhesive layer and the carrier becomes poor, or the adhesive layer becomes porous. Or the adhesiveness between the base film and the adhesive layer is deteriorated, and the photocatalyst is easily peeled off from the film.
[0022]
Further, as the adhesive layer coating solution in the present invention, a monoalkyltrimethoxysilane or a hydrosiloxane polysiloxane which is a hydrolysis product thereof and a silica sol coating solution, and a silane coupling agent as a curing agent to the coating solution 0.1. An example of the coating solution added is ˜5% by weight. As monoalkyltrimethoxysilane which can be used, monomethyltrimethoxysilane and monoethyltrimethoxysilane are preferable. The silica sol preferably has a small primary particle diameter, and particularly preferably 20 nm or less in order to obtain a transparent film. From the viewpoint of adhesiveness and catalytic activity, the coating solution may contain 1 to 10% by weight of monoalkyltrimethoxysilane or polysiloxane which is a hydrolysis product thereof and 0.1 to 5% by weight of silica sol. preferable. The ratio of the monoalkyltrimethoxysilane or its hydrolysis product to the silica sol is preferably 20/80 to 60/40 by weight, and an acid catalyst such as a mineral acid can be added to accelerate curing.
[0023]
Even when the adhesive layer coating liquid is a polysiloxane-silicon modified resin or colloidal silica-silicon modified resin, or in the case of a monoalkyltrimethoxysilane-silica sol, the silane coupling agent added as a curing agent is the coating liquid. It is desirable to add 0.1 to 5% by weight based on the weight. When the addition amount of the silane coupling agent is less than 0.1% by weight with respect to the coating solution, a blocking phenomenon occurs in which the coating surface sticks to the back surface of the film when the film is dried and wound during film formation, and the photocatalyst layer is coated. Since it becomes difficult, it is not preferable. On the other hand, when the addition amount of the silane coupling agent is 5% by weight or more with respect to the coating solution, it is not preferable because the curing becomes too fast or the solution gels during film formation. Further, by adding 0.1 to 5% by weight of the silane coupling agent to the coating solution, the photocatalytic activity in the case of laminating the photocatalyst-carrying film on the surface of the resin substrate by heat and pressure treatment is reduced. In addition, the photocatalytic activity of the photocatalyst-supported film before lamination can be maintained.
[0024]
As the silane coupling agent, a general formula: RSi (X) Three Ya (R) 2 Si (X) 2 (Wherein R represents an organic functional group and X represents a chlorine atom or an alkoxy group) can be used. In the formula, R represents a methyl group, an ethyl group, a vinyl group, γ-glycol. Sidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group, γ-mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group, etc. In the formula, X represents a C1 to C5 alkoxy group such as a methoxy group, an ethoxy group, and a β-methoxyethoxy group in addition to a chlorine atom.
[0025]
Moreover, the durability can be improved by mixing a light stabilizer and / or an ultraviolet absorber with the adhesive layer for the purpose of suppressing deterioration due to photocatalytic action. The light stabilizer is preferably a hindered amine system, but other light stabilizers can also be used. As the ultraviolet absorber, a triazole-based ultraviolet absorber 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 adhesive layer coating solution. By adding a light stabilizer or ultraviolet absorber to the adhesive layer, it is possible to improve the weather resistance of the polymer resin film carrying the photocatalyst, which is particularly advantageous when used outdoors. A resin structure in which a good photocatalyst carrying film is laminated can also be obtained by adding a surfactant to the adhesive layer coating solution in an amount of 0.00001 wt% to 0.1 wt%.
[0026]
As a method of applying the adhesive layer to the film, the adhesive layer coating solution is coated by gravure printing method, micro gravure printing method, comma coating method, roll coating method, reverse roll coating method, bar coating method, kiss coating method, flow coating method. And a method of drying. The drying temperature varies depending on the coating method, the solvent, the resin type of the film, and the thickness of the film, but is generally preferably 150 ° C. or lower.
[0027]
The thickness of the adhesive layer is preferably 0.5 μm or more. When the thickness is less than 0.5 μm, the effect of firmly bonding the photocatalyst layer to the film is poor, and the photocatalyst layer is likely to peel off after long-term use. In addition, there is no particular problem when the adhesive layer is thick, but since drying during film formation becomes insufficient, film formation unevenness is likely to occur, and film formation costs increase, so in practice. 5 μm or less is preferable.
[0028]
The photocatalyst-supporting polymer resin film laminated to the resin substrate in the present invention has a structure in which a photocatalyst layer is provided on an adhesive layer as shown in FIG. The photocatalyst layer may be formed, for example, by applying and drying a photocatalyst layer coating solution containing 1 to 10 wt% of a metal oxide sol as a solid content and 1 to 10 wt% of a titanium oxide sol as a solid content on an adhesive layer. it can. The metal oxide sol in the photocatalyst layer coating solution not only fixes and firmly adheres the titanium oxide sol to the adhesive layer, but also has an adsorptive property because the gel obtained by drying the metal oxide sol is porous. Also, it has the effect of increasing the photocatalytic activity. The ratio of the metal oxide sol to the titanium oxide sol in the photocatalyst coating solution is preferably 25/75 to 95/5. If the metal oxide sol is 25% or less, the adhesion with the adhesive layer is insufficient, and if it is 95% or more, the photocatalytic activity is insufficient. The specific surface area of the gel obtained by drying the metal oxide sol is 100 m. 2 When it is at least / g, the adhesion becomes stronger and the catalytic activity is also improved. The material is preferably a metal oxide sol of silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, and tungsten. May be used.
[0029]
When the metal oxide sol is mixed with the titanium oxide sol, it is desirable that the metal oxide sol is mixed in a sol state or mixed at a raw material stage before the sol is prepared. Methods for preparing a sol 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 titanium oxide sol is uniformly dispersed in the sol. Any method can be used as long as it can be obtained in the same state. However, the presence of a large amount of impurities in the sol adversely affects the adhesion and catalytic activity of the photocatalyst, so it is preferable to use a sol with few impurities. In particular, when the organic substance is present in the gel obtained by drying the sol in an amount of 5% or more, the photocatalytic activity is lowered. In particular, when a photocatalyst layer containing an oxide sol of zirconium or aluminum is used, it passes a tape peeling test after a 15-minute boiling water resistance test in tap water, or 168 hours in a 5% sodium carbonate aqueous solution. Since what passes the tape peeling test after an immersion test is obtained, it is especially preferable.
[0030]
Moreover, as a photocatalyst layer, the photocatalyst layer application | coating which consists of 1-10 weight% of silica sol, 1-10 weight% of monoalkyltrimethoxysilane or its hydrolysis product, and 1-10 weight% of titanium oxide sol is apply | coated. Those obtained by applying and drying the liquid on the adhesive layer can be particularly preferably used. As the monoalkyltrimethoxysilane, methyltrimethoxysilane and methyltriethoxysilane can be particularly preferably used. The mixing ratio of the silica sol and the monoalkyltrimethoxysilane or the hydrolysis product thereof is preferably 100/0 to 60/40 by weight, and the ratio of the titanium oxide sol to these silicon compound components is titanium oxide / silicon compound. The weight ratio is preferably 5/95 to 75/25. When the ratio of the silicon compound is 95% or more, the photocatalytic activity is lowered, and when it is 25% or less, the adhesion to the adhesive layer is lowered.
[0031]
As a photocatalyst in the photocatalyst layer, TiO 2 , ZnO, SrTiO Three , CdS, GaP, InP, GaAs, BaTiO Three , K 2 NbO Three , Fe 2 O Three , Ta 2 O Five , WO Three , SnO 2 , Bi 2 O Three , NiO, Cu 2 O, SiC, SiO 2 , MoS 2 , InPb, RuO 2 , CeO 2 Examples of these photocatalysts include Pt, Rh, RuO. 2 , Nb, Cu, Sn, NiO, and other metals and metal oxides can be used. The higher the content of the photocatalyst in the photocatalyst layer, the higher the catalytic activity. However, it is preferably 75% by weight or less from the viewpoint of adhesiveness. In order to further improve the antibacterial and antifungal properties, 0.05 to 5% by weight of silver or copper metal or metal compound can be added to the photocatalyst layer with respect to the titanium oxide photocatalyst. If the added amount is 0.05% by weight or less, the effect of improving antibacterial / antifungal properties is poor. If the added amount is 5% by weight or more, the photocatalyst layer may be discolored. May be difficult.
[0032]
In order to form the photocatalyst layer on the adhesive layer, a suspension in which the photocatalyst is dispersed in a metal oxide sol or metal hydroxide sol solution is used, and coating is performed by the same coating method as that for forming the adhesive layer. be able to. 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 adhesion and operability by adding 5% by weight or less of a surfactant or a silane coupling agent to the photocatalyst in the sol suspension. Addition of the agent prevents a decrease in the photocatalytic activity when the photocatalyst-carrying film is laminated on the surface of the resin substrate by heat and pressure treatment, and the photocatalytic activity of the photocatalyst-carrying film before laminating cannot be maintained. The drying temperature during the formation of the photocatalyst layer varies depending on the coating method, the resin material of the film, and the resin material in the adhesive layer, but is generally preferably 150 ° C. or lower.
[0033]
The photocatalyst layer has a higher activity as the thickness increases, but hardly changes when the thickness is 5 μm or more. Even when the thickness is 5 μm or less, high catalytic activity is exhibited, and the catalyst layer becomes inconspicuous because of its translucency. Therefore, high activity cannot be expected. The thickness of the photocatalyst layer is 0.1 μm or more and 5 μm or less, and the photocatalyst particles having a crystal particle diameter of 40 nm or less and a specific surface area of 100 m 2 Use of a metal oxide gel or metal hydroxide gel of / g or more is preferable in terms of aesthetics because it has high photocatalytic activity and does not impair the texture of the resin substrate laminated with the base film.
[0034]
In the present invention, the resin substrate on which the photocatalyst-carrying film is laminated by heat and pressure treatment includes polyvinyl chloride resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, polyethylene resin, polypropylene resin, modified polystyrene resin, impact resistance Examples thereof include those made of a resin selected from a reactive polystyrene resin and an acrylic-butadiene-styrene copolymer resin. The shape of the resin substrate may be any shape as long as it can laminate a photocatalyst-carrying film such as a plate, sheet, woven fabric, nonwoven fabric, resin-impregnated reinforced woven fabric, and tubular. Good.
[0035]
As a method of laminating the photocatalyst-supported polymer resin film on various resin substrates, a method of laminating on a resin substrate such as a resin plate or a coated resin plate while heating and pressurizing with a hot roll, etc., a resin plate, a painted resin plate, a resin coating A method of laminating a photocatalyst-carrying polymer resin film by heat and pressure treatment using the heat of heat treatment during production of a resin substrate such as a resin plate is preferable because it can be industrially efficiently produced. That is, in order to laminate the photocatalyst-carrying film on the resin substrate by heat and pressure treatment, although it depends on the material of the resin of the base film and the material of the resin substrate, it is usually heated for a short time in the temperature range of 60 ° C to 200 ° C. It is preferable to employ a laminating method in which pressure treatment is performed, a laminating method in which residual heat at the time of extrusion molding of a resin substrate to be a resin structure is pressed, a laminating method in which a hot roll is used or heat pressing is performed.
[0036]
In addition, the surface of the resin substrate to be heated and pressurized is subjected to corona discharge treatment or ultraviolet irradiation treatment, or a substrate obtained by applying and drying an acrylic, urethane or epoxy adhesive as a primer layer is used. By doing this, the film adhesion and durability of the heat-laminated product can be further enhanced. By selecting the appropriate temperature, pressure, and time according to the material of the resin substrate, such as a resin plate or painted resin plate, and the material of the film carrying the photocatalyst, it has excellent durability and photocatalytic activity even when used for a long time. Can be obtained. Further, in the present invention, since the heat and pressure treatment is adopted for the laminating process, the photocatalyst layer is extremely firmly fixed to the adhesive layer, and durability, adhesion, and resistance to resistance are compared with those before the heat and pressure treatment. There is an advantage that the peelability is improved.
[0037]
The resin structure obtained by laminating the photocatalyst-supporting film according to the present invention by heat and pressure treatment has an ultraviolet temperature in the UV-A region (400 to 315 nm) of 3 mW / cm at an atmospheric temperature of 25 ° C. and a relative humidity of 70%. 2 5 μg / cm triolein when irradiated 2 ・ It can be decomposed for more than a day. The resin structure laminated with the photocatalyst carrying film according to the present invention has an ultraviolet intensity of 3 mW / cm. 2 Even after 1000 hours of irradiation with light from a black light at a temperature of 40 ° C. and a relative humidity of 90%, the adhesion of the photocatalyst layer examined by the cross-cut tape method of JIS K 5400 maintains an evaluation score of 6 or more. The thing which shows such high durability is also obtained.
[0038]
The photocatalyst carrying film provided with the adhesive layer and the photocatalyst layer according to the present invention has high productivity and can be formed at a speed of several tens of meters or more per minute, and is also processed when laminating the photocatalyst carrying film on various resin substrates. By optimizing the conditions, machining can be performed at a high speed of several meters per minute or more. Therefore, film formation at a much faster rate is possible compared to the method of applying and drying a photocatalyst layer on a resin substrate simply by the usual dipping method, spraying method or roll coating method, etc., production efficiency, film thickness uniformity, etc. It has a great advantage in improving the film forming quality. In addition, the resin structure obtained by laminating the photocatalyst film obtained by the present invention can be formed into a resin product with a complicated shape by pressing the resin substrate after the photocatalyst film is laminated or by cutting and cutting. Therefore, its application range is extremely wide.
[0039]
The resin structure obtained by laminating the photocatalyst-supported polymer resin film of the present invention is widely used as a general building material or outdoor installation structure material, such as outdoor advertising towers, road sound insulation walls, roadside telephone boxes, road signs, etc. Can be used as a surface building material for household equipment such as bathroom vanities, bathrooms, toilets, bathrooms, toilets, kitchens, toilets, and various sinks. .
[0040]
In addition, the resin structure laminated with the photocatalyst carrying film of the present invention is a signboard made of a polyvinyl chloride marking film used for an outdoor signboard, a resin window of a transport body such as a train / bus, an outdoor use Tent fabrics, field sheets, tent warehouses, awnings for shops, tent roofs for various arcades, tent roofs and side tent covers for exhibition pavilions, gas station roofs and side covers, waterproof protection It can be used for seats, snow protection sheets, air domes, pool covers, etc., and a resin structure laminated with a photocatalyst-supporting film is installed on the surface of wood or mortar. It can also be used for equipment. Thus, the resin structure laminated with the photocatalyst-supporting film of the present invention can be used in many places that require deodorizing, antifouling, antibacterial, and antifungal actions, and has excellent deodorizing properties. Antifouling, antibacterial and antifungal properties can maintain the surface in a beautiful state for a long time.
[0041]
And, when the resin structure laminated with the film carrying the photocatalyst of the present invention is used for an outdoor display board, an outdoor signboard, an outdoor tent fabric, a telephone box, etc., it is exhausted by the excellent photocatalytic decomposition activity of this film. Since soot and oily smoke contained in gas etc. is decomposed, dust, dust, sand, clay, etc. adhering to the surface can be easily removed by their adhesive action, and it will be removed by wind and rain, etc. It becomes. In addition, when using an acrylic plate water tank laminated with the photocatalyst-supported polymer resin film according to the present invention, organic substances and bacteria attached to the inner surface of the water tank are decomposed by ultraviolet rays emitted from the fluorescent lamp, and the surface Dirt due to water stains is reduced and dirt is less noticeable. The resin plate laminated with the photocatalyst-supporting film according to the present invention can be suitably used as a material for a system kitchen, a bathroom vanity, and a unit bath used in kitchens, toilets, and bathrooms. However, the antifouling and antibacterial functions can be exhibited, which is preferable. The photocatalyst-supported polymer resin film according to the present invention is laminated on the surface of a resin casing of a household electrical product such as a refrigerator, washing machine, personal computer, radio / TV, and various plastic cases such as a dish basket and a seasoning case. When processed products are used, the amount of ultraviolet rays irradiated in the indoor environment is small, but oil mist floating in the room and sebum components due to contact with fingers are gradually decomposed by the photocatalytic decomposition action, resulting in adhesion to the surface. An excellent effect of reducing hand dirt and darkening is achieved.
[0042]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1 Production of a photocatalyst-carrying film
The adhesive layer coating solution and the photocatalyst layer coating solution were applied to an acrylic resin film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. using a microgravure printing machine manufactured by Yasui Seiki Co., Ltd. A 20% ethanol solution of methyl silicate MS51 manufactured by Colcoat Co., Ltd. as a polysiloxane was added to an ethanol-ethyl acetate (50/50 weight ratio) solution containing 8% by weight of an acrylic silicon resin having a silicon content of 3 mol% as a solid content. 35% by weight as a solid content with respect to the resin and 1% by weight of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent were added to the coating solution to obtain a coating solution for the adhesive layer. An adhesive layer was formed at a temperature of 60 ° C. at a speed of 20 m / min, and then allowed to cool at room temperature. In the presence of a surfactant, a solution of water-ethanol 50/50 in a weight ratio of titanium oxide-containing titania sol having a titanium oxide content of 10% by weight was dispersed in a water-ethanol 50/50 weight ratio. A photocatalyst layer coating solution was prepared by adding an equal amount of a dispersion of nitric acid acidic silica sol so that the silicon oxide content was 10% by weight. Using this solution, a film was formed under the same conditions as those for the adhesive layer, and the photocatalyst layer was supported to obtain a photocatalyst-supporting film (A). In the same manner, the adhesive layer and the photocatalyst layer were formed on other film materials while changing the film formation temperature and drying conditions. An acrylic film “Sanduren 008NCT” 50 μm thick (B) manufactured by Kaneka Chemical Co., Ltd., Sumitomo A photocatalyst-supporting film was prepared using a Bakelite hard polyvinyl chloride film 50 μm thick (C).
[0043]
Example 2 Polycarbonate resin laminated with a photocatalyst carrying film
The photocatalyst carrying film (A) obtained in Example 1 was subjected to a pressure of 50 kg / cm at room temperature using a hot plate press manufactured by Toyo Seiki Seisakusho. 2 Was repeated 5 times for 10 seconds, and air was vented, then the temperature was raised to 120 ° C. and 50 kg / cm 2 2 minutes, 100 kg / cm at the same temperature 2 2 minutes, 150kg / cm 2 After heating and pressurizing at a temperature pressure of 1 minute, cool down to 50 ° C. or less with the pressure applied, and paste it on a 10 mm × 10 cm square of 3 mm thickness of polycarbonate resin plate Polyace Ace EC100 manufactured by Plastic Co., Ltd. A polycarbonate plate laminated with a photocatalyst carrying film was obtained. This sample had a very high transparency with a haze ratio of 0.7% for visible light and a total light transmittance of 90.2%. (Sample 1)
[0044]
Example 3 Vinyl chloride resin laminated with a photocatalyst carrying film
The photocatalyst-supporting film (C) obtained in Example 1 was cut into a 10 × 10 cm square of a 3 mm thickness of a transparent hard polyvinyl chloride resin plate manufactured by Sekisui Chemical Co., Ltd. under the same method and conditions as in Example 2. A hard vinyl chloride plate laminated with a photocatalytic film was used. (Sample 2)
[0045]
Example 4 Acrylic resin laminated with a photocatalyst carrying film
The photocatalyst-supporting film (A) obtained in Example 1 was subjected to acrylic plate Delaglass A No. 1 manufactured by Asahi Kasei Corporation using the same apparatus as in Example 2. Affixed to 999 3 mm thickness cut to 10 × 10 cm square, 160 kg / cm for 10 minutes at 140 ° C. using a hot press device 2 An acrylic resin plate laminated with a photocatalyst film was hot-pressed at a pressure of 1 mm. (Sample 3)
[0046]
Example 5 ABS resin laminated with photocatalyst carrying film
Using a heat press device, a 3 mm thick plate of ABS resin Psycolac EX215 manufactured by Ube Saikon Co., Ltd. was cut to the back of the photocatalyst carrying film (B) obtained in Example 1 and cut into a 10 × 10 cm square. 160 kg / cm for 10 minutes at 120 ° C 2 An ABS resin plate laminated with a photocatalyst film was hot-pressed at a pressure of 1 mm. (Sample 4)
[0047]
Example 6 HIPS resin laminated with photocatalyst carrying film
A hot press apparatus in which a 3 mm thick plate of HIPS resin Idemitsu styrene HT-54 manufactured by Idemitsu Petrochemical Co., Ltd. was cut into a 10 × 10 cm square on the back surface of the photocatalyst-supporting film (B) obtained in Example 1. 160kg / cm for 10 minutes at 100 ° C 2 An ABS resin plate laminated with a photocatalyst film was hot-pressed at a pressure of 1 mm. (Sample 5)
[0048]
Example 7 Vinyl chloride resin laminated with a copper-added photocatalyst carrying film
In Example 1, the same method and apparatus as in Example 1 were used except that 0.01 wt% copper nitrate hydrate was added to and dissolved in the coating solution of the photocatalyst layer. A photocatalyst-supporting film having a base film of a 50 μm thick acrylic film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. was prepared. This photocatalyst-supported acrylic resin film was laminated to a 10 mm × 10 cm square cut of a transparent rigid polyvinyl chloride resin plate manufactured by Sekisui Chemical Co., Ltd. under the same method and conditions as in Example 3. Hard vinyl chloride plate was used. (Sample 6)
[0049]
Example 8 A vanity using an ABS resin plate laminated with a photocatalytic film
Using the same photocatalyst carrying film and ABS resin as used in Example 5, using a hot roll laminator, the nib pressure is 3 kg / cm, the sheet surface temperature is 130 ° C. with the lamination roll, and the sheet feeding speed is 10 m / min. Using the laminated ABS resin plate, a double door with a lower part of the bathroom vanity was prototyped. For the evaluation, a sample cut out 5 × 5 cm from this plate was used. (Sample 7)
[0050]
Example 9 Outdoor signboard using acrylic plate laminated with photocatalyst film
The acrylic resin plate is affixed to Sumitomo 3M's colored vinyl chloride marking film for outdoor display plates, cut into a letter shape for signboard, and the photocatalyst-supporting film (C) prototyped in Example 1 is applied thereon. In the same manner as in Example 8, an outdoor signboard using an acrylic resin plate laminated with a nib pressure of 3 kg / cm, a sheet surface temperature of 120 ° C. with a lamination roll, and a sheet feeding speed of 10 m / min was produced. For the evaluation, a sample cut out 5 × 5 cm from this plate was used. (Sample 8)
[0051]
Example 10 A unit bath comprising a polyester plate laminated with a photocatalytic film
The photocatalyst-supporting film (C) produced in Example 1 was laminated on the polyester resin plate in the same manner as in Example 8 at a nib pressure of 3 kg / cm, a sheet surface temperature of 120 ° C. with a lamination roll, and a sheet feed speed of 10 m / min. We made a prototype of a resin plate for unit baths using the polyester resin plate. For the evaluation, a sample cut out 5 × 5 cm from this plate was used. (Sample 9)
[0052]
Example 11 Water tank made of an acrylic plate laminated with a photocatalytic film
The photocatalyst film (C) produced in Example 1 was laminated on an acrylic resin plate using a hot roll laminator at a nib pressure of 3 kg / cm, a sheet surface temperature of 120 ° C. with a lamination roll, and a sheet feed speed of 10 m / min. An acrylic resin plate was manufactured. A water tank was prototyped using an acrylic resin plate laminated with this photocatalyst carrying film. For the evaluation, a sample cut out 5 × 5 cm from this plate was used. (Sample 10)
[0053]
Example 12
Storage door for system chitin made of HIPS board laminated with photocatalyst film
Laminate the photocatalyst film (C) produced in Example 1 on a HIPS resin plate using a hot roll laminator at a nib pressure of 3 kg / cm, a sheet surface temperature of 120 ° C. with a lamination roll, and a sheet feed speed of 10 m / min. An HIPS resin plate was manufactured. A storage door for a system kitchen was prototyped using a HIPS resin plate obtained by laminating this photocatalyst carrying film. A sample of 30cm x 30cm was pasted on the door of an existing system kitchen, and after 6 months, the stain resistance of the part where the HIPS plate laminated with the photocatalyst film was pasted was measured by the discoloration degree measured with the spectrocolorimeter. In the evaluation, the change value of ΔE was 4.5, whereas the portion of the wallpaper where the photocatalytic film was not laminated was 16.5 with a change value of ΔE, and the contamination was more advanced. .
[0054]
Example 13 Wallpaper made of a PVC sheet laminated with a photocatalytic film
Using a hot roll laminating apparatus in which the photocatalyst film (C) produced in Example 1 is attached to the PVC sheet for wallpaper to which the foaming agent has been added, the embossing roll is attached, the nib pressure is 3 kg / cm, the sheet surface temperature at the embossing roll A foamed PVC wallpaper laminated at 140 ° C. and a sheet feed rate of 10 m / min was produced. In the evaluation where the sample of 1m × 1m was pasted on the wall of the room, the stain resistance of the part where the wallpaper with the photocatalyst film laminated was pasted after 6 months, and the degree of discoloration measured with a spectrocolorimeter, While the change value of ΔE was 6.5, the portion of the wallpaper on which the photocatalytic film was not laminated was 26.5 with a change value of ΔE, and the contamination was more advanced.
[0055]
Example 14 Food Tray Laminated with Photocatalytic Film
After applying a urethane adhesive to the surface of a 0.5 mm thick polypropylene sheet subjected to corona discharge treatment, the photocatalytic film (A) produced in Example 1 was subjected to a nib pressure of 3 kg using a hot roll laminator. A polypropylene sheet laminated with a photocatalytic film at a sheet surface temperature of 140 ° C. with a lamination roll at 140 ° C. and a sheet feed speed of 10 m / min was produced. The sheet was further heated and pressed to produce a tray for food sales. 200g of beef is put in this tray (length 25cm x width 10cm x depth 3cm), covered with polyethylene wrap film, placed in a constant temperature bath at a temperature of 20 ° C, and irradiated with four 10W fluorescent lamps at a distance of 15cm. The film was stored together with the same beef in a polypropylene tray with no laminated film. The tray without the photocatalytic film laminated already turned black after 4 hours and had a little decaying odor, whereas the one with the photocatalytic film laminated had almost no decaying odor even after 4 hours. The degree was also small.
[0056]
Example 15 Packaging film laminated with photocatalytic film
After the surface of the polyethylene film was subjected to corona discharge treatment as in Example 14 and an acrylic adhesive was applied, the photocatalytic film (A) produced in Example 1 was subjected to a nib pressure of 3 kg / cm using a hot roll laminator. A polyethylene sheet laminated with a photocatalytic film was produced at a sheet surface temperature of 130 ° C. with a lamination roll and a sheet feed rate of 10 m / min. Using this polyethylene sheet, one bundle of spinach was squeezed and compared with spinach struck with a polyethylene film with no photocatalyst film laminated under irradiation with three 15 W fluorescent lamps. After 4 hours, spinach wrapped with a polyethylene film laminated with a photocatalyst film was hardly discolored, whereas spinach wrapped with a polyethylene film not laminated with a photocatalyst film turned dark green and wilted. It was. This is probably because ethylene gas emitted from spinach was decomposed.
[0057]
Comparative Example 1
An acrylic film “Acryprene HBS-006” made by Mitsubishi Rayon Co., Ltd., having a thickness of 50 μm, is formed in the same manner and under the same conditions as in Example 2. A polycarbonate plate laminated with an acrylic film was attached to what was cut out.
[0058]
Comparative Example 2
A 50 μm-thick acrylic film “Sandulen 008NCP” manufactured by Kaneka Chemical Co., Ltd., Delaglass A No. An acrylic resin plate laminated with an acrylic film was heat-pressed under the same conditions and method as in Example 4 using a heat press apparatus, pasted on a 999-mm 3 mm-thick cut out 5 × 5 cm square.
[0059]
Comparative Example 3
A 50 μm thick hard PVC film made by Sumitomo Bakelite was pasted onto a 5 mm × 5 cm square of a 3 mm thick transparent polyvinyl chloride resin plate made by Sekisui Chemical Co., Ltd. under the same method and conditions as in Example 3. A rigid vinyl chloride plate laminated with a vinyl chloride film was used.
[0060]
(Evaluation of photocatalytic activity)
Using the samples 1 to 10 and the sample of the comparative example, the following evaluation was performed, and the results shown in Table 1 were obtained.
[0061]
1) Pollution resistance (antifouling properties)
A sample cut into a 5cm x 5cm square is pasted together with a blank sample of the same size and size that does not carry a photocatalyst on a fence facing a general road (traffic volume of 500 to 1000 units / day), and the surface of the sample after 3 months The degree of contamination was evaluated by a spectral color difference meter based on a comparative control sample stored in a cool and dark place.
2) Triolein degradation characteristics (oil degradation activity)
Using Kimwipe on a sample cut into a 5 cm square, 0.1 mg / cm of triolein (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) 2 After coating, the sample is placed in a constant temperature and humidity chamber with a temperature of 25 ° C. and a relative humidity of 70%, and irradiated with a commercially available 15 W black light fluorescent lamp, and the UV light in the UV-A region is 3 mW / cm on the sample surface. 2 The distance between the light source and the sample surface was adjusted so that The amount of triolein decreased with respect to the light irradiation time was quantified with a precision balance to determine the triolein decomposition activity.
3) Antibacterial evaluation
A sample cut into 5 cm square was disinfected with 80% ethanol, dried at 150 ° C., sterilized, pre-cultured and diluted to adjust the bacterial concentration to 105 cells / ml in advance. 2 ml was dropped on the sample surface and set in the incubator. Four samples were set for each of two types of light irradiation conditions: a white fluorescent lamp (15 W x 2 pieces, a distance of 10 cm from the light source) irradiated with light, and a case where light irradiation was not performed at all. Remove the sample after a predetermined time (1, 2, 3, 4 hours), wipe off the bacterial solution on the sample with sterile gauze soaked in sterile physiological saline, and put the wiped sterile gauze into 10 ml of sterile physiological saline Stir well. This supernatant bacterial solution was planted in a 95 mmφ petri dish agar medium sterilized by autoclaving, and the number of E. coli colonies was counted after incubation at 36 ° C. for 24 hours. A reference bacterial count sample with exactly the same operation up to the incubator was prepared by the same method, and the supernatant of sterilized physiological saline was planted on a Petri dish agar medium, and the number of colonies of E. coli after 24 hours of culture was counted. . Based on the numerical value, the survival rate of E. coli after a predetermined time of each sample was calculated. Evaluation was made based on the residual rate of Escherichia coli in the sample irradiated with fluorescent light after 4 hours, and the evaluation criteria were as follows.
4) Antifungal property
The degree of the occurrence of green mold on the surface of the sample used for the evaluation of the stain resistance was evaluated by comparing with the sample stored in a cool and dark place according to the following criteria.
Evaluation of the degree of mold on the sample surface
Almost no occurrence A
Some occurrence is observed B
Evidently observed C
[0065]
(Evaluation of adhesion)
Adhesion was evaluated by a cross-cut tape method test specified in JIS K 5400. The interval between the cuts was 2 mm, and the number of squares was 25. The evaluation score was based on the criteria described in JIS K 5400.
[0066]
(Durability evaluation)
UV light intensity of 3mW / cm with black light on the supported sample 2 Was irradiated for 1000 hours in a constant temperature and humidity chamber at a temperature of 40 ° C. and a humidity of 90%, and then adhesion was measured by a cross-cut tape method specified in JIS K 5400 to evaluate durability. The evaluation score is the same as the adhesion evaluation.
[0067]
[Table 1]
Comparative Example 4
In accordance with Example 48 described in WO97-134, an acrylic silicon resin emulsion aqueous solution having a silicon content of 20% was applied to the SiO2 in the dry adhesive layer as a coating solution for the adhesive layer. 2 Cataloid SI-350 manufactured by Catalytic Chemicals Co., Ltd. was added so that the content was 10%, and the total dry solid content was adjusted to 20%. As photocatalyst layer coating liquid, titanium oxide P-25 for photocatalyst manufactured by Nippon Aerosil Co., Ltd. is 30% as solid content, silica sol cataloid SI-30 manufactured by Catalytic Chemicals Co., Ltd. is 20% as solid content, alumina sol manufactured by Nissan Chemical Co., Ltd. -200 as a dry solid content, 10% by weight of an acrylic silicone resin emulsion aqueous solution having a silicon content of 20% by weight as a non-volatile residue, and tri (β-methoxyethoxy) vinylsilane manufactured by Nihon Unicar Co., Ltd. as a silane coupling agent. A non-volatile residue was prepared so that a total of 5% became a dry residue of 10%. Using these coating liquids, an acrylic film “Acryprene HBS-006” manufactured by Mitsubishi Rayon Co., Ltd. was applied to a 50 μm thick film using a micro gravure printer manufactured by Yasui Seiki Co., Ltd. The film could not be formed due to insufficient curing. Therefore, the same adhesive layer coating solution and photocatalyst layer coating solution were coated on the above-mentioned acrylic film manufactured by Mitsubishi Rayon Co., Ltd. and dried at a drying temperature of 80 ° C. The time required 1 hour. This photocatalyst-supporting acrylic film was attached to a 3 mm thick 10 × 10 cm square polycarbonate resin plate manufactured by Plastics Co., Ltd., and was heat laminated by the same method and conditions as in Example 2. Table 1 shows the stain resistance, oil decomposition activity, antibacterial activity, antifungal property, adhesion and durability of this heat-laminated polycarbonate resin plate. This sample was inferior in photocatalytic activity and durability. Thus, application of this photocatalyst-supporting film prepared without containing a silane coupling agent in the adhesive layer coating solution to a transparent polycarbonate was inappropriate.
[0069]
【The invention's effect】
The resin structure obtained by laminating the photocatalyst-supporting film of the present invention has high photocatalytic activity, excellent durability, antifouling, antibacterial, antifungal, etc., for various building materials, outdoor signs, outdoor displays It can be used for boards, roadside equipment, indoor building materials, indoor appliances, kitchen appliances, toilet sinks, etc., and has an excellent price / performance ratio. In addition, the photocatalyst-supporting film provided with the adhesive layer and the photocatalyst layer according to the present invention is highly productive and can be formed at a speed of several tens of meters per minute. In addition, when the photocatalyst-supported film is laminated on various resin substrates, However, it is possible to process at a high speed of several meters per minute or more by optimizing the processing conditions.
[Brief description of the drawings]
FIG. 1 is a schematic view of a cross section of a resin structure laminated with a photocatalyst carrying film of the present invention.
Claims (14)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32224897A JP4046250B2 (en) | 1997-11-07 | 1997-11-07 | A resin structure obtained by laminating a photocatalyst-carrying film |
| US09/530,196 US7208443B1 (en) | 1997-11-07 | 1998-11-05 | Structure having photocatalyst-supporting film laminated thereto |
| EP98951695A EP1029659B1 (en) | 1997-11-07 | 1998-11-05 | Metallic plate or resin structure having photocatalyst-supporting film laminated thereto |
| AT98951695T ATE424296T1 (en) | 1997-11-07 | 1998-11-05 | METAL PLATE OR PLASTIC STRUCTURE WITH PHOTOCATALYST CARRYING FILM LAMINATED THEREON |
| PCT/JP1998/004981 WO1999024253A1 (en) | 1997-11-07 | 1998-11-05 | Metallic plate or resin structure having photocatalyst-supporting film laminated thereto |
| DE69840635T DE69840635D1 (en) | 1997-11-07 | 1998-11-05 | METALLIC PLATE OR PLASTIC STRUCTURE WITH A LAMINATED PHOTOCYCATOR-CARRYING FILM THEREOF |
| US11/715,943 US7419539B2 (en) | 1997-11-07 | 2007-03-09 | Metallic plate or resin structure having photocatalyst-supporting film laminated thereto |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32224897A JP4046250B2 (en) | 1997-11-07 | 1997-11-07 | A resin structure obtained by laminating a photocatalyst-carrying film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11138686A JPH11138686A (en) | 1999-05-25 |
| JP4046250B2 true JP4046250B2 (en) | 2008-02-13 |
Family
ID=18141562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32224897A Expired - Lifetime JP4046250B2 (en) | 1997-11-07 | 1997-11-07 | A resin structure obtained by laminating a photocatalyst-carrying film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4046250B2 (en) |
Cited By (1)
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|---|---|---|---|---|
| KR20180055332A (en) * | 2016-11-17 | 2018-05-25 | (주) 이루팩 | Cosmetic impregnated foam manufacyuring method for manufacturing method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001323189A (en) * | 2000-05-12 | 2001-11-20 | Showa Highpolymer Co Ltd | Composition for adhesion protective layer of titanium oxide photocatalytic coating film |
| JP4863180B2 (en) * | 2000-12-27 | 2012-01-25 | 大塚化学株式会社 | Water-based paint and wallpaper for wallpaper |
| JP2002201567A (en) * | 2000-12-28 | 2002-07-19 | Shozo Miya | Antifouling sheet and its suture |
| JP2002225191A (en) * | 2001-02-02 | 2002-08-14 | Daiken Trade & Ind Co Ltd | Decorative plate and manufacturing method thereof |
| JP4806785B2 (en) * | 2001-03-01 | 2011-11-02 | 日東グラステックス株式会社 | Photocatalytic functional sheet material |
| JP4156821B2 (en) * | 2001-08-23 | 2008-09-24 | 三菱樹脂株式会社 | Photocatalyst-coated acrylic film and photocatalyst-coated laminate |
| JP4436038B2 (en) * | 2002-12-20 | 2010-03-24 | 株式会社シーボン | Method for suppressing sebum adhesion of cosmetic tool and cosmetic tool |
| JP2010143193A (en) * | 2008-12-22 | 2010-07-01 | Mitsubishi Plastics Inc | Hydrophilic polycarbonate plate, method for manufacturing the same, roof material, and wall material for road |
-
1997
- 1997-11-07 JP JP32224897A patent/JP4046250B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180055332A (en) * | 2016-11-17 | 2018-05-25 | (주) 이루팩 | Cosmetic impregnated foam manufacyuring method for manufacturing method using the same |
| KR101898672B1 (en) * | 2016-11-17 | 2018-09-14 | (주) 이루팩 | Cosmetic impregnated foam manufacyuring method for manufacturing method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11138686A (en) | 1999-05-25 |
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