JP5256693B2 - Production method of titanium oxide photocatalyst thin film - Google Patents
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- JP5256693B2 JP5256693B2 JP2007284457A JP2007284457A JP5256693B2 JP 5256693 B2 JP5256693 B2 JP 5256693B2 JP 2007284457 A JP2007284457 A JP 2007284457A JP 2007284457 A JP2007284457 A JP 2007284457A JP 5256693 B2 JP5256693 B2 JP 5256693B2
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- titanium oxide
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- peroxotitanium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 64
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 53
- 239000010409 thin film Substances 0.000 title claims description 47
- 239000011941 photocatalyst Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000009832 plasma treatment Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 description 20
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229910001872 inorganic gas Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Catalysts (AREA)
Description
本発明は酸化チタン系光触媒薄膜の製造法に関する。更に詳しくは、触媒活性が高い酸化チタン系光触媒薄膜の製造法に関する。 The present invention relates to a method for producing a titanium oxide photocatalyst thin film. More specifically, the present invention relates to a method for producing a titanium oxide photocatalytic thin film having high catalytic activity.
種々の基材の表面に酸化チタン薄膜をコーティングし、光による酸化チタンの強い分解力及び親水性を活用して、基材表面の清浄化、脱臭、抗菌化等の用途に活用してきた。 Titanium oxide thin films have been coated on the surfaces of various substrates, and the strong decomposition power and hydrophilicity of titanium oxide by light have been utilized to make use of them for applications such as cleaning, deodorizing, and antibacterializing the substrate surface.
しかし現在、酸化チタン薄膜のコーティングは、外装用タイル、ガラス、外壁塗装、空気清浄機内部のフィルター等、無機系の基材（セラミック、金属等）へのコーティングが主体的に応用されており、プラスティック材料等の有機材料の基材へのコーティングについても応用が検討されている（特許文献１、２）。プラスティックフィルム等の有機材料に酸化チタン薄膜を形成する方法が提案されている。この方法により酸化チタン系光触媒薄膜を得ることはできるが、十分に高い触媒活性を得ることができなく、触媒活性についてはその向上が望まれていた。 However, at present, the coating of titanium oxide thin film is mainly applied to coatings on inorganic base materials (ceramics, metals, etc.) such as exterior tiles, glass, exterior wall coating, filters inside air cleaners, etc. The application of organic materials such as plastic materials to the base material has been studied (Patent Documents 1 and 2). A method of forming a titanium oxide thin film on an organic material such as a plastic film has been proposed. Although a titanium oxide photocatalytic thin film can be obtained by this method, a sufficiently high catalytic activity cannot be obtained, and improvement of the catalytic activity has been desired.
本発明は上記問題点を解決するものであり、触媒活性が高い酸化チタン系光触媒薄膜の製造法を提供する。 The present invention solves the above problems and provides a method for producing a titanium oxide photocatalytic thin film having high catalytic activity.
即ち、本発明は、基材上にペルオキソチタンを含有する酸化チタン系材料の薄膜を形成し、次いで該酸化チタン系薄膜面をプラズマ処理する事を特徴とする、酸化チタン系光触媒薄膜の製造法を提供する。 That is, the present invention provides a method for producing a titanium oxide photocatalytic thin film characterized by forming a thin film of a titanium oxide-based material containing peroxotitanium on a substrate and then plasma-treating the titanium oxide-based thin film surface. I will provide a.
本発明によると、触媒活性が向上した酸化チタン系光触媒薄膜を製造することができる。 According to the present invention, a titanium oxide photocatalyst thin film having improved catalytic activity can be produced.
［基材］
酸化チタン系薄膜を形成する基材は、特に限定されない。特に本発明で効果が期待できる基材としては、プラスティックのフィルム若しくは成形品、繊維製品等の有機材料が挙げられる。その他、アルミニウム、ステンレス鋼、鉄などの金属、及びガラス、タイル等のセラミック製品も使用できる。具体的には、塩化ビニル樹脂、ポリエチレン、ポリプロピレン、ポリカーボネート、アクリル樹脂、ポリアセタール、フッ素樹脂、シリコーン樹脂、ＥＶＡ（エチレン−酢酸ビニル共重合体）、ＮＢＲ（アクリロニトリル−ブタジエンゴム）、ＰＥＴ（ポリエチレンテレフタレート）、ＥＶＯＨ（エチレン−ビニルアルコール共重合体）、ポリイミド樹脂、ＰＰＳ（ポリフェニレンサルファイド）、ＡＢＳ（アクリロニトリル−ブタジエン−スチレン）樹脂、メラミン樹脂等のフィルム、積層体若しくは成形品が挙げられる。
[Base material]
The base material which forms a titanium oxide type thin film is not specifically limited. In particular, examples of the substrate that can be expected to be effective in the present invention include organic materials such as plastic films or molded products, and textile products. In addition, metals such as aluminum, stainless steel, and iron, and ceramic products such as glass and tiles can be used. Specifically, vinyl chloride resin, polyethylene, polypropylene, polycarbonate, acrylic resin, polyacetal, fluororesin, silicone resin, EVA (ethylene-vinyl acetate copolymer), NBR (acrylonitrile-butadiene rubber), PET (polyethylene terephthalate) , EVOH (ethylene-vinyl alcohol copolymer), polyimide resin, PPS (polyphenylene sulfide), ABS (acrylonitrile-butadiene-styrene) resin, melamine resin film, laminate or molded product.
［酸化チタン系薄膜の形成］
本発明で薄膜の形成に使用し得る酸化チタン系材料は、光触媒として従来知られている酸化チタン系材料の中で、ペルオキソチタンを含有する酸化チタン系材料である。特にアナターゼ型の結晶構造を持つペルオキソチタンを含有する酸化チタン系材料が好ましい。ペルオキソチタンは、下記構造式に示すような、Ti-O-Ti結合の一部がTi-O-O-Ti結合に転化した過酸化チタンである。
[Formation of titanium oxide thin film]
The titanium oxide-based material that can be used for forming a thin film in the present invention is a titanium oxide-based material containing peroxotitanium among titanium oxide-based materials conventionally known as a photocatalyst. In particular, a titanium oxide-based material containing peroxotitanium having an anatase type crystal structure is preferable. Peroxotitanium is titanium peroxide in which a part of Ti—O—Ti bond is converted to Ti—OO—Ti bond as shown in the following structural formula.
ペルオキソチタンを含有する酸化チタン系材料の塗液としては、ペルオキソチタン酸水溶液、ペルオキソ改質アナターゼゾル、それらの混合液、及び他の材料の複合液であるペルオキソチタン系コーティング剤が挙げられる。市販のペルオキソチタン含有酸化チタン系材料の塗液としては、サガンコート（商品名TPXゾル、アナターゼ型ペルオキソチタン含有二酸化チタン水分散液、ペルオキソチタン固形分濃度０．８５質量％、鯤コーポレーション製）、ティオスカイコート（商品名TAK-A、ペルオキソチタン含有二酸化チタンの水分散体、ペルオキソチタン固形分濃度０．８５質量％、ティオテクノ製）等が挙げられる。これらの塗液は１種でも２種以上混合して使用してもよい。
ペルオキソチタンは酸化チタン系材料中に０．１質量％以上、特に０．２〜５質量％含まれるのが好ましい。
Examples of the coating liquid of titanium oxide-based material containing peroxotitanium include peroxotitanic acid aqueous solution, peroxo-modified anatase sol, a mixed liquid thereof, and a peroxotitanium-based coating agent that is a composite liquid of other materials. As a coating liquid of a commercially available peroxotitanium-containing titanium oxide material, Sagancoat (trade name TPX sol, anatase-type peroxotitanium-containing titanium dioxide aqueous dispersion, peroxotitanium solid content concentration 0.85% by mass, manufactured by Sakai Corporation), Tio Sky Coat (trade name TAK-A, aqueous dispersion of titanium dioxide containing peroxotitanium, peroxotitanium solid content concentration 0.85% by mass, manufactured by Tiotechno). These coating liquids may be used alone or in combination of two or more.
Peroxotitanium is preferably contained in the titanium oxide-based material in an amount of 0.1% by mass or more, particularly 0.2 to 5% by mass.
塗液のコーティングは、既に技術的に確立した方法により実施することができる。具体的には、ディップコーティング法、スピンコーティング法、スプレーコーティング法、刷毛塗り法、含浸法、ロール法、ワイヤーバー法、ダイコーティング法、グラビア印刷法、インクジェット法等を利用して酸化チタン系薄膜を形成する。また、ドライコーティング法としての真空蒸着、スパッタリング、イオンプレーティング等の方法を利用して薄膜を形成してもよい。 Coating of the coating liquid can be carried out by a method already established in the art. Specifically, titanium oxide thin film using dip coating method, spin coating method, spray coating method, brush coating method, impregnation method, roll method, wire bar method, die coating method, gravure printing method, ink jet method, etc. Form. Further, the thin film may be formed using a method such as vacuum deposition, sputtering, or ion plating as a dry coating method.
酸化チタン系薄膜の厚さは通常0.01〜10μm、好ましくは0.05〜2μmである。酸化チタン系薄膜層が薄すぎると光触媒活性が劣り、また厚すぎると剥離、割れ、そり等が発生し、好適な薄膜が形成できない。 The thickness of the titanium oxide thin film is usually 0.01 to 10 μm, preferably 0.05 to 2 μm. If the titanium oxide thin film layer is too thin, the photocatalytic activity is inferior, and if it is too thick, peeling, cracking, warping, etc. occur, and a suitable thin film cannot be formed.
［酸化チタン系薄膜のプラズマ処理］
基材に酸化チタン系薄膜を形成した面にプラズマ処理をして、酸化チタン系薄膜の触媒活性を向上させる。この処理法としては特に低圧低温の無機ガスプラズマ処理法が望ましい。
[Plasma treatment of titanium oxide thin film]
Plasma treatment is performed on the surface on which the titanium oxide thin film is formed on the base material, thereby improving the catalytic activity of the titanium oxide thin film. As this treatment method, a low-pressure and low-temperature inorganic gas plasma treatment method is particularly desirable.
低圧低温無機ガスプラズマ処理法では、減圧可能な低温プラズマ処理装置内に酸化チタン系薄膜を形成した基材を通し、該装置内を無機ガスの雰囲気にして、圧力0.001〜10Torr、好ましくは0.01〜1Torrに保持した状態で電極間に周波数50Hz〜13.6MHzの電力を印加する。電力は0.1〜50kWを印加し、グロー放電させることにより、無機ガスの低温プラズマを発生させる。その中に酸化チタン系薄膜を形成した基材を設置し、順次処理する。該基材を連続して処理する場合は該基材を順次移動させながら該基材上の酸化チタン系薄膜表面をプラズマ処理する。該無機ガスとしてはヘリウム、ネオン、アルゴンなどの希ガス、及び酸素、窒素、空気、炭酸ガス、アンモニア等が使用できる。これらのガスは１種でも、２種以上の混合物でもよい。プラズマ処理時間は通常0.1〜1,000秒、好ましくは１〜500秒である。 In the low-pressure low-temperature inorganic gas plasma processing method, a base material on which a titanium oxide-based thin film is formed is passed through a low-pressure plasma processing apparatus capable of reducing pressure, and the inside of the apparatus is set to an inorganic gas atmosphere, and pressure is 0.001 to 10 Torr, preferably 0.01 to A power of 50 Hz to 13.6 MHz is applied between the electrodes while maintaining 1 Torr. A low-temperature plasma of inorganic gas is generated by applying a glow discharge of 0.1-50 kW. A base material on which a titanium oxide-based thin film is formed is placed therein and sequentially processed. When the substrate is continuously treated, the titanium oxide thin film surface on the substrate is subjected to plasma treatment while sequentially moving the substrate. As the inorganic gas, rare gases such as helium, neon, and argon, and oxygen, nitrogen, air, carbon dioxide, ammonia, and the like can be used. These gases may be one kind or a mixture of two or more kinds. The plasma treatment time is usually 0.1 to 1,000 seconds, preferably 1 to 500 seconds.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
なお、実施例及び比較例において、酸化チタン系光触媒薄膜を以下のようにして評価した。
［光触媒活性の評価法］
メチレンブルー水溶液をサンプルに塗布し、光触媒評価チェッカーPCC-2（商品名、ULVAC製）により、青色色素の吸光度の減少を測定した。
In Examples and Comparative Examples, titanium oxide photocatalytic thin films were evaluated as follows.
[Evaluation method of photocatalytic activity]
A methylene blue aqueous solution was applied to the sample, and the decrease in absorbance of the blue dye was measured using a photocatalyst evaluation checker PCC-2 (trade name, manufactured by ULVAC).
［実施例１〜３及び比較例１〜３］
PET（ポリエチレンテレフタレート）フィルムから成る25μm厚の基材フイルムを7cm×7cmに裁断した。裁断した基材フイルムの表面に、下記の酸化チタン系光触媒塗液を、デップコーターMICRODIP MD0408（商品名、EINTESLA製）を用いて、引き上げ速度0.1mm/sec〜1.0mm/secの間でコーティングした。風乾した薄膜をそれぞれ80℃で30分間加熱することで完全に乾燥した酸化チタン系光触媒薄膜を得た。次に酸化チタン系光触媒薄膜面に、実施例１〜３及び比較例１では下記に示すプラズマ処理条件でプラズマ処理を施した。
得られた酸化チタン系光触媒薄膜について、下記に示す膜厚測定を行い、そして上記の光触媒活性の評価法で光触媒活性を測定して、膜厚の変化及びプラズマ処理の有無による光触媒活性の変化を評価した。その結果を下記表１に示す。
[Examples 1 to 3 and Comparative Examples 1 to 3 ]
A 25 μm-thick base film made of PET (polyethylene terephthalate) film was cut into 7 cm × 7 cm. The surface of the cut base film was coated with the following titanium oxide photocatalyst coating solution using a dip coater MICRODIP MD0408 (trade name, manufactured by EINTESLA) at a lifting speed of 0.1 mm / sec to 1.0 mm / sec. . Each of the air-dried thin films was heated at 80 ° C. for 30 minutes to obtain a completely dried titanium oxide photocatalyst thin film. Next, plasma treatment was performed on the titanium oxide photocatalyst thin film surface under the plasma treatment conditions shown below in Examples 1 to 3 and Comparative Example 1 .
About the obtained titanium oxide photocatalyst thin film, the film thickness measurement shown below is performed, and the photocatalytic activity is measured by the above-described evaluation method of photocatalytic activity. evaluated. The results are shown in Table 1 below.
・酸化チタン系光触媒塗液
市販のサガンコート（商品名TPXゾル、アナターゼ型ペルオキソチタン含有二酸化チタン水分散液、ペルオキソチタン固形分濃度０．８５質量％、鯤コーポレーション製）を使用した。
-Titanium oxide photocatalyst coating solution A commercially available sagan coat (trade name TPX sol, anatase-type peroxotitanium-containing titanium dioxide aqueous dispersion, peroxotitanium solid content concentration 0.85 mass%, manufactured by Sakai Corporation) was used.
・酸化チタン系光触媒薄膜のプラズマ処理
小型バッチ式プラズマ処理機PC-300（商品名、SAMCO製）によりプラズマ処理を実施した。高周波電源13.56MHz/250W、酸素又は窒素のガス圧力12Pa、処理時間60秒である。
-Plasma treatment of titanium oxide photocatalyst thin film Plasma treatment was carried out with a small batch type plasma treatment machine PC-300 (trade name, manufactured by SAMCO). High frequency power supply 13.56MHz / 250W, oxygen or nitrogen gas pressure 12Pa, treatment time 60 seconds.
・酸化チタン系光触媒薄膜の膜厚測定
光触媒薄膜の膜厚は、薄膜測定装置FILMETRICS F20（商品名、松下テクノトレーディング製）及び走査型電子顕微鏡S-3400NX（商品名、日立ハイテクノロジーズ）を用いて測定した。
・ Measurement of film thickness of titanium oxide photocatalytic thin film The film thickness of the photocatalytic thin film is measured using a thin film measuring device FILMETRICS F20 (trade name, manufactured by Matsushita Techno Trading) and a scanning electron microscope S-3400NX (trade name, Hitachi High-Technologies). It was measured.
＊１：光触媒活性は、測定開始10分後のメチレンブルー吸光度の変化量×103。
* 1: The photocatalytic activity of methylene blue absorbance after start of measurement 10 minutes variation × 10 3.
［実施例４〜９及び比較例３〜４］
基材として表２に示す樹脂フィルムを使用し、実施例４及び５では酸化チタン系薄膜の形成にティオスカイコート（商品名TAK-A、ペルオキソチタン含有二酸化チタンの水分散体、ペルオキソチタン固形分濃度０．８５質量％、ティオテクノ製）を使用した以外は実施例１または比較例２と同様にして酸化チタン系光触媒薄膜を製造し、その光触媒活性を実施例１と同様に測定して、基材別の光触媒活性、及びプラズマ処理の有無による光触媒活性の変化を評価した。その結果を下記表２に示す。
[Examples 4 to 9 and Comparative Examples 3 to 4 ]
The resin film shown in Table 2 was used as the substrate, and in Examples 4 and 5 , Tio Sky Coat (trade name TAK-A, aqueous dispersion of peroxotitanium-containing titanium dioxide, peroxotitanium solid content was used to form a titanium oxide thin film. A titanium oxide photocatalyst thin film was produced in the same manner as in Example 1 or Comparative Example 2 except that a concentration of 0.85% by mass, manufactured by Tiotechno) was used, and its photocatalytic activity was measured in the same manner as in Example 1. The photocatalytic activity for each substrate and the change in photocatalytic activity with and without plasma treatment were evaluated. The results are shown in Table 2 below.
＊２：光触媒活性は、測定開始10分後のメチレンブルー吸光度の変化量×103。
* 2: The photocatalytic activity of methylene blue absorbance after start of measurement 10 minutes variation × 10 3.
［実施例１０及び比較例５〜８］
酸化チタン系薄膜の形成に、比較例ではペルオキソチタンを含まないMPT-623（商品名、石原産業製）の1.0質量％水分散体、又はペルオキソチタンを含まないビストレイター（商品名、日本曹達製）を使用し、それ以外は実施例１又は比較例２と同様にして酸化チタン系光触媒薄膜を製造し、その光触媒活性を実施例１と同様に測定して、酸化チタン系薄膜のペルオキソチタン含有／非含有による光触媒活性の変化を評価した。その結果を下記表３に示す。
[Example 10 and Comparative Examples 5 to 8 ]
For the formation of titanium oxide thin films, in the comparative example, 1.0 mass% aqueous dispersion of MPT-623 (trade name, manufactured by Ishihara Sangyo) which does not contain peroxotitanium, or bis-traiter (trade name, manufactured by Nippon Soda Co., Ltd.) which does not contain peroxotitanium. ), And a titanium oxide photocatalyst thin film was produced in the same manner as in Example 1 or Comparative Example 2, and the photocatalytic activity was measured in the same manner as in Example 1, and the titanium oxide thin film contained peroxotitanium. / The change in photocatalytic activity due to the absence was evaluated. The results are shown in Table 3 below.
表１〜３の結果から、酸化チタン系薄膜の形成にペルオキソチタンを含有する酸化チタン系材料を使用し、且つ酸化チタン系薄膜の形成後にプラズマ処理した場合に、光触媒活性が著しく向上することがわかる。 From the results shown in Tables 1 to 3, the photocatalytic activity is remarkably improved when a titanium oxide-based material containing peroxotitanium is used to form a titanium oxide-based thin film and plasma treatment is performed after the formation of the titanium oxide-based thin film. Recognize.
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