JP3851935B2 - Photocatalyst production method - Google Patents
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- JP3851935B2 JP3851935B2 JP2003283656A JP2003283656A JP3851935B2 JP 3851935 B2 JP3851935 B2 JP 3851935B2 JP 2003283656 A JP2003283656 A JP 2003283656A JP 2003283656 A JP2003283656 A JP 2003283656A JP 3851935 B2 JP3851935 B2 JP 3851935B2
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- titanium oxide
- photocatalytic
- film
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- production method
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- 239000011941 photocatalyst Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 3
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本発明は、光触媒酸化チタン膜とその製造方法に関する。 The present invention relates to a photocatalytic titanium oxide film and a method for producing the same.
紫外線の照射により有機物を分解する光触媒酸化チタンを応用した素材開発が盛んに行われている。その中で薄膜作成法による光触媒酸化チタンの被覆も数多く試みられている。光触媒の市場が拡大するための要因の１つに、繊維やプラスチックなどの有機高分子材料表面への光触媒酸化チタンを担持する方法の確立が挙げられている。即ち有機基材に直接酸化チタンを被覆すれば基材自身が光触媒反応を受け脆化する。そのためそれを防ぐ酸化チタンの担持法の開発が望まれており、薄膜作成の分野においても、これまでに有機基材の脆化防止を目的とした光触媒酸化チタン膜の担持方法が提案されている。（例えば、特許文献１、特許文献２。） Material development using photocatalytic titanium oxide, which decomposes organic substances by ultraviolet irradiation, has been actively conducted. Among them, many attempts have been made to coat photocatalytic titanium oxide by a thin film preparation method. One factor for the expansion of the photocatalyst market is the establishment of a method for supporting photocatalytic titanium oxide on the surface of organic polymer materials such as fibers and plastics. That is, if the organic substrate is directly coated with titanium oxide, the substrate itself undergoes a photocatalytic reaction and becomes brittle. Therefore, it is desired to develop a method for supporting titanium oxide to prevent this, and in the field of thin film preparation, a method for supporting a photocatalytic titanium oxide film for the purpose of preventing embrittlement of an organic substrate has been proposed. . (For example, Patent Document 1 and Patent Document 2)
特許文献１では基材の劣化を防止するための下地膜として金属薄膜（Ａｇ、Ｎｉ、Ｃｕ、Ａｕ、Ｔｉ、Ａｌ、Ｐｔ、Ｐｄ等）あるいは金属酸化物薄膜（ＳｉＯ、ＳｉＯ２、Ａｌ２Ｏ３、ＳｎＯ２等）を、また、特許文献２では耐食性被膜として二酸化珪素、酸化アルミニウムまたは酸化ジルコニウムを形成させることをそれぞれ提案している。
しかし、金属薄膜を下地膜として形成させることは不透明になり基材の意匠効果をなくすことになり、また、金属によってはその上に被覆された光触媒により酸化を受ける。一方、金属酸化物薄膜を下地とする両提案とも下地の組成が光触媒層の組成と異なり、光触媒薄膜層への下地層組成の混入による光触媒性能の低下の恐れがある。また、下地層と光触媒層を積層させるにはターゲットの交換が必要となる。
However, when a metal thin film is formed as a base film, it becomes opaque and the design effect of the substrate is lost, and some metals are oxidized by a photocatalyst coated thereon. On the other hand, in both proposals using a metal oxide thin film as a base, the composition of the base is different from the composition of the photocatalyst layer, and the photocatalytic performance may be deteriorated due to the mixture of the base layer composition into the photocatalytic thin film layer. In addition, the target needs to be replaced in order to stack the underlayer and the photocatalyst layer.
以上のことから、薄膜の透明性を活かし、有機基材の脆化を防ぐ構造を持ち、そしてできるだけ少ない処理工程で光触媒膜を作成する方法の開発が課題となる。 From the above, the development of a method for making a photocatalytic film having the structure that prevents the embrittlement of the organic base material by utilizing the transparency of the thin film and with as few processing steps as possible becomes an issue.
本発明者等は、ターゲットとして金属チタンを用いてスパッタリングすることによって、有機基材表面に非晶質の酸化チタン層を形成させ、続いてさらにその上に少なくともアナターゼタイプの結晶を含む酸化チタン層を形成させることで上記課題を解決できることを見いだした。 The inventors of the present invention formed an amorphous titanium oxide layer on the surface of an organic base material by sputtering using metal titanium as a target, and then further a titanium oxide layer containing at least anatase type crystals thereon. It was found that the above problems can be solved by forming
この方法で形成される酸化チタン膜は非晶質層とアナターゼタイプの結晶を含む層との２層構造になっている。有機基材と接している非晶質の酸化チタン層は光触媒活性がなく、また、化学的に安定な酸化物であるため、その上に積層された光触媒活性を有するアナターゼタイプの結晶を含む酸化チタン層の光触媒による酸化作用から保護する役割をもつ。 The titanium oxide film formed by this method has a two-layer structure of an amorphous layer and a layer containing anatase type crystals. Since the amorphous titanium oxide layer in contact with the organic substrate has no photocatalytic activity and is a chemically stable oxide, it contains an anatase type crystal having photocatalytic activity laminated thereon. It has a role to protect the titanium layer from oxidation by the photocatalyst.
この方法により、１つのターゲットかつ１バッチという少ない工程で有機基材表面に保護層と光触媒活性層が積層した酸化チタン膜が形成される。 By this method, a titanium oxide film in which a protective layer and a photocatalytic active layer are laminated on the surface of an organic base material is formed with a small number of steps of one target and one batch.
金属チタンをターゲットとして用い、スパッタリング装置内へのアルゴン−酸素混合ガスの導入量および成膜電力を調節して、基板上に先ず非晶質の酸化チタン層を形成させ、引き続きその上にアナターゼタイプの結晶を含む酸化チタン層を形成させる。 First, an amorphous titanium oxide layer is formed on the substrate by adjusting the amount of argon-oxygen mixed gas introduced into the sputtering apparatus and the deposition power by using titanium metal as a target, and then anatase type on the substrate. A titanium oxide layer containing the crystal is formed.
マグネトロンスパッタリング装置で、ターゲットとして金属チタン（フルウチ化学(株)）を用い、アルゴンガスおよび酸素ガス（配合比 ２：１）を導入しながら、ポリエステルフィルム（６×６cm）上に、チャンバー圧力５．０Ｐａ、供給電力３００ｗで６０分処理した。なお、この条件でポリエステルフィルム表面に形成された酸化チタンの結晶形態は非晶質であることを、前もって、スパッタ時間を長くしたもので薄膜Ｘ線回折装置により確認している。 In a magnetron sputtering apparatus, metal titanium (Furuuchi Chemical Co., Ltd.) was used as a target, and while introducing argon gas and oxygen gas (mixing ratio 2: 1), a chamber pressure of 5.6 on a polyester film (6 × 6 cm). The treatment was performed at 0 Pa and supply power of 300 w for 60 minutes. Note that it has been confirmed in advance by a thin film X-ray diffractometer that the sputter time is long and the crystal form of the titanium oxide formed on the surface of the polyester film under this condition is amorphous.
このスパッタリング処理したフィルム表面に１０ｐｐｍのメチレンブルー水溶液を０．１ｍｌ滴下し、ブラックライト（紫外線（３１０〜４００ｎｍ）強度１０Ｗ／m2）で１時間照射後の呈色の有無を調べたところ、青色が残っており光触媒活性はみられなかった。 When 0.1 ml of a 10 ppm methylene blue aqueous solution was dropped on the surface of the film subjected to the sputtering treatment and the presence or absence of coloration after irradiation for 1 hour with black light (ultraviolet (310 to 400 nm) intensity 10 W / m 2 ) was examined, It remained and no photocatalytic activity was observed.
実施例１と同じ条件で先ず非晶質の酸化チタン層を形成させ、次に取り出すことなくそのまま引き続き、チャンバー圧力および供給電力をそれぞれ０．５Ｐａおよび５００ｗに変えてさらに６０分スパッタリング処理をした。後者の条件で形成される酸化チタンはアナターゼタイプであることを、スパッタリング時間を長くしたもので、前もって、同様に確認している。 First, an amorphous titanium oxide layer was formed under the same conditions as in Example 1, and then, without removing them, the chamber pressure and supply power were changed to 0.5 Pa and 500 w, respectively, and sputtering was further performed for 60 minutes. The titanium oxide formed under the latter condition is anatase type with a longer sputtering time, and has been confirmed in advance as well.
このスパッタリング処理したフィルム表面に１０ｐｐｍのメチレンブルー水溶液を０．１ｍｌ滴下し、ブラックライト（紫外線（３１０〜４００ｎｍ）強度１０Ｗ／m2）で１時間照射後の呈色の有無を調べたところ、青色が完全に消え光触媒活性が示された。
When 0.1 ml of a 10 ppm methylene blue aqueous solution was dropped on the surface of the film subjected to the sputtering treatment and the presence or absence of coloration after irradiation for 1 hour with black light (ultraviolet (310 to 400 nm) intensity 10 W / m 2 ) was examined, It completely disappeared and showed photocatalytic activity.
Claims (1)
A photocatalyst characterized in that an amorphous titanium oxide layer is formed on a substrate by sputtering using metallic titanium as a target, and then a titanium oxide layer containing at least anatase type crystals is further formed thereon. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003283656A JP3851935B2 (en) | 2003-07-31 | 2003-07-31 | Photocatalyst production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003283656A JP3851935B2 (en) | 2003-07-31 | 2003-07-31 | Photocatalyst production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005046793A JP2005046793A (en) | 2005-02-24 |
| JP3851935B2 true JP3851935B2 (en) | 2006-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003283656A Expired - Fee Related JP3851935B2 (en) | 2003-07-31 | 2003-07-31 | Photocatalyst production method |
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| Country | Link |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5700485B2 (en) * | 2010-12-27 | 2015-04-15 | 芝浦メカトロニクス株式会社 | Photocatalyst body manufacturing method and photocatalyst body manufacturing apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3863620B2 (en) * | 1997-02-24 | 2006-12-27 | 株式会社ティオテクノ | Photocatalyst and method for producing the same |
| JP2003019764A (en) * | 2001-07-09 | 2003-01-21 | Achilles Corp | Decorative sheet with photocatalytic function |
| JP2003049265A (en) * | 2001-08-08 | 2003-02-21 | Toto Ltd | Film deposition method for photocatalytic titanium dioxide film |
| JP2003137603A (en) * | 2001-10-25 | 2003-05-14 | Sun Tec Corp Kk | Thermally tempered glass formed body having photocatalyst layer and method of manufacturing the same |
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| JP2005046793A (en) | 2005-02-24 |
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