JP4446560B2 - Colored photocatalyst carrying structure and coating liquid for forming the structure - Google Patents
Colored photocatalyst carrying structure and coating liquid for forming the structure Download PDFInfo
- Publication number
- JP4446560B2 JP4446560B2 JP2000165683A JP2000165683A JP4446560B2 JP 4446560 B2 JP4446560 B2 JP 4446560B2 JP 2000165683 A JP2000165683 A JP 2000165683A JP 2000165683 A JP2000165683 A JP 2000165683A JP 4446560 B2 JP4446560 B2 JP 4446560B2
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- Japan
- Prior art keywords
- photocatalyst
- weight
- resin
- coating solution
- silicon
- 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.)
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- 230000001699 photocatalysis Effects 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
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- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- LIZIAPBBPRPPLV-UHFFFAOYSA-N niobium silicon Chemical compound [Si].[Nb] LIZIAPBBPRPPLV-UHFFFAOYSA-N 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
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- SHBDDIJUSNNBLQ-UHFFFAOYSA-M sodium;3-[[4-[(2-chlorophenyl)-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)Cl)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SHBDDIJUSNNBLQ-UHFFFAOYSA-M 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- LLWJPGAKXJBKKA-UHFFFAOYSA-N victoria blue B Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C(C=C1)C2=CC=CC=C2C1=[NH+]C1=CC=CC=C1 LLWJPGAKXJBKKA-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、着色した光触媒担持構造体及び該構造体を形成する塗布液に関する。
【０００２】
【従来の技術】
最近、光の作用により表面の汚れ等を分解する光触媒機能を有する基材が幾つか提案されている。しかし、基材の外観等を損なうことなく光触媒機能を持たせるためには、光触媒機能を有する塗膜は透明性が高く、更に膜厚が薄いので、塗布済み部と未塗布部分の区別が付かず、塗り残し部分の発生、及び重ね塗り部分が多く薬剤使用量の増加等の問題が生じていた。
【０００３】
これに対して、光触媒層に着色し光触媒機能を用いて色素を分解し、消色させるという方法が提案されているが、日当たりの良い場所と、日陰で光量が異なるので光触媒効果に差が生じ、消色程度に差ができ、むらに見える等の問題があった。
一般的に、無色透明であり、特に薄い塗膜を塗り残しや塗りむらなく基材表面に２重に塗布する方法としては以下に示す方法が知られている。
【０００４】
たとえば、特開２０００−５１７８２号公報には、塗布液として蛍光色素を含有するものを使用し、得られた塗膜から発せられる蛍光により前記基材の塗布済み部と未塗布部とを識別し、該識別に基づいて塗布作業を進めることを特徴とする塗布方法が記載されている。
【０００５】
また、特開平５−２５８９９号公報には、透明塗布液に退色性色素材料を添加して着色し、着色された状態で透明塗布液を塗布し、光化学反応、昇華、又は雨水による流出を利用して退色させる方法が記載されている。
【０００６】
【発明が解決しようとする課題】
しかし、特開２０００−５１７８２号に記載されている方法では、塗膜中に蛍光色素が残留するため、光のあたる角度によっては基材の外観を損なう場合があるという問題があった。また、特開平５−２５８９９号公報に記載の方法は、最外層に適用する場合にはある程度効果を有するものの、光や雨水は塗装する場所によっては十分に供給されない場合があり、退色するまでに時間がかかるという問題があった。
【０００７】
本発明は、特に、外の作業現場において基材表面に塗り残し、重ね塗り等の塗りむらがなく、使用場面が限定されず、しかも、基材表面の色や模様等の特徴を損なうことない光触媒担持構造体及び、該塗布方法を用いた光触媒担持構造体形成用塗布液を提供することを目的とする。
【０００８】
【課題を解決する手段】
本発明者等は、上記課題を解決すべく多くの染料を鋭意検討した結果、トリフェニルメタン系染料を用いて着色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。
【０００９】
即ち、本発明は、（１）基材表面に接着層、光触媒層を順次積層してなる光触媒担持構造体において、接着層及び／又は光触媒層にトリフェニルメタン系染料を含むことを特徴とする光触媒担持構造体、（２）トリフェニルメタン系染料が、クリスタルバイオレットであることを特徴とする（１）に記載の光触媒担持構造体、（３）接着層が、シリコン含有量２〜６０重量％のシリコン変性樹脂、コロイダルシリカを５〜４０重量％含有する樹脂、又は式［１］
ＳｉＣｌn1（ＯＨ）n2Ｒ1n3 （ＯＲ2）n4 ・・・式［１］
〔式中、Ｒ1は（アミノ基、カルボキシル基、または塩素原子で置換されてもよい）炭素数１〜８のアルキル基、Ｒ2は、炭素数１〜８のアルキル基もしくはアルコキシ基で置換された炭素数１〜８のアルキル基を表し、ｎ1は０から２の整数を表し、ｎ4は２から４の整数であり、かつｎ1＋ｎ2＋ｎ3＋ｎ4＝４を示す。〕で表される化合物の重縮合反応生成物であるポリシロキサンを３〜６０重量％含有する樹脂であり、光触媒層が、金属酸化物ゲルもしくは金属水酸化物ゲルを２５〜９５％含有する光触媒粒子複合体であることを特徴とする（１）又は（２）に記載の光触媒担持構造体、（４）光触媒担持構造体の表面が、光励起に応じて親水性を呈することを特徴とする（１）〜（３）のいずれかに記載の光触媒担持構造体、に関する。
【００１０】
また、（５）基体上に接着層、光触媒層を順次積層してなる光触媒担持構造体形成用塗布液が接着層形成用塗布液及び光触媒層形成用塗布液からなり、接着層形成用塗布液及び／又は光触媒層形成塗布液にトリフェニルメタン系染料を含有することを特徴とする光触媒担持構造体形成用塗布液、（６）接着層塗布液が、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、または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％含む溶液からなる塗布液であり、光触媒層形成用塗布液が、シリコン化合物を０．００１〜５重量％、金属の酸化物および／または水酸化物のゾルを固形分として０．１〜３０重量％、および光触媒の粉末および／またはゾルを固形分として０．１〜３０重量％を含む液からなる塗布液であることを特徴とする（５）に記載の光触媒担持構造体形成用塗布液、に関する。
【００１１】
【発明の実施の形態】
本発明の光触媒担持構造体は、基体上に順次積層してなる接着層、及び光触媒層を有することを特徴とする。光触媒層の構造は、光触媒が、その光触媒機能を有しつつ基体上に好ましくは強固に担持されていれば特に制限されない。具体的には、光触媒作用に対して難分解性の化合物を結着剤として光触媒が担持された構造を例示することができる。前記難分解性の化合物としては、例えば、水ガラス、コロイダルシリカ、ポリオルガノシロキサンなどのケイ素化合物、リン酸亜鉛、リン酸アルミニウムなどのリン酸塩、重リン酸塩、セメント、石灰、セッコウ、ほうろう用フリット、グラスライニング用うわぐすり、プラスターなどの無機系結着剤、フッ素系ポリマー、シリコン系ポリマーなどの有機系結着剤などを例示することができ、これらの結着剤を単一または２種以上を組み合わせて用いることができる。特に、接着強度の観点から無機系結着剤、フッ素系ポリマー、シリコン系ポリマーが好ましい。セメントとしては、例えば早強セメント、普通セメント、中庸熱セメント、耐硫酸塩セメント、ホワイト（白色）セメント、油井セメント、地熱井セメントなどのポルトランドセメント、フライアッシュセメント、高硫酸塩セメント、シリカセメント、高炉セメントなどの混合セメント、アルミナセメントなどを用いることができる。プラスターとしては、例えばセッコウプラスター、石灰プラスター、ドロマイトプラスターなどを用いることができる。フッ素系ポリマーとしては、例えばポリフッ化ビニル、ポリフッ化ビニリデン、ポリ塩化三フッ化エチレン、ポリ四フッ化エチレン、ポリ四フッ化エチレン−六フッ化プロピレンコポリマー、エチレン−ポリ四フッ化エチレンコポリマー、エチレン−塩化三フッ化エチレンコポリマー、四フッ化エチレン−パーフルオロアルキルビニルエーテルコポリマーなどの結晶性フッ素樹脂、パーフルオロシクロポリマー、ビニルエーテル−フルオロオレフィンコポリマー、ビニルエステル−フルオロオレフィンコポリマーなどの非晶質フッ素樹脂、各種のフッ素系ゴムなどを用いることができる。特に、ビニルエーテル−フルオロオレフィンコポリマー、ビニルエステル−フルオロオレフィンコポリマーを主成分としたフッ素系ポリマーが分解・劣化が少なく、また、取扱が容易であるため好ましい。シリコン系ポリマーとしては、直鎖シリコン樹脂、アクリル変性シリコン樹脂、各種のシリコン系ゴムなどを用いることができる。特に、金属酸化物ゲルもしくは金属水酸化物ゲルを２５〜９５％含有する光触媒粒子複合体である光触媒層が好ましい。また、金属酸化物ゲルもしくは金属水酸化物ゲルの比表面積が好ましくは１５０℃で乾燥後５０ｍ2／ｇ以上、更に好ましくは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。
【００１２】
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もしくは水酸化物ゲルを好ましく例示することができる。
また、金属成分として、珪素、アルミニウム、チタニウム、ジルコニウム、ニオビウムの中から選ばれた２種以上の金属を含有する酸化物もしくは水酸化物ゲルを使用することにより、沸騰水に浸漬した後の光触媒層の付着性を高めることが可能である。耐沸騰水性に優れた金属成分の組み合わせの例としては、珪素−アルミニウム、珪素−チタニウム、珪素−ジルコニウム、珪素−ニオビウム、アルミニウム−チタニウム、アルミニウム−ジルコニウム、アルミニウム−ニオビウム、アルミニウム−タンタラム、チタニウム−ジルコニウム、チタニウム−ニオビウム、チタニウム−タンタラム、珪素−アルミニウム−ジルコニウム、珪素−アルミニウム−チタニウムなどが好ましく、更に好ましくは、珪素−アルミニウム、珪素−チタニウム、珪素−ジルコニウム、珪素−チタニウム−アルミニウム、珪素−アルミニウム−ジルコニウムなどの酸化物ゲルもしくは水酸化物ゲル等を挙げることができる。
【００１３】
これらの酸化物ゲルもしくは水酸化物ゲルの比表面積が５０ｍ2／ｇ以上あると、接着性が高く、触媒活性も向上し、沸騰水中に浸漬した後でも優れた接着性を有している。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、もしくは、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。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。
【００１４】
また、光触媒層中にシリコン変性樹脂あるいはシランカップリング剤を１０〜５０重量％加えることによっても高い触媒活性を維持したまま、沸騰水中へ１５分間浸漬した後でＪＩＳ Ｋ５４００に規定された碁盤目テープ法による付着性試験で評価点数が６点以上の優れた付着性のものを得ることができる。
【００１５】
光触媒層中に添加するシリコン変性樹脂あるいはシランカップリング剤は、沸騰水中での光触媒層の付着性を高める効果を有している。シリコン変性樹脂としては通常市販されているシリコン−アクリル系やシリコン−エポキシ系のものが使用可能であり、溶剤に溶解したものでもエマルジョンとなって水中に分散しているものでもいずれも使用可能である。また、シランカップリング剤としては、一般式：ＲＳｉ(Ｙ)3や(Ｒ)2Ｓｉ(Ｙ)2（但し、Ｒは有機性官能基を、Ｙは塩素原子またはアルコキシ基を示す。）等で示されるものが使用可能である。前記一般式において、Ｒとしては、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があり、Ｙとしては塩素原子以外にメトキシ基、エトキシ基、β−メトキシエトキシ基、β−エトキシエトキシ基等Ｃ1〜Ｃ5のアルコキシ基のものがいずれも使用可能である。
【００１６】
シリコン変性樹脂あるいはシランカップリング剤の添加量は、固形分として光触媒層中に１０〜５０重量％加えることが望ましい。光触媒層中へのシリコン変性樹脂あるいはシランカップリング剤の添加方法としては、光触媒粉末や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ゲルを形成するための金属の酸化物もしくは水酸化物のゾル液中へ添加する方法など種々の方法が可能である。なお、エマルジョンタイプのシリコン変性樹脂を前記のゾル液中へ添加することは、光触媒活性を殆ど低下させることなく沸騰水中での光触媒層の付着性を著しく高めることができるので特に望ましい。
また、架橋剤などの添加物をシリコン変成樹脂あるいはシランカップリング剤に含めることもできる。
【００１７】
また、光触媒は、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、接着層と固着して光触媒活性を示すものであればいずれも使用可能である。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と、光触媒層の透明性が向上し、直線透過率が高くなるため、透明性を要求されるガラス基板やプラスチック成形体に塗布する場合に特に好ましい。また下地の担体に色や模様が印刷されたものの場合にこうした透明な光触媒層を塗布すると下地の色や柄を損なうことがない。
【００１８】
光触媒層中の光触媒としては、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、これらの光触媒に、Ｐｔ、Ｒｈ、ＲｕＯ2 、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅなどの金属及びそれらの金属の酸化物を添加したものが使用することができる。また、これらの光触媒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も全て使用可能である。光触媒層中の光触媒の含有量は、多量なほど触媒活性が高くなるが、接着性の点から好ましくは７５重量％以下である。
光触媒層の形成方法は、特に限定されないが、光触媒を含む塗布液（光触媒層形成用塗布液）を塗布し、乾燥する方法が好ましい。光触媒層形成用塗布液を塗布する方法としては、塗布溶液の印刷法、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、スピンコーティング法、刷毛塗装方法、ローラー塗装方法等あらゆる方法を採用することができる。
【００１９】
光触媒層の厚みは、厚い方が活性が高いが、５μｍ以上になるとほとんど変わらなくなる。５μｍ以下で、高い触媒活性を示し、しかも、透光性を示すようになり、触媒層が目立たなくなり好ましい。しかし、厚さが、０．１μｍ未満になると透光性は良くなるものの、光触媒が利用してい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以下の光触媒粒子および比表面積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、担体が透明な場合、透過した可視光線を照明として利用でき、また、担体が不透明な場合でも、担体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。
光触媒形成用塗布液としては、シリコン化合物を０．００１〜５重量％、金属の酸化物および／または水酸化物のゾルを固型分として０．１〜３０重量％、並びに光触媒の粉末および／またはゾルを固型分として０．１〜３０重量％を含有した光触媒層形成用塗布液が、長期にわたり安定で粘度増加や粒子沈降がない点で好ましく使用することができる。
【００２０】
光触媒層形成用塗布液中に添加するシリコン化合物としては、一般式（２）
ＳｉＲ3n5（ＯＲ4）４−n5 ・・・（２）
〔但し、式中、Ｒ3は（アミノ基、塩素原子、若しくはカルボキシル基で置換されてもよい）炭素数１〜８のアルキル基を表し、Ｒ4は炭素数１〜８のアルキル基またはアルコキシ基で置換された炭素数１〜８のアルキル基を表し、ｎ5は０、１、２、３のいずれかの数を表す。〕で表されるアルコキシシラン類またはそれらの加水分解生成物の１種または２種以上をで表されるアルコキシシラン類またはそれらの加水分解生成物の１種または２種以上の混合物が使用可能である。
【００２１】
一般式（２）において、Ｒ3としては、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があり、−ＯＲ4としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−プトキシ基、β−メメトキシエトキシ基、β−エトキシエトキシ基、２−エチルヘキシロキシ基等Ｃ1〜Ｃ8のアルコキシ基のものが望ましい。
【００２２】
一般式（２）で表されるシリコン化合物の例として、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種以上の混合物を好ましく挙げることができる。
【００２３】
光触媒層の塗布液中へのシリコン化合物の添加方法としては、光触媒粉末も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および／または水酸化物のゾルの液中へ添加する方法など種々の方法が可能である。また、部分加水分解されたシリコン化合物が添加されていても良い。この光触媒層の塗布液中に添加するシリコン化合物は、沸騰水中での光触媒層の付着性を高める効果も有するため、前述のシランカップリング剤等が添加されている場合はシリコン化合物の添加量を減らすことが可能である。
【００２４】
光触媒層の塗布液中に添加する金属の酸化物および／または水酸化物のゾルは、固型分として塗布液に対して０．１〜３０重量％、光触媒の粉末および／またはゾルは固型分として塗布液に対して０．１〜３０重量％をそれぞれ加えるのが望ましい。
【００２５】
前記した光触媒層形成塗布液の調整は、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、２００℃以下が好ましい。
【００２６】
本発明に使用される接着層の材質として、基体及び光触媒層に密着し、光触媒機能による分解から基体を保護し、更に、基体に含まれる光触媒機能を阻害する物質等の移行を抑制できるものであれば、特に制限されない。例えば、シリコン含有量２〜６０重量％のアクリル−シリコン樹脂、エポキシ−シリコン樹脂等のシリコン変性樹脂、コロイダルシリカを５〜４０重量％含有する樹脂、又は一般式（１）
ＳｉＣｌn1（ＯＨ）n2Ｒ1n3 （ＯＲ2）n4 ・・・（１）
〔式中、Ｒ1は（アミノ基、カルボキシル基、または、塩素原子で置換されてもよい）炭素数１〜８のアルキル基、Ｒ2は炭素数１〜８のアルキル基もしくはアルコキシ基で置換された炭素数１〜８のアルキル基を表し、ｎ4は０から２の整数を表し、ｎ4は２から４の整数を表し、かつｎ1＋ｎ2＋ｎ3 ＋ｎ4＝４を示す〕で表される化合物の重縮合反応生成物であるポリシロキサンを３〜６０重量％含有する樹脂を主成分とする塗布液を好ましく例示することができる。
【００２７】
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の場合の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。
【００２８】
シリコンが導入される樹脂としては、アクリル樹脂やエポキシ樹脂が成膜性、強靭性、担体との密着性の点で最も優れているが、アルキッド樹脂、ウレタン樹脂、ポリエステル樹脂等のような物でも使用できる。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。
【００２９】
接着層樹脂が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あるいは該加水分解物からの生成物である場合に、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。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いので、樹脂中で硬化させるのが困難になり、接着性や耐久性が悪くなる。
【００３０】
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り、担体が腐食したり、接着性を悪くする。
【００３１】
ポリシロキサンの樹脂への導入方法としては、シリコンアルコキシドモノマーの状態で樹脂溶液へ混合し、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。
【００３２】
ポリシロキサンが導入される樹脂としては、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、アルキッド樹脂等が使用できるが、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が耐久性の点で最も優れている。
【００３３】
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５０ｎｍ以下が好ましい。５０ｎｍ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を混合後、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およ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。
【００３４】
コロイダルシリカが導入される樹脂としては、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例示することができるが、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が最も耐久性の点で優れている。
【００３５】
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。
【００３６】
また、接着層樹脂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耐久性を向上させることができる。使用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、その他の物でも使用可能である。紫外線吸収剤としてはトリアゾール系などが使用できる。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。なお、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。
【００３７】
接着層を形成する方法は、例えば、真空蒸着、スパッタ法等特に制限されないが、接着層を形成する成分を有する塗布液を塗布し、乾燥する方法を好ましく例示することができる。基材に塗布する方法としては、塗布溶液の印刷法、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、スピンコーティング法、刷毛塗装方法、ローラー塗装方法等あらゆる方法を例示することができる。乾燥する温度は、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。接着層の厚さは、０．１μｍ以上であれば光触媒層を強固に接着し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。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。接着層の塗布液としては、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、好ましく例示することができる。接着層形成用塗布液は、有機溶剤溶液としてもしくは水性エマルジョンとして、樹脂固形分１〜５０重量％の塗布液を使用するのが望ましい。樹脂固形分濃度が１％以下の塗布液では、接着層が薄くなり過ぎて光触媒層の接着が困難になり、樹脂固形分が５０重量％以上の塗布液では、接着層が厚くなり過ぎて良好な塗膜にならないだけでなく、粘度が高くなり過ぎてハンドリングが困難になったりする。接着層形成用塗布液は、樹脂等の有機成分、コロイダルシリカ等の無機成分を適宜溶媒中に溶解又は、分散させて用いるのが好ましい。溶媒としては、水やトルエン、アルコールなどの有機溶媒を例示することができ、これらを単独又は２種以上混合して用いることができる。前記塗布液には、必要に応じて架橋剤、分散剤、充填剤、酸化防止剤、光安定剤、帯電防止剤、難燃剤、抗菌剤、抗かび剤な等を配合させることができる。架橋剤としては、イソシアネート系、メラミン系などの通常の架橋剤を、分散剤としては、カップリング剤などを使用することができる。接着層は必要に応じて２層以上設けることもでき、この場合、各層の組成はそれぞれに独立に、同一又は相異なった組成の層を形成することができる。例えば、基材から順に、接着層、無機層、光触媒層を有する光触媒担持構造体を例示することができる。この場合、無機層とは、光触媒層と接着層との接着性を向上させる効果と光触媒層の耐摩耗性を向上させる効果、更に、光触媒層膜厚に由来する干渉縞による発色を低減させる効果がある。無機層の材質としては、一般式（３）
ＲnＳｉ（ＯＲ1）4-n
（式中、Ｒは炭素数１〜４の置換基を有していてもよいアルキル基を表わし、Ｒ1は、炭素数１〜５の置換基を有していもよいアルキル基または炭素数１〜４の置換基を有していてもよいアシル基を表わし、ｎは０又は１を表わす。)で表わされるオルガノアルコキシシランもしくはアルコキシシランの加水分解・縮合物を主成分とする。硬化速度の制御、膜のひび割れ防止、化学的耐久性向上、屈折率の制御等の目的で、シリカゾル、アルミナゾル、ジルコニアゾルなどを添加することもできる。無機層を接着層へ形成するには、接着層を基体上に形成するのと同様のコート方法を用いることができる。接着性及び／または操作性をよくするために、５重量％以下の界面活性剤、消泡剤やシランカップリング剤などを添加するこことができる。無機層形成時の乾燥温度としては、基材シート材質によっても異なるが、５０℃以上１５０℃以下が好ましい。無機層の厚みは、０．１μｍ以上２μｍ以下が好ましい。
【００３８】
本発明は、上記光触媒層及び／又は接着層にトリフェニルメタン系染料を含有することを特徴とする。光触媒層形成塗布液及び接着層塗布液を基板上に塗布し成膜した場合、もともとは透明であるため、光触媒層及び／又は接着層を該染料で着色することにより、塗り残し、重ね塗り等の塗りむらを防止することができる。また、外壁等の屋外に、着色した光触媒層を形成した場合、トリフェニルメタン系染料は、一般的に日光堅牢度が低いため太陽光等の光照射下では、次第に消色して透明な膜となり、基材の色彩、装飾を損なうことのない、透明の層を形成することができる。
一方他の日光堅牢度の低い染料を用いても、太陽光等の光照射下では同様の性質を有する層を形成することが可能であるが、光強度が比較的小さい日陰等では消色せずに色が残り、外観を損なうという問題があった。トリフェニルメタン系染料は、基体上に光触媒層を形成した場合、光強度の比較的小さい日陰等においても消色するという特徴を有するため屋外において使用場面を限定されることなく使用することができるという利点がある。その理由の詳細については明らかではないが、光触媒とトリフェニルメタン化合物間に何らかの相互作用があり、それが原因となっていると推測している。
本発明に用いられるトリフェニルメタン系染料としては、中心炭素に対して、ｐ−アミノ基又は水酸基がｐ−キノン構造をとって発色するトリフェニルメタン骨格を有する化合物を成分とする染料であれば、特に限定されず、例えば、Ｍａｌａｃｈｉｔｅ Ｇｒｅｅｎ、Ａｓｔｒａｚｏｎｅ Ｂｌｕｅ Ｇ、Ｂｒｉｌｌｉａｎｔ Ｇｒｅｅｎ ＧＸ、Ｎａｐｈｔｈａｌｅｎ Ｇｒｅｅｎ Ｇ、Ｂｒｉｌｌｉａｎｔ Ｍｉｌｌｉｎｇ Ｇｒｅｅｎ Ｂ、Ｎａｐｈｔｈａｌｅｎｅ Ｇｒｅｅｎ ＶＳ、Ｍｇｅｎｔａ、Ｍｅｔｈｙｌ Ｖｉｏｌｅｔ、Ｃｒｙｓｔａｌ Ｖｉｏｌｅｔ、Ｖｉｃｔｏｒｉａ Ｂｌｕｅ Ｂ、Ｗｏｏｌ Ｖｉｏｌｅｔ ５ＢＮ、Ｓｏｌｕｂｌｅ Ｂｌｕｅ、Ａｕｒｉｎｅ、Ｃｈｒｏｍｅ Ｐｕｒｅ Ｂｌｕｅ ＢＸ、Ｃｈｒｏｍｅ Ｂｒｉｌｌｉａｎｔ Ｂｌｕｅ ＦＢＧ等を例示することができ、中でもＣｒｙｓｔａｌ Ｖｉｏｌｅｔ（クリスタルバイオレット）が好ましい。各層に添加する量は、特に限定されない。各層の固形分又は各層塗布液中の固形分に対して０．０２重量％以上であれば、着色を確認することができ好ましい。添加量の上限については、消色させる時間、光量との関係で任意に設定することができるが、例えば、０．０１ｍＷ／ｃｍ２以上の光量で１週間以内に消色させるためには、各層の固形分又は各層塗布液中の固形分に対して０．０５重量％以下であるのが好ましい。
各層をトリフェニルメタン系染料で着色させる方法は、簡便性の点から、各層形成用塗布液中に該染料を混合して着色させ、該塗布液を用いて塗布する方法が好ましい。
【００３９】
本発明に使用される基材は特に制限されない。具体的には、ガラス、プラスチック、布帛、金属、木材等を例示することができる。
【００４０】
ガラスの形状としては、板状、管状、球状、繊維状等どのような複雑な形状にでも使用することができる。また、施工済の窓ガラス、ショーケース、めがね等用途によっては、加工済のガラスに応用することもできる。
【００４１】
窓ガラス、計器用カバーガラス、照明器具、照明灯、ブラックライト、水処理用充填剤をはじめ、カメラ、眼鏡レンズ等、あらゆる使用場面に使用できる。 プラスチック成形体は、壁紙、内装用ボード、家具、電気機器、車輛用部品をはじめ、カメラ、メガネのレンズ等、多くの使用場面に使用できる。
【００４２】
プラスチック成形体の形状としては、フィルム状、板状、管状、球状、繊維状等どのような複雑な形状にでも、使用することができる。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、加工済のプラスチック成形体の処理に使用することができる。
【００４３】
布帛としては、毛、絹、綿、麻などの天然繊維、レーヨン、アセテートなどの再生繊維、ナイロン、アクリル、ポリアミド、ポリエステル、ポリアクリロニトリル、ポリ塩化ビニルなどの合成繊維、アラミドなどの耐熱性繊維の単独あるいは混紡繊維からなる織布、編布、不織布などを基材として用いることができる。また、シリコン系撥水剤、パーフルオロアルキルアクリレートなどのフッ素撥水剤、ジルコニウム塩系撥水剤、エチレン尿素系撥水剤などの撥水剤で処理された布帛、必要に応じて耐久性を向上させるためにエチレンイミン系、エポキシ系、メラミン系等の架橋剤を併用している撥水加工された布帛、ポリアミドとポリエステルのフィブリル化型複合繊維等からなる擬革、織布、不織布、編布等の基材にポリウレタン接着剤を介してポリウレタン樹脂層が形成されてなる合成皮革等を用いることもできる。また、傘、テント、バッグ等、加工済の布帛の処理に使用することができる。本発明の方法により処理された布帛は、多くの使用場面、たとえばカーテン、壁紙等のインテリア製品、テント、傘、テーブルクロス等の日用品、食品包装材等としてまた育苗シート等農業分野にも使用できる。
【００４４】
金属としては、アルミニウム、鉄、銅等の単体金属の他、ステンレス、しんちゅう、黄銅、アルミ合金、チタン合金等の各種合金なども基材として使用可能である。また、使用する金属の形状、材質によっては、通常の塗料で塗装した金属シートや板、着色したカラー鋼板やカラーアルミサッシ等にも使用することができる。
【００４５】
金属の形状としては、板状、管状、球状、繊維状、シート状等どのような複雑な形状にでも、使用できる。また、施工済の窓枠、家具、ショーケース、めがねフレーム等用途によっては、加工済の金属の処理にも使用することができる。
本発明に示す方法で処理した金属は、窓枠、家具、装飾品、内装パネル、外装パネル、水処理用充填剤をはじめ、ストレーナー、フィルター等、抗菌、脱臭、防汚等の効果を必要とする多くの使用場面に使用できる。
【００４６】
木材および木質材料の形状としては、板状、板状、球状、シート状等どのような複雑な形状でも可能である。また、施工済の壁、天井板、柱のほか、家具、木工細工等の加工済の木材および木質材料の処理にも使用することができる。
本発明に示す方法で処理した木材および木質材料は、建築用材、家具、木工品、インテリア材および内装材等、抗菌、脱臭、防汚等の効果を必要とする多くの使用場面に使用できる。
【００４７】
プラスチックフィルムは、処理を施していない面に粘着剤を塗布したフィルムとすることで、自動車や各種輸送機器の窓ガラス、建築物の窓ガラス、冷凍・冷蔵ショーケースや温室などの内側に貼り付けることが可能になり、ガラス表面の汚染防止と破損時の飛散防止に有効な透視性の高いフィルムとすることが可能である。また、薄いプラスチックフィルムは食品包装用のラップフィルムとしても使用可能である。このプラスチックフィルムに使用できる樹脂としては、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のフィルム状に成形加工した時に５５０ｎｍの波長の光の直線透過率が５０％以上である透明性の高い合成樹脂フィルムまたはシートがいずれも使用できる。また、壁紙や化粧シートなどの裏面に粘着層と剥離フィルムを設け表面に模様を印刷した不透明な素材の表面にも、下地の壁紙や化粧シートに印刷された柄や模様を損なうことがないので好ましく採用できる。
【００４８】
これらの基材に、本発明の方法を用いて、先に示した、接着層塗布液、光触媒層塗布液を用いて光触媒機能を付加した構造体は、紫外線等により表面の光触媒が励起され、有機物等の汚れ、汚染物質、菌等を分解する能力を有することから、抗菌、防汚、脱臭等の効果を必要とする多くの場面に使用することができる。また、紫外線等の光励起により親水性を呈する構造体も、防汚、防曇等の効果を必要とする多くの場面で使用することでき好ましい。この場合、親水性とは、表面における水の接触角を指標に計られ、接触角が２０度以下、更には１０度以下のものが好ましい。
【００４９】
以下実施例により本発明を詳細に説明するが、本発明の範囲は実施例に限定されるものではない。
【００５０】
【実施例】
実施例１
酸化物換算でシリコン含有量が３重量％のアクリルシリコン樹脂（ガラス転移温度２０℃）、テトラメトキシシランの部分加水分解生成物であり重合度が３〜６であるオリゴマーを固形分重量比６５：３５に混合し、エタノール−酢酸エチル混合溶媒で固形分濃度が１０重量％になるように希釈し、接着層用塗布液を調製した。更に表１に示したトリフェニルメタン系染料を固形分に対し、０．０２重量％になるように混合して着色した接着層形成用塗布液を得た。
【００５１】
また、光触媒ゾル（石原産業（株）製、商品番号：ＳＴＳ−０１、固形分濃度３０重量％、平均粒子径７ｎｍ）、コロイダルシリカ（粒子径２０ｎｍ）を固形分重量比５０：５０に混合し、エタノール及び水を用いて固形分１０重量％になるように希釈し、硝酸でｐＨ＝２．０になるように調整して光触媒層形成用塗布液を調製した。更に表１に示したトリフェニルメタン系染料を固形分に対し、０．０２重量％になるように混合して着色した接着層形成用塗布液を得た。
【００５２】
次いで、ガラス基板に白色塗料（カンペパピオ（株）製合成樹脂エナメル塗料；ヒットスプレー（ホワイト））を塗布した白色基板を準備した。前記白色基板上に、上記着色した又は染料無添加の接着層塗布液を刷毛で塗布し、室温で３時間乾燥した後、上記着色した又は染料無添加の光触媒塗布液を同様に刷毛で塗布した。
塗布は各層での塗料の発色／退色状態を確認するため以下の３種類の組み合わせで塗り分けた。
【００５３】
【表１】
各サンプルを２枚ずつ作成し、うち１枚は、日陰（照度０．０１２ｍＷ／ｍ２以下）に３週間屋外暴露し、うち一枚は、室内に１週間放置した後、ひなた（照度１．２ｍＷ／ｍ２以下）に２週間屋外暴露した。退色の状況は、目視で判断し、退色：○ 目視で色が確認できない
△ 目視で色が確認できるが、当初と比較して退色が見られる。
× 目視で当初と同等の色を確認できる。
上記の記号で表した結果を第２表に示す。
【００５５】
【表２】
【００５６】
実施例２
トリフェニルメタン系染料としてクリスタルバイオレットを用い、実施例１と同様にして着色パターンＣのサンプルを作成し、屋外に１週間暴露し、光強度と染料濃度の関係を調べた。評価は、色差計を用いて基板の白色との差（ΔΔＥ）を測定した。その結果を第３表に示す。
【００５７】
【表３】
初期ΔＥの値より、染料濃度は０．０２重量％以上が好ましいことがわかる。
また、ΔΔＥの値より、染料濃度が０．０６重量％以上では、短期間で消色させるのが困難となることがわかる。また、光強度が０．００６〜０．０２４ｍＷ／ｃｍ2程度では、短期間で消色させるには困難であることがわかる。
【００５９】
【発明の効果】
以上述べたように、本発明の方法を用いることにより、塗り残し、塗り重ね等の塗りむらの問題を生じることがなくなった。しかも、トリフェニルメタン系染料は、光触媒層を設けることで、比較的光強度の弱い、日陰においても短期間で消色させることができることから、基材の外観を損ねることなく、屋外であれば、場所を限定することなく使用することが可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colored photocatalyst.CarryingThe present invention relates to a structure and a coating solution for forming the structure.
[0002]
[Prior art]
Recently, several base materials having a photocatalytic function for decomposing surface dirt and the like by the action of light have been proposed. However, in order to have a photocatalytic function without deteriorating the appearance of the substrate, the coating film having the photocatalytic function is highly transparent and the film thickness is thin, so that the coated part and the uncoated part are distinguished. However, there were problems such as the occurrence of unpainted portions and many overcoated portions, and an increase in the amount of drug used.
[0003]
On the other hand, a method has been proposed in which the photocatalyst layer is colored and the dye is decomposed and decolored using the photocatalytic function, but the photocatalytic effect is different because the amount of light is different in a sunny place and in the shade. There was a problem that the degree of decoloring could be different and it looked uneven.
In general, the following method is known as a method of applying a double coating on the surface of a base material without being left uncoated or unevenly coated, which is colorless and transparent.
[0004]
For example, in JP-A No. 2000-51782, a coating solution containing a fluorescent dye is used, and the coated portion and the uncoated portion of the base material are identified by fluorescence emitted from the obtained coating film. The coating method is characterized in that the coating operation is advanced based on the identification.
[0005]
Japanese Patent Laid-Open No. 5-25899 discloses that a fading colorant material is added to a transparent coating solution for coloring, and the transparent coating solution is applied in a colored state to utilize photochemical reaction, sublimation, or outflow due to rainwater. The method of fading is described.
[0006]
[Problems to be solved by the invention]
However, the method described in Japanese Patent Application Laid-Open No. 2000-51782 has a problem in that the appearance of the substrate may be impaired depending on the angle of light, because the fluorescent dye remains in the coating film. Moreover, although the method described in JP-A-5-25899 is effective to some extent when applied to the outermost layer, light and rainwater may not be sufficiently supplied depending on the place where the paint is applied. There was a problem that it took time.
[0007]
In particular, the present invention is not applied to the surface of the base material at the outside work site, there is no uneven coating such as overcoating, the use scene is not limited, and the characteristics such as the color and pattern of the base material surface are not impaired. photocatalystCarryingStructure and photocatalyst using the coating methodCarryingIt is an object to provide a coating liquid for forming a structure.
[0008]
[Means for solving the problems]
As a result of intensive studies on many dyes to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by coloring with a triphenylmethane dye, and have completed the present invention.
[0009]
That is, the present invention is (1) a photocatalyst obtained by sequentially laminating an adhesive layer and a photocatalyst layer on a substrate surface.CarryingA photocatalyst comprising a triphenylmethane dye in an adhesive layer and / or a photocatalyst layer in a structureCarryingThe photocatalyst according to (1), wherein the structure, (2) the triphenylmethane dye is crystal violetCarryingA structure, (3) a silicon-modified resin having a silicon content of 2 to 60% by weight, a resin containing 5 to 40% by weight of colloidal silica, or the formula [1]
SiCln1(OH) n2R1nThree (OR2) NFour ... Formula [1]
[In the formula, R1Is an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom), R2Represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and n1Represents an integer from 0 to 2 and nFourIs an integer from 2 to 4 and n1+ N2+ NThree+ NFour= 4. ] A photocatalyst containing 3 to 60% by weight of polysiloxane which is a polycondensation reaction product of a compound represented by formula (1), wherein the photocatalyst layer contains 25 to 95% of metal oxide gel or metal hydroxide gel. A photocatalyst-supporting structure according to (1) or (2), which is a particle composite, (4) a photocatalystCarryingThe photocatalyst according to any one of (1) to (3), wherein the surface of the structure exhibits hydrophilicity in response to photoexcitation.CarryingRelated to the structure.
[0010]
(5) A photocatalyst-supporting structure-forming coating solution obtained by sequentially laminating an adhesive layer and a photocatalyst layer on a substrate comprises an adhesive layer-forming coating solution and a photocatalyst layer-forming coating solution, and the adhesive layer-forming coating solution. And / or a photocatalyst layer-forming coating solution containing a triphenylmethane dyeCarrying(6) The adhesive layer coating solution is a silicon-modified resin having a silicon content of 2 to 60% by weight, a resin containing 3 to 60% by weight of polysiloxane, or 5 to 40% by weight of colloidal silica. It is a coating liquid comprising a solution containing 1 to 50% by weight of the resin contained as a resin solid content, and the coating liquid for forming the photocatalyst layer is 0.001 to 5% by weight of silicon compound, metal oxide and / or hydroxylation A coating liquid comprising a liquid containing 0.1 to 30% by weight of a solid sol as a solid content and 0.1 to 30% by weight of a photocatalyst powder and / or sol as a solid content (5) ) PhotocatalystCarryingThe present invention relates to a coating liquid for forming a structure.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Photocatalyst of the present inventionCarryingThe structure has an adhesive layer and a photocatalyst layer that are sequentially laminated on the substrate. The structure of the photocatalyst layer is preferably strong on the substrate while the photocatalyst has its photocatalytic function.CarryingIf it is done, it is not particularly limited. Specifically, a photocatalyst using a compound that is hardly decomposable to photocatalysis as a binderCarryingAn example of such a structure can be illustrated. Examples of the hardly decomposable compound include silicon compounds such as water glass, colloidal silica and polyorganosiloxane, phosphates such as zinc phosphate and aluminum phosphate, heavy phosphates, cement, lime, gypsum and enamel. Examples include inorganic binders such as frits for glass, glazes for glass lining, plaster, and organic binders such as fluorine-based polymers and silicone-based polymers. Two or more kinds can be used in combination. In particular, from the viewpoint of adhesive strength, an inorganic binder, a fluorine polymer, and a silicon polymer are preferable. Examples of the cement include early-strength cement, ordinary cement, medium heat cement, sulfate resistant cement, white (white) cement, oil well cement, geothermal well cement and other Portland cement, fly ash cement, high sulfate cement, silica cement, Mixed cement such as blast furnace cement, alumina cement and the like can be used. As a plaster, gypsum plaster, lime plaster, dolomite plaster, etc. can be used, for example. Examples of the fluorine-based polymer include polyvinyl fluoride, polyvinylidene fluoride, polychloroethylene trifluoride, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, ethylene-polytetrafluoroethylene copolymer, ethylene. -Crystalline fluororesins such as ethylene chloride trifluoride copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, amorphous fluororesins such as perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, Various fluorine-based rubbers can be used. In particular, a fluorine-based polymer mainly composed of a vinyl ether-fluoroolefin copolymer and a vinyl ester-fluoroolefin copolymer is preferable because it is less decomposed and deteriorated and is easy to handle. As the silicon-based polymer, linear silicon resin, acrylic-modified silicon resin, various silicon-based rubbers, and the like can be used. In particular, a photocatalyst layer that is a photocatalyst particle composite containing 25 to 95% of metal oxide gel or metal hydroxide gel is preferable. The specific surface area of the metal oxide gel or metal hydroxide gel is preferably 50 m after drying at 150 ° C.2/ G or more, more preferably 100 m2When it is at least / g, the adhesion becomes stronger and the catalytic activity is also improved.
[0012]
Preferred examples of the metal component include oxide gels or hydroxide gels of metals such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin.
Moreover, the photocatalyst after being immersed in boiling water by using an oxide or hydroxide gel containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium as the metal component It is possible to increase the adhesion of the layer. Examples of combinations of metal components having excellent boiling water resistance include silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-niobium, aluminum-titanium, aluminum-zirconium, aluminum-niobium, aluminum-tantalum, titanium-zirconium. , Titanium-niobium, titanium-tantalum, silicon-aluminum-zirconium, silicon-aluminum-titanium, etc., more preferably silicon-aluminum, silicon-titanium, silicon-zirconium, silicon-titanium-aluminum, silicon-aluminum- Examples thereof include oxide gels such as zirconium or hydroxide gels.
[0013]
The specific surface area of these oxide gels or hydroxide gels is 50 m.2When it is at least / g, the adhesiveness is high, the catalytic activity is improved, and the adhesive property is excellent even after being immersed in boiling water. 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 preferable.
[0014]
Further, by adding 10 to 50% by weight of a silicon-modified resin or a silane coupling agent in the photocatalyst layer, it is immersed in boiling water for 15 minutes while maintaining high catalytic activity, and then a cross-cut tape defined in JIS K5400 In the adhesion test by the method, an excellent adhesion having an evaluation score of 6 points or more can be obtained.
[0015]
The silicon-modified resin or silane coupling agent added to the photocatalyst layer has an effect of improving the adhesion of the photocatalyst layer in boiling water. As the silicone-modified resin, commercially available silicon-acrylic or silicon-epoxy resins can be used, either those dissolved in a solvent or those dispersed in water as an emulsion. is there. As the silane coupling agent, the general formula: RSi (Y)ThreeYa (R)2Si (Y)2(However, R represents an organic functional group, Y represents a chlorine atom or an alkoxy group.), Etc. can be used. In the above general formula, R is methyl group, ethyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group. , .Gamma.-mercaptopropyl group, .gamma.-aminopropyl group, .gamma.-acryloxypropyl group, etc., and Y is methoxy group, ethoxy group, .beta.-methoxyethoxy group, .beta.-ethoxyethoxy group, etc. in addition to chlorine atom. Any of the alkoxy groups of C5 can be used.
[0016]
The addition amount of the silicon-modified resin or the silane coupling agent is desirably 10 to 50% by weight as a solid content in the photocatalyst layer. As a method for adding a silicon-modified resin or a silane coupling agent into the photocatalyst layer, a method for adding the photocatalyst powder or a sol to the liquid, a metal oxide for forming a metal oxide gel to be added together with the photocatalyst, or Various methods such as a method of adding a hydroxide to a sol solution are possible. Note that it is particularly desirable to add an emulsion type silicon-modified resin to the sol solution because adhesion of the photocatalyst layer in boiling water can be remarkably improved without substantially reducing the photocatalytic activity.
Moreover, additives, such as a crosslinking agent, can also be included in a silicone modified resin or a silane coupling agent.
[0017]
Any photocatalyst can be used as long as it is fixed to the adhesive layer and exhibits photocatalytic activity when dried at the drying temperature of the photocatalyst layer, such as powder, sol, and solution. When using a sol-like photocatalyst, if a particle size of 20 nm or less, preferably 10 nm or less is used, the transparency of the photocatalyst layer is improved and the linear transmittance is increased. It is particularly preferable when applied to a plastic molded body. In addition, in the case where a color or pattern is printed on the base carrier, if the transparent photocatalyst layer is applied, the base color or pattern is not impaired.
[0018]
As a photocatalyst in the photocatalyst layer, TiO2 , ZnO, SrTiOThree, CdS, GaP, InP, GaAs, BaTiOThree, KNbOThree, Fe2OThree , Ta2OFive , WOThree, SnO2, Bi2OThree, NiO, Cu2O, SiC, SiO2, MoS2, InPb, RuO2, CeO2And these photocatalysts added with metals such as Pt, Rh, RuO2, Nb, Cu, Sn, Ni, Fe and oxides of these metals can be used. In addition, these photocatalysts utilize Pt, Rh, RuO by utilizing the photocatalytic reduction action.2, Nb, Cu, Sn, Ni, Fe and other metals added can all be used. The higher the content of the photocatalyst in the photocatalyst layer, the higher the catalytic activity. However, from the viewpoint of adhesion, it is preferably 75% by weight or less.
The method for forming the photocatalyst layer is not particularly limited, but a method of applying a coating solution containing a photocatalyst (a coating solution for forming a photocatalyst layer) and drying it is preferable. As a method for applying the photocatalyst layer-forming coating solution, any method such as a coating solution printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, a brush coating method, or a roller coating method may be adopted. it can.
[0019]
The thicker the photocatalyst layer, the higher the activity, but almost no change when the thickness is 5 μm or more. When the thickness is 5 μm or less, high catalytic activity is exhibited, and translucency is exhibited, so that the catalyst layer is not noticeable, which is preferable. However, when the thickness is less than 0.1 μm, the translucency is improved, but the ultraviolet ray used by the photocatalyst is also transmitted, so that 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 m2When a metal oxide gel or metal hydroxide gel of / g or more is used, the total light transmittance at a wavelength of 550 nm of the photocatalyst layer and the adhesive layer becomes 70% or more. In the structure supported so that the total light transmittance at a wavelength of 550 nm is 70% or more, the transmitted visible light can be used as illumination when the carrier is transparent, and even when the carrier is opaque, Since it does not damage the handle, it is also useful for decorativeness.
As a photocatalyst-forming coating solution, 0.001 to 5% by weight of a silicon compound, 0.1 to 30% by weight of a metal oxide and / or hydroxide sol as a solid component, and a photocatalyst powder and / or Alternatively, a coating solution for forming a photocatalyst layer containing 0.1 to 30% by weight of a sol as a solid component can be preferably used because it is stable for a long period of time and does not increase in viscosity or cause particle sedimentation.
[0020]
The silicon compound added to the coating solution for forming the photocatalyst layer is represented by the general formula (2)
SiRThreenFive(ORFour4-nFive ... (2)
[However, in the formula, RThreeRepresents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom, or a carboxyl group), and RFourRepresents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and nFiveRepresents any number of 0, 1, 2, and 3. Or one or a mixture of two or more of the alkoxysilanes represented by these or the hydrolysis products thereof can be used. is there.
[0021]
In the general formula (2), RThreeAs methyl group, ethyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group, γ-mercaptopropyl group , Γ-aminopropyl group, γ-acryloxypropyl group, etc., and —ORFourAs methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-ptoxy group, β-memethoxyethoxy group, β-ethoxyethoxy group, 2-ethylhexyloxy group, etc. C1-C8 alkoxy group Is desirable.
[0022]
Examples of the silicon compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and one or a mixture of two or more of hydrolysis products thereof. Can be preferably mentioned.
[0023]
As a method for adding the silicon compound to the coating solution for the photocatalyst layer, a method for adding it to the photocatalyst powder or sol solution, or a method for adding the metal oxide and / or hydroxide sol solution added together with the photocatalyst. Various methods such as methods are possible. Further, a partially hydrolyzed silicon compound may be added. Since the silicon compound added to the coating solution for the photocatalyst layer also has the effect of increasing the adhesion of the photocatalyst layer in boiling water, the amount of silicon compound added should be reduced when the silane coupling agent is added. It is possible to reduce.
[0024]
The metal oxide and / or hydroxide sol added to the coating solution of the photocatalyst layer is 0.1 to 30% by weight of the coating solution as a solid component, and the photocatalyst powder and / or sol is a solid type. It is desirable to add 0.1 to 30% by weight with respect to the coating solution.
[0025]
The photocatalyst layer forming coating solution is prepared by dispersing the photocatalyst in the state of a precursor solution of a metal oxide sol or metal hydroxide sol, and hydrolyzing or neutralizing and decomposing at the time of coating. Also good. 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 during the formation of the photocatalyst layer is preferably 200 ° C. or lower, although it varies depending on the carrier material and the resin material in the adhesive layer.
[0026]
As the material of the adhesive layer used in the present invention, it can adhere to the substrate and the photocatalyst layer, protect the substrate from decomposition due to the photocatalytic function, and can further suppress the migration of substances that inhibit the photocatalytic function contained in the substrate. If there is, there is no particular limitation. For example, a silicon-modified resin such as an acrylic-silicon resin or an epoxy-silicon resin having a silicon content of 2 to 60% by weight, a resin containing 5 to 40% by weight of colloidal silica, or the general formula (1)
SiCln1(OH) n2R1nThree (OR2) NFour ... (1)
[In the formula, R1Is an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom), R2Represents a C 1-8 alkyl group substituted with a C 1-8 alkyl group or alkoxy group, and nFourRepresents an integer from 0 to 2 and nFourRepresents an integer from 2 to 4 and n1+ N2+ NThree + NFourA coating liquid mainly composed of a resin containing 3 to 60% by weight of polysiloxane which is a polycondensation reaction product of a compound represented by the formula:
[0027]
When the adhesive layer resin is a silicon-modified resin such as acrylic-silicon resin or epoxy-silicon resin, the introduction method of silicon into the resin is transesterification reaction, graft reaction using silicon macromer or reactive silicon monomer, hydrosilylation reaction There are various block copolymerization methods and the like, but in the present invention, a product produced by any method can be used.
[0028]
As the resin into which silicon is introduced, acrylic resin and epoxy resin are the most excellent in terms of film formability, toughness, and adhesion to the carrier, but even those such as alkyd resin, urethane resin, polyester resin, etc. Can 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.
[0029]
When the adhesive layer resin contains a polysiloxane, and the polysiloxane is a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product from the hydrolyzate, the adhesiveness and durability are improved. A more improved support structure can be obtained. If the number of carbon atoms in the alkoxy group of the silicon alkoxide is 6 or more, it is expensive and the hydrolysis rate is very slow, making it difficult to cure in the resin, resulting in poor adhesion and durability.
[0030]
Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can be used. However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by the chloride ions of impurities, and the adhesion is reduced. Make it worse.
[0031]
As a method for introducing polysiloxane into a resin, a method in which a silicon alkoxide monomer is mixed into a resin solution and hydrolyzed with moisture in the air when forming an adhesive layer, a product obtained by partially hydrolyzing silicon alkoxide in advance is used as a resin. There are various methods such as mixing and further 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.
[0032]
As the resin into which polysiloxane is introduced, acrylic resin, acrylic-silicon resin, epoxy-silicon resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, alkyd resin, etc. can be used. -Silicon modified resin including silicon resin is most excellent in terms of durability.
[0033]
When the adhesive layer is a resin containing colloidal silica, the particle diameter of the colloidal silica is preferably 50 nm or less. If it is 50 nm or more, the resin in the adhesive layer is not only easily deteriorated by the photocatalyst, but also the adhesion between the photocatalyst layer and the adhesive layer is deteriorated. The most convenient method for introducing the colloidal silica into the resin is to mix the resin solution and the colloidal silica solution, and then apply and dry to form an adhesive layer. The colloidal silica is dispersed in a state where the resin is dispersed. A polymerized and synthesized product may be applied and dried. Further, in order to improve the adhesion and dispersibility between the colloidal silica and the resin, the colloidal silica can be treated with a silane coupling agent.
[0034]
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, and the like. Silicon-modified resins including resins and epoxy-silicon resins are most excellent in terms of durability.
[0035]
The colloidal silica may be any silica sol made by cation exchange of a sodium silicate solution or silica sol made by hydrolyzing silicon alkoxide.
[0036]
Moreover, durability can be improved by mixing a light stabilizer and / or a UV absorber or the like with the purpose of suppressing deterioration due to photocatalytic action to the adhesive layer resin. The light stabilizer that can be used is preferably a hindered amine system, but other substances can also be used. As the UV 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.
[0037]
The method for forming the adhesive layer is not particularly limited, for example, vacuum deposition, sputtering, etc., but a method of applying and drying a coating solution having a component for forming the adhesive layer can be preferably exemplified. Examples of the method of applying to the substrate include all methods such as a printing method of a coating solution, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, a brush coating method, and a roller coating method. The drying temperature varies depending on the type of solvent and resin, but is generally preferably 150 ° C. or lower. If the thickness of the adhesive layer is 0.1 μm or more, the photocatalyst layer can be firmly adhered to form a highly durable photocatalyst carrying structure. 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. As a coating solution for the adhesive layer, a silicon-modified resin having a silicon content of 2 to 60% by weight, a resin containing 3 to 60% by weight of polysiloxane or a resin containing 5 to 40% by weight of colloidal silica is used as a resin solid content. A solution containing ˜50% by weight can be preferably exemplified. As the adhesive layer forming coating solution, it is desirable to use a coating solution having a resin solid content of 1 to 50% by weight as an organic solvent solution or as an aqueous emulsion. When the coating liquid with a resin solid content concentration of 1% or less is used, the adhesive layer becomes too thin and it becomes difficult to bond the photocatalyst layer. When the coating liquid has a resin solid content of 50% by weight or more, the adhesive layer becomes too thick and good. Not only does the film become difficult, but the viscosity becomes too high and handling becomes difficult. The coating liquid for forming the adhesive layer is preferably used by appropriately dissolving or dispersing an organic component such as a resin or an inorganic component such as colloidal silica in a solvent. As a solvent, organic solvents, such as water, toluene, alcohol, can be illustrated, These can be used individually or in mixture of 2 or more types. If necessary, the coating solution may contain a crosslinking agent, a dispersant, a filler, an antioxidant, a light stabilizer, an antistatic agent, a flame retardant, an antibacterial agent, an antifungal agent, and the like. As the crosslinking agent, an ordinary crosslinking agent such as isocyanate or melamine can be used, and as the dispersing agent, a coupling agent or the like can be used. If necessary, two or more adhesive layers can be provided. In this case, the composition of each layer can independently form layers having the same or different compositions. For example, a photocatalyst having an adhesive layer, an inorganic layer, and a photocatalyst layer in order from the base materialCarryingA structure can be illustrated. In this case, the inorganic layer is an effect of improving the adhesion between the photocatalyst layer and the adhesive layer, an effect of improving the wear resistance of the photocatalyst layer, and an effect of reducing the color development due to interference fringes derived from the film thickness of the photocatalyst layer. There is. As the material of the inorganic layer, the general formula (3)
RnSi (OR1)4-n
(In the formula, R represents an alkyl group which may have a substituent having 1 to 4 carbon atoms;1Represents an alkyl group which may have a substituent having 1 to 5 carbon atoms or an acyl group which may have a substituent having 1 to 4 carbon atoms, and n represents 0 or 1. ) Or an alkoxysilane hydrolyzate / condensate. Silica sol, alumina sol, zirconia sol, and the like can be added for the purpose of controlling the curing rate, preventing cracking of the film, improving chemical durability, and controlling the refractive index. In order to form the inorganic layer on the adhesive layer, the same coating method as that for forming the adhesive layer on the substrate can be used. In order to improve adhesion and / or operability, 5% by weight or less of a surfactant, an antifoaming agent, a silane coupling agent, or the like can be added. The drying temperature at the time of forming the inorganic layer varies depending on the material of the base sheet, but is preferably 50 ° C. or higher and 150 ° C. or lower. The thickness of the inorganic layer is preferably 0.1 μm or more and 2 μm or less.
[0038]
The present invention is characterized in that the photocatalyst layer and / or the adhesive layer contains a triphenylmethane dye. When the photocatalyst layer forming coating solution and the adhesive layer coating solution are coated on the substrate and formed into a film, the coating is transparent, so that the photocatalyst layer and / or the adhesive layer is colored with the dye to leave behind, overcoat, etc. Can prevent uneven coating. In addition, when a colored photocatalyst layer is formed on the outside such as an outer wall, the triphenylmethane dye generally has a low fastness to sunlight, so that it gradually loses its color under light irradiation such as sunlight. Thus, a transparent layer that does not impair the color and decoration of the substrate can be formed.
On the other hand, it is possible to form a layer having the same properties under light irradiation such as sunlight even when using other dyes with low fastness to sunlight. There was a problem that the color remained without damaging the appearance. When a photocatalyst layer is formed on a substrate, the triphenylmethane dye can be used outdoors without being limited because it has a characteristic of decoloring even in the shade with a relatively low light intensity. There is an advantage. Although the details of the reason are not clear, it is speculated that there is some interaction between the photocatalyst and the triphenylmethane compound, which is the cause.
The triphenylmethane dye used in the present invention is a dye having as a component a compound having a triphenylmethane skeleton in which a p-amino group or a hydroxyl group takes a p-quinone structure and develops color with respect to the central carbon. is not particularly limited, for example, Malachite Green, Astrazone Blue G, Brilliant Green GX, Naphthalen Green G, Brilliant Milling Green B, Naphthalene Green VS, Mgenta, Methyl Violet, Crystal Violet, Victoria Blue B, Wool Violet 5BN, Soluble Blue , Aurine, Chrome Pure Blue BX, Chrome Bri Illustrative examples include llant Blue FBG, and among these, Crystal Violet is preferred. The amount added to each layer is not particularly limited. If it is 0.02 weight% or more with respect to solid content of each layer or solid content in each layer coating liquid, coloring can be confirmed and it is preferable. The upper limit of the addition amount can be arbitrarily set in relation to the decoloring time and the light amount. For example, in order to decolorize within one week with a light amount of 0.01 mW / cm 2 or more, It is preferable that it is 0.05 weight% or less with respect to solid content or solid content in each layer coating liquid.
As a method of coloring each layer with a triphenylmethane dye, a method of mixing and coloring the dye in each layer-forming coating solution and applying the coating solution using the coating solution is preferable.
[0039]
The substrate used in the present invention is not particularly limited. Specifically, glass, plastic, fabric, metal, wood and the like can be exemplified.
[0040]
As the shape of the glass, any complicated shape such as a plate shape, a tubular shape, a spherical shape, and a fibrous shape can be used. Moreover, depending on uses, such as a constructed window glass, a showcase, and glasses, it can also be applied to processed glass.
[0041]
It can be used in various usage scenes such as window glass, instrument cover glass, lighting equipment, illuminating lamp, black light, water treatment filler, camera, eyeglass lens. Plastic moldings can be used in many applications such as wallpaper, interior boards, furniture, electrical equipment, vehicle parts, cameras, and lenses for glasses.
[0042]
As the shape of the plastic molded body, any complicated shape such as a film shape, a plate shape, a tubular shape, a spherical shape, and a fibrous shape can be used. Moreover, depending on uses such as construction materials, home appliances, and glasses that have already been constructed, they can be used for processing processed plastic moldings.
[0043]
As fabrics, natural fibers such as hair, silk, cotton and hemp, recycled fibers such as rayon and acetate, synthetic fibers such as nylon, acrylic, polyamide, polyester, polyacrylonitrile and polyvinyl chloride, and heat resistant fibers such as aramid A woven fabric, a knitted fabric, a nonwoven fabric, or the like made of a single fiber or a mixed fiber can be used as a base material. Also, fabrics treated with water repellents such as silicon water repellents, fluorine water repellents such as perfluoroalkyl acrylate, zirconium salt water repellents, ethylene urea water repellents, and durability as required. Water-repellent processed fabrics that use ethyleneimine-based, epoxy-based, and melamine-based crosslinkers together, and artificial leather, woven fabrics, non-woven fabrics, knitted fabrics made of polyamide and polyester fibrillated composite fibers, etc. Synthetic leather or the like in which a polyurethane resin layer is formed on a base material such as cloth via a polyurethane adhesive can also be used. It can also be used for processing processed fabrics such as umbrellas, tents and bags. The fabric treated by the method of the present invention can be used in many fields of use, for example, interior products such as curtains and wallpaper, daily necessities such as tents, umbrellas and table cloths, food packaging materials, and the like, and also in the agricultural field such as seedling sheets. .
[0044]
As the metal, in addition to simple metals such as aluminum, iron and copper, various alloys such as stainless steel, brass, brass, aluminum alloy and titanium alloy can be used as the base material. Further, depending on the shape and material of the metal used, it can be used for a metal sheet or plate coated with a normal paint, a colored color steel plate, a color aluminum sash, or the like.
[0045]
The metal can be used in any complicated shape such as a plate shape, a tubular shape, a spherical shape, a fiber shape, and a sheet shape. Moreover, depending on uses such as a window frame, furniture, a showcase, and a spectacle frame that has been installed, it can be used for processing processed metal.
Metals treated by the method shown in the present invention require effects such as antibacterial, deodorizing, and antifouling, including window frames, furniture, decorative items, interior panels, exterior panels, water treatment fillers, strainers, filters, etc. Can be used for many usage scenes.
[0046]
The shape of the wood and the wood material can be any complicated shape such as a plate shape, a plate shape, a spherical shape, and a sheet shape. Moreover, it can be used for the processing of processed wood and wood materials such as furniture, woodwork, etc., in addition to already constructed walls, ceiling boards, and pillars.
The wood and woody materials treated by the method shown in the present invention can be used in many usage scenes that require antibacterial, deodorizing, antifouling and other effects such as building materials, furniture, woodwork, interior materials and interior materials.
[0047]
Plastic film is a film with an adhesive applied to an untreated surface, and is affixed to the inside of window glass of automobiles and various transportation equipment, window glass of buildings, freezer / refrigerated showcases and greenhouses, etc. Therefore, it is possible to obtain a highly transparent film effective for preventing contamination of the glass surface and preventing scattering when broken. The thin plastic film can also be used as a wrap film for food packaging. Resins that can be used for this plastic film include polyethylene terephthalate resin, polycarbonate resin, polyacrylate resin, polymethyl methacrylate resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, polyfluoride resin. A highly transparent synthetic resin having a linear transmittance of light having a wavelength of 550 nm of 50% or more when molded into a film such as vinylidene resin, fluorinated ethylene-propylene copolymer resin, or fluorinated ethylene-ethylene copolymer resin. Either film or sheet can be used. In addition, the pattern or pattern printed on the underlying wallpaper or decorative sheet will not be damaged on the surface of an opaque material with an adhesive layer and release film on the back side of the wallpaper or decorative sheet. Preferably employed.
[0048]
The structure in which the photocatalytic function is added to these base materials by using the method of the present invention using the adhesive layer coating solution and the photocatalyst layer coating solution, the surface photocatalyst is excited by ultraviolet rays or the like, Since it has the ability to decompose organic matter and other contaminants, pollutants, bacteria, etc., it can be used in many scenes that require antibacterial, antifouling, deodorizing and other effects. In addition, a structure that exhibits hydrophilicity by photoexcitation such as ultraviolet rays is also preferable because it can be used in many situations that require effects such as antifouling and antifogging. In this case, the hydrophilicity is measured using the contact angle of water on the surface as an index, and the contact angle is preferably 20 degrees or less, more preferably 10 degrees or less.
[0049]
EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
[0050]
【Example】
Example 1
An acrylic silicon resin having a silicon content of 3% by weight in terms of oxide (glass transition temperature 20 ° C.), an oligomer having a degree of polymerization of 3 to 6 and a partial hydrolysis product of tetramethoxysilane, having a solid content weight ratio of 65: 35 and diluted with an ethanol-ethyl acetate mixed solvent so that the solid concentration was 10% by weight to prepare a coating solution for an adhesive layer. Further, a coating solution for forming an adhesive layer was obtained by mixing the triphenylmethane dye shown in Table 1 to 0.02% by weight with respect to the solid content and coloring.
[0051]
Further, a photocatalyst sol (manufactured by Ishihara Sangyo Co., Ltd., product number: STS-01, solid content concentration 30 wt%, average particle size 7 nm), colloidal silica (particle size 20 nm) was mixed at a solid content weight ratio of 50:50. A photocatalyst layer-forming coating solution was prepared by diluting with ethanol and water to a solid content of 10% by weight and adjusting the pH to 2.0 with nitric acid. Further, a coating solution for forming an adhesive layer was obtained by mixing the triphenylmethane dye shown in Table 1 to 0.02% by weight with respect to the solid content and coloring.
[0052]
Then, a white substrate was prepared by applying a white paint (synthetic resin enamel paint manufactured by Campe Papio Co., Ltd .; hit spray (white)) to a glass substrate. On the white substrate, the colored or dye-free adhesive layer coating solution was applied with a brush, dried at room temperature for 3 hours, and then the colored or dye-free photocatalyst coating solution was similarly applied with a brush. .
In order to confirm the color development / fading state of the paint in each layer, the coating was applied in the following three combinations.
[0053]
[Table 1]
Two samples were prepared, one of which was exposed outdoors in the shade (illuminance of 0.012 mW / m2 or less) for 3 weeks, and one of which was left indoors for 1 week, and then the chick (illuminance of 1.2 mW) / M2 or less) for 2 weeks. The condition of fading is judged visually, fading: ○ Color cannot be confirmed visually
Δ: The color can be confirmed visually, but fading is observed compared to the original.
× A color equivalent to the original color can be confirmed visually.
The results represented by the above symbols are shown in Table 2.
[0055]
[Table 2]
[0056]
Example 2
Using crystal violet as a triphenylmethane dye, a sample of colored pattern C was prepared in the same manner as in Example 1, exposed to the outdoors for one week, and the relationship between light intensity and dye concentration was examined. For the evaluation, a difference (ΔΔE) from the white color of the substrate was measured using a color difference meter. The results are shown in Table 3.
[0057]
[Table 3]
From the value of the initial ΔE, it can be seen that the dye concentration is preferably 0.02% by weight or more.
Further, it can be seen from the value of ΔΔE that when the dye concentration is 0.06% by weight or more, it is difficult to decolorize in a short period of time. The light intensity is 0.006 to 0.024 mW / cm.2It can be seen that it is difficult to erase the color in a short period.
[0059]
【The invention's effect】
As described above, by using the method of the present invention, the problem of uneven coating such as unpainted and repeated coating is eliminated. Moreover, the triphenylmethane dye can be discolored in a short period of time even in the shade by providing a photocatalyst layer, so that it can be discolored in a short period of time. It became possible to use without limiting the location.
Claims (6)
ＳｉＣｌn1（ＯＨ）n2Ｒ1n3 （ＯＲ2）n4 ・・・式（１）
〔式中、Ｒ1は（アミノ基、カルボキシル基、または塩素原子で置換されてもよい）炭素数１〜８のアルキル基、Ｒ2は、炭素数１〜８のアルキル基もしくはアルコキシ基で置換された炭素数１〜８のアルキル基を表し、ｎ1は０から２の整数を表し、ｎ4は２から４の整数であり、かつｎ1＋ｎ2＋ｎ3＋ｎ4＝４を示す。〕で表される化合物の重縮合反応生成物であるポリシロキサンを３〜６０重量％含有する樹脂であり、光触媒層が、金属酸化物ゲルもしくは金属水酸化物ゲルを２５〜９５％含有する光触媒粒子複合体であることを特徴とする請求項１又は２に記載の光触媒担持構造体。The adhesive layer contains a silicon-modified resin having a silicon content of 2 to 60% by weight, a resin containing 5 to 40% by weight of colloidal silica, or the formula (1)
SiCln 1 (OH) n 2 R 1 n 3 (OR 2 ) n 4 Formula (1)
[Wherein, R 1 is an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom), and R 2 is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms. Represents an alkyl group having 1 to 8 carbon atoms, n 1 represents an integer of 0 to 2, n 4 represents an integer of 2 to 4, and n 1 + n 2 + n 3 + n 4 = 4. ] A photocatalyst containing 3 to 60% by weight of polysiloxane which is a polycondensation reaction product of a compound represented by formula (1), wherein the photocatalyst layer contains 25 to 95% of metal oxide gel or metal hydroxide gel. 3. The photocatalyst-supporting structure according to claim 1, wherein the photocatalyst-supporting structure is a particle composite.
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| JP2003231827A (en) * | 2002-02-12 | 2003-08-19 | Canon Inc | Fog-resistant coating material, fog-resistant coated film and fog-resistant optical member |
| JP4626129B2 (en) * | 2003-06-30 | 2011-02-02 | 太陽工業株式会社 | Surface treatment agent, base material coated with the same, and production method and quality inspection method thereof |
| JP5527839B2 (en) * | 2007-01-30 | 2014-06-25 | ベック株式会社 | Aqueous coating solution |
| JP2009235326A (en) * | 2008-03-28 | 2009-10-15 | Asahi Kasei Chemicals Corp | Organic-inorganic composite |
| JP5903149B2 (en) * | 2014-10-29 | 2016-04-13 | ベック株式会社 | Film formation method |
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