JP2001207082A - Hydrophilic material - Google Patents
Hydrophilic materialInfo
- Publication number
- JP2001207082A JP2001207082A JP2000017634A JP2000017634A JP2001207082A JP 2001207082 A JP2001207082 A JP 2001207082A JP 2000017634 A JP2000017634 A JP 2000017634A JP 2000017634 A JP2000017634 A JP 2000017634A JP 2001207082 A JP2001207082 A JP 2001207082A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- substance
- water storage
- photocatalytic
- titanium oxide
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 79
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 230000001699 photocatalysis Effects 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims description 32
- 238000003860 storage Methods 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- 239000011232 storage material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000003426 co-catalyst Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011593 sulfur Substances 0.000 abstract description 21
- 229910011210 Ti—O—N Inorganic materials 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 34
- 229910010413 TiO 2 Inorganic materials 0.000 description 15
- 238000010586 diagram Methods 0.000 description 14
- 238000005299 abrasion Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000011941 photocatalyst Substances 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005468 ion implantation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 229910019899 RuO Inorganic materials 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- -1 hydroxyl ions Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001616 ion spectroscopy Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、可視光で光触媒反
応を生起して親水性を発揮する親水性材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic material which exhibits a photocatalytic reaction with visible light to exhibit hydrophilicity.
【０００２】[0002]
【従来の技術】従来より、光触媒材料として、ＴｉＯ2
（酸化チタン：チタニア）、ＣｄＳ（硫化カドミニウ
ム）、ＷＯ3（三酸化タングステン）、ＺｎＯ（酸化亜
鉛）等、数多くのものが知られている。これらの光触媒
材料は、光を吸収して電子と正孔を生成する。従って、
それらの酸化・還元反応により表面に、抗菌性、防汚
性、防曇性等を付与できる。ここで、現在まで、光触媒
として実用化されているものは、ＴｉＯ2のみである。
これは、ＴｉＯ2が、毒性および材料自体の安定性（耐
酸性、耐アルカリ性等）の観点で他の材料に比べ優れて
いるからである。また、酸化チタンの中では、アナター
ゼ構造の方がより光触媒活性が高いということで多く使
用されている。例えば、特許２７５６４７４号公報、２
８６５０６５号公報等においては、基本的に、このアナ
ターゼ型チタニアと蓄水性（親水性）のシリカ（ＳｉＯ
2）とを複合したり、積層したりして、親水性を実現し
ている。 2. Description of the Related Art Conventionally, TiO 2 has been used as a photocatalytic material.
(Titanium oxide: titania), CdS (cadmium sulfide), WO 3 (tungsten trioxide), ZnO (zinc oxide) and many others are known. These photocatalytic materials absorb light to generate electrons and holes. Therefore,
Antibacterial properties, antifouling properties, antifogging properties, etc. can be imparted to the surface by these oxidation / reduction reactions. Here, only TiO 2 has been put to practical use as a photocatalyst until now.
This is because TiO 2 is superior to other materials in terms of toxicity and stability of the material itself (acid resistance, alkali resistance, etc.). In addition, among titanium oxides, an anatase structure is more often used because of its higher photocatalytic activity. For example, Japanese Patent No. 2756474, 2
No. 865065 and the like, basically, this anatase type titania and water storage (hydrophilic) silica (SiO 2
2 ) is combined or laminated to achieve hydrophilicity.
【０００３】[0003]
【発明が解決しようとする課題】しかし、チタニアは、
吸収できる光が紫外光に限られており、太陽光や蛍光灯
光などを効率的に利用することができないという問題が
あった。すなわち、アナターゼ型酸化チタンのバンドギ
ャップが約３．２ｅＶで、３８０ｎｍ以下の波長の紫外
線でのみ光触媒活性を呈する。このため、太陽光の下で
は若干は活性があるものの、約４００ｎｍ〜８００ｎｍ
の可視光では活性がなく、蛍光灯やランプが利用されて
いる室内や車内では十分な親水の効果を得ることは全く
困難であった。However, titania is
Light that can be absorbed is limited to ultraviolet light, and there has been a problem that sunlight and fluorescent light cannot be used efficiently. That is, the band gap of the anatase type titanium oxide is about 3.2 eV, and the photocatalytic activity is exhibited only by ultraviolet rays having a wavelength of 380 nm or less. For this reason, although slightly active under sunlight, about 400 nm to 800 nm
Has no activity with visible light, and it has been quite difficult to obtain a sufficient hydrophilic effect in a room or a car where a fluorescent lamp or a lamp is used.
【０００４】この欠点を改良した酸化チタンとしては、
特開平９−２６２４８２号公報に記載されたものが知ら
れている。この公報では、チタニアに、Ｃｒ（クロ
ム）、Ｖ（バナジウム）などの金属をイオン注入して、
可視域でも光吸収し光触媒動作を可能にしている。しか
し、Ｃｒ，Ｖ等のドーピングについては、１９７０年代
前半から数多くの報告があるが、これらの報告では可視
光での動作が可能になったとはしていなく、特開平９−
２６２４８２号公報は、Ｃｒ，Ｖ等のドーピングの手法
をイオン注入という特別なものとすることで、可視光に
おける動作を可能としたものである。[0004] As titanium oxide which has improved this disadvantage,
Japanese Patent Application Laid-Open No. 9-262482 is known. In this publication, a metal such as Cr (chromium) and V (vanadium) is ion-implanted into titania,
It absorbs light even in the visible range and enables photocatalytic operation. However, there have been many reports on doping of Cr, V, and the like since the early 1970's. However, these reports do not indicate that operation with visible light is possible,
Japanese Patent Publication No. 264822 discloses an operation in visible light by using a special doping method such as ion implantation of Cr, V or the like.
【０００５】そして、イオン注入法は半導体産業におい
て一般化された方法ではあるが、装置が大がかりで運転
コストも非常に高く、汎用性の光触媒の製造にそのまま
適用することは難しい。Although the ion implantation method is a method generalized in the semiconductor industry, it is difficult to apply the ion implantation method as it is to the production of a general-purpose photocatalyst because the apparatus is large and the operation cost is very high.
【０００６】また、特開平１０−３１０６５３号公報で
は、ＷＯ3やＦｅ2Ｏ3等の光半導体材料を用いて、可視
域でも光吸収し光触媒動作を可能にした親水性部材が提
案されている。しかし、ここで提案されている材料は、
化学的な安定性がなく、酸性またはアルカリ性の溶液に
よって溶出し、実用性に乏しい。Japanese Patent Application Laid-Open No. Hei 10-310653 proposes a hydrophilic member that uses a photo-semiconductor material such as WO 3 or Fe 2 O 3 to absorb light even in the visible region and to enable photocatalytic operation. . However, the materials proposed here are:
It has no chemical stability, is eluted by acidic or alkaline solutions, and is not practical.
【０００７】本発明は、上記課題に鑑みなされたもので
あり、可視光で機能する光触媒性の親水材料であって、
実用的なものを提供することを目的とする。The present invention has been made in view of the above problems, and is a photocatalytic hydrophilic material that functions with visible light,
The aim is to provide something practical.
【０００８】[0008]
【課題を解決するための手段】本発明は、酸化チタン結
晶の酸素サイトの一部を窒素原子で置換、酸化チタン結
晶の格子間に窒素原子をドーピング、あるいは酸化チタ
ン結晶の多結晶集合体の粒界に窒素原子を配してなる光
触媒物質と、蓄水性を有する蓄水性物質と、を含み、基
板上に層を形成し得ることを特徴とする。According to the present invention, a part of the oxygen site of a titanium oxide crystal is replaced with a nitrogen atom, a nitrogen atom is doped between lattices of the titanium oxide crystal, or a polycrystalline aggregate of the titanium oxide crystal is formed. It includes a photocatalyst substance in which nitrogen atoms are arranged in grain boundaries and a water storage substance having water storage properties, and is characterized in that a layer can be formed on a substrate.
【０００９】また、本発明は、酸化チタン結晶の酸素サ
イトの一部をイオウ原子で置換、格子間にイオウ原子を
ドーピング、あるいは多結晶集合体の粒界にイオウ原子
を配してなる光触媒物質と、蓄水性を有する蓄水性物質
と、を含み、基板上に層を形成し得ることを特徴とす
る。Further, the present invention provides a photocatalytic substance comprising a titanium oxide crystal in which a part of oxygen sites are replaced with sulfur atoms, sulfur atoms are doped between lattices, or sulfur atoms are arranged at grain boundaries of a polycrystalline aggregate. And a water-storing substance having a water-storing property, and a layer can be formed on the substrate.
【００１０】酸化チタンに窒素またはイオウをドープす
ることにより、酸素が支配する半導体の価電子帯が影響
を受け、ＴｉＯ2酸化物のバンドギャップの内側に新し
いエネルギー準位が形成され、バンドギャップが狭くな
る。その結果、紫外線より長波長の可視光をも吸収し
て、電子と正孔を生成することが可能となる。これらの
生成した電子と正孔は、蓄水性物質に含まれる水と反応
して、水酸イオン等を生成する。この生成した水酸基
は、光触媒性物質および蓄水性物質の表面に水に対して
非常に濡れやすい状態を形成し、親水性を発現する。さ
らに、生成した電子と正孔は、表面に付着した有機物等
を分解する。また、本発明の光触媒性物質は、化学的に
安定なＴｉＯ2をベースに使用しているので、耐環境性
を有している。By doping titanium oxide with nitrogen or sulfur, the valence band of the semiconductor dominated by oxygen is affected, and a new energy level is formed inside the band gap of the TiO 2 oxide. Narrows. As a result, it becomes possible to absorb even visible light having a wavelength longer than that of ultraviolet rays and generate electrons and holes. These generated electrons and holes react with water contained in the water storage material to generate hydroxyl ions and the like. The generated hydroxyl group forms a state of being very wettable with water on the surface of the photocatalytic substance and the water storage substance, and expresses hydrophilicity. Further, the generated electrons and holes decompose organic substances and the like attached to the surface. Further, the photocatalytic substance of the present invention has environmental resistance since it is based on chemically stable TiO 2 .
【００１１】また、前記蓄水性物質は、少なくとも酸化
シリコンを含むことが好適である。酸化シリコンは、蓄
水性物質であり、親水性を改善できるだけでなく、硬度
的にも硬く、層自体の耐摩耗性等の機械的強度も向上す
る。Further, it is preferable that the water storage material contains at least silicon oxide. Silicon oxide is a water storage material, and can improve not only hydrophilicity but also hardness, and also enhances mechanical strength such as abrasion resistance of the layer itself.
【００１２】また、前記光触媒物質と蓄水性物質とは複
合されて１つの複合層に形成されてもよいし、それぞれ
層状に形成されこれらが積層されていてもよい。いずれ
の構成においても、光触媒物質と蓄水性物質の相乗作用
により十分な親水性能を得ることができる。The photocatalyst substance and the water storage substance may be combined to form a single composite layer, or they may be formed in layers and laminated. In any configuration, a sufficient hydrophilic property can be obtained by the synergistic action of the photocatalytic substance and the water storage substance.
【００１３】また、前記複合層の表面近傍に、Ｐｔ、Ｐ
ｄ、Ｎｉ、ＲｕＯX、ＮｉＯx、ＳｎＯxのうちの少なく
とも１種の助触媒物質を担持させたり、光触媒物質層と
蓄水性物質層との境界領域に、Ｐｔ、Ｐｄ、Ｎｉ、Ｒｕ
ＯX、ＮｉＯx、ＳｎＯxのうちの少なくとも１種の助触
媒物質を担持させることが好適である。In the vicinity of the surface of the composite layer, Pt, P
d, Ni, RuO x , NiO x , SnO x , at least one type of co-catalyst material, or Pt, Pd, Ni, Ru at a boundary region between the photocatalytic material layer and the water storage material layer.
It is preferable to support at least one co-catalyst substance of O x , NiO x , and SnO x .
【００１４】これら助触媒は、電子または正孔を捕捉す
る機能を有する。従って、これを配置することによっ
て、電子と正孔の再結合を防止することができ、光触媒
機能の劣化を防止することができる。These cocatalysts have a function of capturing electrons or holes. Therefore, by arranging them, recombination of electrons and holes can be prevented, and deterioration of the photocatalytic function can be prevented.
【００１５】前記光触媒物質層と、蓄水性物質層との間
に酸化チタンからなる層を有することが好適である。酸
化チタンは親水性を発揮するのに非常に好適な物質であ
り、酸化チタンの層を含むことによって、親水性の向上
を図ることができる。It is preferable that a layer made of titanium oxide is provided between the photocatalytic substance layer and the water storage substance layer. Titanium oxide is a substance that is very suitable for exhibiting hydrophilicity. By including a layer of titanium oxide, the hydrophilicity can be improved.
【００１６】また、本発明は、Ｔｉ、Ｚｎ、Ｓｎの中か
ら少なくとも１種選択された第１物質と、Ｖ、Ｃｒ、Ｍ
ｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｒｕ、Ｒｈ、Ｒ
ｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ｐｄの中から少なくとも１種選
択された第２物質と、これらの複合酸化物の酸素サイト
との一部を窒素原子またはイオウ原子で置換、複合酸化
物の格子間に窒素原子またはイオウ原子をドーピング、
あるいは複合酸化物の多結晶集合体の粒界に窒素原子ま
たはイオウ原子を配してなる光触媒物質と、蓄水性を有
する蓄水性物質と、を含み、基板上に層を形成し得るこ
とを特徴とする。Further, the present invention provides a method for manufacturing a semiconductor device, comprising: a first material selected from at least one of Ti, Zn, and Sn;
n, Fe, Co, Ni, Cu, Zn, Ru, Rh, R
e, a second substance selected from Os, Ir, Pt, and Pd, and a part of the oxygen site of these composite oxides are replaced with nitrogen atoms or sulfur atoms, and the interstitial of the composite oxides is removed. Doping with nitrogen or sulfur atoms,
Alternatively, a layer containing a photocatalyst substance in which nitrogen atoms or sulfur atoms are arranged at grain boundaries of a polycrystalline aggregate of a composite oxide and a water storage substance having water storage ability can be formed on a substrate. It is characterized by.
【００１７】光触媒物質としては、チタニアだけでなく
ＺｎＯ、ＳｎＯXも利用することができ、これらについ
ても窒素またはイオウおよびＶ、Ｃｒ等の遷移金属をド
ープすることにより半導体の伝導帯ならびに価電子帯が
影響を受け、金属酸化物のバンドギャップの内側に新し
いエネルギー準位が形成され、バンドギャップが狭くな
る。従って、吸収する光を長波長側にシフトすることが
でき、可視光を動作光としてより好適な親水性能を発揮
することができる。[0017] The photocatalytic material, ZnO well titania, also SnO X can be used, a semiconductor conduction band and valence band by doping a transition metal, such as nitrogen or sulfur and V, Cr also these Is affected, a new energy level is formed inside the band gap of the metal oxide, and the band gap is narrowed. Therefore, the light to be absorbed can be shifted to the longer wavelength side, and more suitable hydrophilic performance can be exhibited using visible light as operating light.
【００１８】[0018]
【発明の実施の形態】「実施形態１」図１は実施形態１
の構成を示す図である。基材１１の表面に、光触媒物質
と蓄水物質の複合層１２が形成されている。この複合層
１２は、酸化チタン結晶の酸素のサイトの一部を窒素ま
たはイオウで置換したＴｉ−Ｏ−ＮまたはＴｉ−Ｏ−Ｓ
構成を有し、可視光域において光触媒作用を発現する光
触媒物質と、ＳｉＯ2、ＳｉＯ等の蓄水物質とを複合し
た複合層であり、親水性を示す。DESCRIPTION OF THE PREFERRED EMBODIMENTS First Embodiment FIG.
FIG. 3 is a diagram showing the configuration of FIG. A composite layer 12 of a photocatalytic substance and a water storage substance is formed on the surface of a substrate 11. This composite layer 12 is made of Ti—O—N or Ti—O—S in which part of the oxygen sites of the titanium oxide crystal is replaced with nitrogen or sulfur.
It is a composite layer having a configuration and a composite of a photocatalytic substance that exhibits a photocatalytic action in the visible light region and a water storage substance such as SiO 2 or SiO, and exhibits hydrophilicity.
【００１９】基材１１には、板ガラス、セラミックス基
板等が使用できる。また、複合層１２を構成する光触媒
物質は、酸化チタン（ＴｉＯ2）結晶の酸素サイトの一
部が窒素またはイオウで置換された構造を基本的に有し
ている。なお、酸化チタン結晶の格子間に窒素またはイ
オウがドーピングされた構造や多結晶集合体の粒界に窒
素原子またはイオウが配された構成でもよく、これらが
混在していてもよい。As the substrate 11, a plate glass, a ceramic substrate or the like can be used. In addition, the photocatalytic substance constituting the composite layer 12 basically has a structure in which a part of oxygen sites of a titanium oxide (TiO 2 ) crystal is replaced with nitrogen or sulfur. Note that a structure in which nitrogen or sulfur is doped between lattices of the titanium oxide crystal or a structure in which nitrogen atoms or sulfur is arranged at grain boundaries of a polycrystalline aggregate may be used, or a mixture of these may be used.
【００２０】しかし、Ｔｉと、ＮまたはＳとは、直接の
化学結合を有している。例えば、Ｔｉ−Ｏ−Ｎにおいて
は、Ｍｇ−ＫαＸ線を用いたＸＰＳ（X-ray Photoemiss
ionSpectroscopy）による窒素Ｎの１ｓ殻の測定結果に
おいて窒素原子は、３９６〜３９７ｅＶ付近にＴｉ−Ｎ
結合に由来するピークを示す。However, Ti and N or S have a direct chemical bond. For example, in Ti-ON, XPS (X-ray Photoemiss) using Mg-Kα X-ray is used.
In the measurement result of the 1 s shell of nitrogen N by ion spectroscopy), the nitrogen atom is Ti-N near 396 to 397 eV.
The peak resulting from the binding is shown.
【００２１】また、Ｔｉ−Ｏ−ＮまたはＴｉ−Ｏ−Ｓの
組成比は、０＜（ＮまたはＳ）＜１３％である。酸化チ
タン結晶はルチルでもアナターゼでもよい。また、蓄水
物質は、ＳｉＯ2、ＳｉＯ、Ｔａ2Ｏ5等の水が吸着しや
すい材料であり、構造は結晶性でも無定型でもかまわな
い。The composition ratio of Ti-ON or Ti-OS is 0 <(N or S) <13%. The titanium oxide crystal may be rutile or anatase. The water storage material is a material such as SiO 2 , SiO, and Ta 2 O 5 to which water is easily adsorbed, and may have a crystalline or amorphous structure.
【００２２】これらの光触媒物質および蓄水物質を複合
して基材１１の表面に複合層１２を形成する。ここで、
複合する比率は、光触媒物質および蓄水物質がともに含
まれていればよく、さらには光触媒物質が、５〜９５％
含まれていればよい。なお、複合層１２を形成すると
き、光触媒物質の結晶性が保持される必要がある。A composite layer 12 is formed on the surface of the substrate 11 by combining the photocatalytic substance and the water storage substance. here,
The compounding ratio may be such that the photocatalyst substance and the water storage substance are both contained.
It only has to be included. Note that when forming the composite layer 12, it is necessary to maintain the crystallinity of the photocatalytic substance.
【００２３】特に、本実施形態の親水材料をミラーや窓
ガラス等可視光の透過する用途に適用する場合、光触媒
物質は可視光を一部吸収するので、蓄水物質にＳｉＯ2
等の透明な材料を使用し、層厚および複合比率によっ
て、透明性および着色性を調整することが好ましい。[0023] In particular, when applying the hydrophilic material of the present embodiment the transmission to the use of mirrors and windowpanes visible light, since the photocatalytic material absorbs some of the visible light, SiO 2 in water storage material
It is preferable to use a transparent material such as the above and adjust the transparency and the coloring property according to the layer thickness and the composite ratio.
【００２４】次に、実施形態１の製造方法の一例である
Ｔｉ−Ｏ−ＮとＳｉＯ2の複合層１２の場合について説
明する。Next, the case of the composite layer 12 of Ti—O—N and SiO 2 , which is an example of the manufacturing method of Embodiment 1, will be described.
【００２５】まず、結晶性ＴｉＯ2微粒子をアンモニア
雰囲気下での７００℃熱処理によって、窒素をドーピン
グする。その微粒子と無機バインダーのコロイダルシリ
カを混合し、溶媒として水とエタノールを用いて塗布液
を作製する。この溶液を基材１１の表面に、塗布、スプ
レーまたはディッピングすることによって複合層１２を
形成する。その後室温乾燥後、１５０℃の熱処理を行い
安定化させる。First, the crystalline TiO 2 fine particles are doped with nitrogen by a heat treatment at 700 ° C. in an ammonia atmosphere. The fine particles and colloidal silica as an inorganic binder are mixed, and a coating liquid is prepared using water and ethanol as a solvent. The composite layer 12 is formed by applying, spraying or dipping this solution on the surface of the substrate 11. After drying at room temperature, a heat treatment at 150 ° C. is performed to stabilize.
【００２６】また、Ｔｉ−Ｏ−Ｎ微粒子は、ゾルゲル法
その他微粒子作製法において、酸化チタン結晶の酸素サ
イトの一部が窒素原子で置換されるような方法であれ
ば、どのような方法で作製してもよい。The Ti—O—N fine particles can be prepared by any method, such as a sol-gel method or other fine particle preparation method, in which a part of the oxygen sites of the titanium oxide crystal is replaced by nitrogen atoms. May be.
【００２７】イオウ導入の場合も同様である。ただし、
窒素やイオウが酸素と結合した状態、例えばＮＯ3、Ｓ
Ｏ3のような結合状態だけで酸化チタンに混入しても本
発明のような可視光応答性は発現できない。The same applies to the case of sulfur introduction. However,
Nitrogen or sulfur combined with oxygen, eg NO 3 , S
Even if it is mixed with titanium oxide only in a bonding state such as O 3, the visible light response as in the present invention cannot be exhibited.
【００２８】上記のようにして作製される本実施形態の
複合層１２は、紫外光だけでなく４００ｎｍ以上の波長
の可視光入射によっても光触媒機能が発現し、表面が親
水化する。さらに、その結果、汚れ防止および防曇性を
安定に維持することができる。しかも、イオン注入のよ
うな高価な方法ではないので、安価に製造することがで
きる。The composite layer 12 of the present embodiment produced as described above exhibits a photocatalytic function by not only ultraviolet light but also visible light having a wavelength of 400 nm or more, and the surface becomes hydrophilic. Further, as a result, the stain prevention and anti-fogging properties can be stably maintained. Moreover, since it is not an expensive method such as ion implantation, it can be manufactured at low cost.
【００２９】したがって、本発明の可視光応答親水材料
は、建築用のガラス板材、ミラー、車両用の板ガラス、
ミラー等、特に室内、車内の紫外線があたらない環境で
も、可視光照射によって親水性を発揮できる用途に利用
できる。Accordingly, the visible light responsive hydrophilic material of the present invention can be used for building glass plates, mirrors, plate glass for vehicles,
It can be used for applications such as mirrors, which can exhibit hydrophilicity by irradiating with visible light even in an environment where indoors and vehicles are not exposed to ultraviolet rays.
【００３０】「実施形態２」図２は、実施形態２の構成
を示す図である。この実施形態２では、実施形態１の構
成に、Ｐｔ、Ｐｄ、Ｎｉ、ＲｕＯx、ＮｉＯx、ＳｎＯx
のいずれか一種類以上の助触媒１３を坦持した構成を有
する。助触媒１３により、紫外光だけでなく可視光に対
する光触媒活性が向上する。これは、基本的に、これら
の助触媒が電子または正孔を捕捉する機能を有してお
り、光触媒反応によって生成された電子、正孔の再結合
が防止されることによる。[Second Embodiment] FIG. 2 is a diagram showing a configuration of a second embodiment. In the second embodiment, Pt, Pd, Ni, RuO x , NiO x , and SnO x are added to the configuration of the first embodiment.
Of any one of the above types. The cocatalyst 13 improves the photocatalytic activity not only for ultraviolet light but also for visible light. This is basically because these cocatalysts have a function of capturing electrons or holes, and recombination of electrons and holes generated by the photocatalytic reaction is prevented.
【００３１】「実施形態３」図３は実施形態３の構成を
示す図である。基材１１の表面には、光触媒物質層１４
が形成されている。この光触媒物質層１４は、酸化チタ
ン結晶に、酸素のサイトの一部を窒素またはイオウで置
換したＴｉ−Ｏ−ＮまたはＴｉ−Ｏ−Ｓ構成を有し、可
視光域において光触媒作用を発現する。この光触媒物質
層１４の上には、ＳｉＯ2等の光を透過しかつ蓄水性の
蓄水物質層１５が形成されている。[Third Embodiment] FIG. 3 is a diagram showing a configuration of a third embodiment. A photocatalytic substance layer 14 is provided on the surface of the base material 11.
Are formed. The photocatalytic substance layer 14 has a titanium oxide crystal having a Ti-ON or Ti-OS configuration in which a part of oxygen sites is replaced with nitrogen or sulfur, and exhibits a photocatalytic action in a visible light region. . On this photocatalyst material layer 14, a water storage material layer 15 that transmits light such as SiO 2 and stores water is formed.
【００３２】光触媒物質層１４は、実施形態１の光触媒
物質で構成されており、酸化チタン結晶の酸素サイトの
一部が窒素またはイオウで置換された構造を基本的に有
している。なお、酸化チタン（ＴｉＯ2）結晶の格子間
に窒素またはイオウがドーピングされた構造や多結晶集
合体の粒界に窒素原子またはイオウが配された構成でも
よく、これらが混在していてもよい。The photocatalyst material layer 14 is made of the photocatalyst material of the first embodiment, and basically has a structure in which a part of oxygen sites of a titanium oxide crystal is replaced with nitrogen or sulfur. It should be noted that a structure in which nitrogen or sulfur is doped between lattices of titanium oxide (TiO 2 ) crystals or a structure in which nitrogen atoms or sulfur is arranged at grain boundaries of a polycrystalline aggregate may be used, or these may be mixed. .
【００３３】また、Ｔｉ−Ｏ−ＮまたはＴｉ−Ｏ−Ｓの
組成比は、０＜（ＮまたはＳ）＜１３％である。酸化チ
タン結晶はルチルでもアナターゼでもよい。また、透光
性かつ蓄水物質層１５は、ＳｉＯ2、ＳｉＯ、Ｔａ2Ｏ5
等の可視光を透過し（紫外線は透過してもしないでもよ
い）、かつ、水が吸着しやすい材料である。構造は結晶
性でも無定型でもかまわない。また、図３に示されるよ
うな均質な層でなくてもよく、凹凸があってもかまわな
い。なお、可視に対し透光性である必要は、光触媒物質
層１４において光触媒反応をおこすためである。この透
光性かつ蓄水物質層１５の層厚は、光触媒物質層１４に
おいて生成した電子と正孔が移動できる距離と関係す
る。すなわち、２ｎｍ以上かつ１００ｎｍ以下が好適で
ある。The composition ratio of Ti-ON or Ti-OS is 0 <(N or S) <13%. The titanium oxide crystal may be rutile or anatase. The translucent and water storage material layer 15 is made of SiO 2 , SiO, Ta 2 O 5
It is a material that transmits visible light (whether ultraviolet light may or may not be transmitted) and easily adsorbs water. The structure may be crystalline or amorphous. Further, the layer need not be a uniform layer as shown in FIG. 3 and may have irregularities. The translucency with respect to visible light is required to cause a photocatalytic reaction in the photocatalytic substance layer 14. The thickness of the translucent and water-storing substance layer 15 is related to the distance over which electrons and holes generated in the photocatalytic substance layer 14 can move. That is, the thickness is preferably 2 nm or more and 100 nm or less.
【００３４】次に、実施形態３の製造方法の一例につい
て説明する。ここでは、スパッタリング法を用いた方法
について示す。ガラス板等の用意した基材１１表面を洗
浄し、スパッタリング装置の真空チェンバー内にＴｉＯ
2ターゲットおよびＳｉＯ2ターゲットとともにセット
し、真空排気する。所定の真空度まで排気した後、Ａｒ
等の不活性ガスおよび窒素ガスを導入し、（Ａｒ＋
Ｎ2）プラズマ中でＴｉＯ2ターゲットをスパッタし、基
材表面にＴｉ−Ｏ−Ｎ層を形成する。その後、真空チェ
ンバー内もしくは一旦空気中に取り出した後、窒素雰囲
気中において、例えば５５０℃で熱処理する。この熱処
理によって、光触媒物質層１４を結晶化させる。そし
て、結晶化した光触媒物質層１４が形成された基材１１
上に、スパッタリング装置内において、（Ａｒ＋Ｏ2）
プラズマ中で、ＳｉＯ2ターゲットをスパッタし、透光
性かつ蓄水物質層１５であるＳｉＯ2層等を形成する。Next, an example of the manufacturing method according to the third embodiment will be described. Here, a method using a sputtering method is described. The surface of the prepared substrate 11 such as a glass plate is washed, and TiO is placed in a vacuum chamber of a sputtering apparatus.
2 sets with the target and SiO 2 targets, evacuated. After evacuation to a predetermined degree of vacuum, Ar
And an inert gas such as nitrogen,
N 2 ) A TiO 2 target is sputtered in plasma to form a Ti-ON layer on the surface of the base material. Thereafter, after being taken out of the vacuum chamber or once into the air, a heat treatment is performed at, for example, 550 ° C. in a nitrogen atmosphere. By this heat treatment, the photocatalytic substance layer 14 is crystallized. Then, the substrate 11 on which the crystallized photocatalytic substance layer 14 is formed
Above, in the sputtering apparatus, (Ar + O 2 )
In the plasma, an SiO 2 target is sputtered to form an SiO 2 layer or the like which is a translucent and water-storing substance layer 15.
【００３５】また、この積層構造である実施形態３を、
ゾルゲル法等別の手法によって作製してもよい。イオウ
導入の場合も同様である。ただし、窒素やイオウが酸素
と結合した状態、例えばＮＯ3、ＳＯ3のような結合状態
だけで酸化チタンに混入しても本発明のような可視光応
答性は発現できない。The third embodiment having the laminated structure is
It may be produced by another method such as a sol-gel method. The same applies to the case of sulfur introduction. However, even when nitrogen or sulfur is mixed with oxygen, for example, only in a bonded state such as NO 3 or SO 3 , the visible light responsiveness as in the present invention cannot be exhibited even when mixed with titanium oxide.
【００３６】上記のようにして作製される本発明は、紫
外光だけでなく４００ｎｍ以上の波長の可視光入射によ
っても光触媒機能が光触媒物質層１４において発現し、
透光性かつ蓄水物質層１５の表面が親水化する。さら
に、その結果、汚れ防止および防曇性を安定に維持する
ことができる。また、表面が透光性かつ蓄水物質層１５
であるので、材料としてＳｉＯ2、ＳｉＯのようなかた
い材料を選べば、耐摩耗性等がさらに向上する。According to the present invention prepared as described above, the photocatalytic function is exhibited in the photocatalytic substance layer 14 by not only ultraviolet light but also visible light having a wavelength of 400 nm or more,
The surface of the translucent and water storage material layer 15 becomes hydrophilic. Further, as a result, the stain prevention and anti-fogging properties can be stably maintained. Further, the surface is translucent and the water storage material layer 15 is formed.
Therefore, if a hard material such as SiO 2 or SiO is selected as the material, the wear resistance and the like are further improved.
【００３７】「実施形態４」図４は、実施形態４の構成
を示す図である。この実施形態４では、実施形態３の構
成において、Ｐｔ、Ｐｄ、Ｎｉ、ＲｕＯx、ＮｉＯx、Ｓ
ｎＯxのいずれか一種類以上の助触媒１３を光触媒物質
層１４上に坦持した構成を示す図である。助触媒１３に
より、紫外光だけでなく可視光に対する光触媒活性が向
上する。[Fourth Embodiment] FIG. 4 is a diagram showing a configuration of the fourth embodiment. In the fourth embodiment, in the configuration of the third embodiment, Pt, Pd, Ni, RuO x , NiO x , S
FIG. 3 is a view showing a configuration in which any one or more types of promoters 13 of nO x are supported on a photocatalytic substance layer 14. The cocatalyst 13 improves the photocatalytic activity not only for ultraviolet light but also for visible light.
【００３８】「実施形態５」図５は実施形態５の構成を
示す図である。基材１１の表面には、光触媒物質層１４
が形成されている。この光触媒物質層１４の上に酸化チ
タン（ＴｉＯ2）結晶層１６を形成し、さらにその上に
ＳｉＯ2等の可視光を透過しかつ蓄水性の物質層１５を
形成する。[Fifth Embodiment] FIG. 5 is a diagram showing a configuration of a fifth embodiment. A photocatalytic substance layer 14 is provided on the surface of the base material 11.
Are formed. A titanium oxide (TiO 2 ) crystal layer 16 is formed on the photocatalytic substance layer 14, and a water-storing substance layer 15 such as SiO 2 that transmits visible light is formed thereon.
【００３９】光触媒物質層１４は、酸化チタン結晶の酸
素サイトの一部が窒素またはイオウで置換したＴｉ−Ｏ
−ＮまたはＴｉ−Ｏ−Ｓ構成を有し、可視光域において
光触媒作用を発現する。なお、ＴｉＯ2結晶の格子間に
窒素またはイオウがドーピングされた構造や多結晶集合
体の粒界に窒素原子またはイオウが配された構成でもよ
く、これらが混在していてもよい。また、Ｔｉ−Ｏ−Ｎ
またはＴｉ−Ｏ−Ｓの組成比は、０＜（ＮまたはＳ）＜
１３％である。酸化チタン結晶はルチルでもアナターゼ
でもよい。The photocatalytic substance layer 14 is made of Ti—O in which a part of oxygen sites of a titanium oxide crystal is replaced by nitrogen or sulfur.
It has a -N or Ti-OS configuration, and exhibits photocatalysis in the visible light region. It should be noted that a structure in which nitrogen or sulfur is doped between lattices of the TiO 2 crystal or a structure in which nitrogen atoms or sulfur is arranged at grain boundaries of a polycrystalline aggregate may be used, or these may be mixed. Also, Ti-ON
Alternatively, the composition ratio of Ti—O—S is 0 <(N or S) <
13%. The titanium oxide crystal may be rutile or anatase.
【００４０】酸化チタン結晶層１６は、アナターゼまた
はルチル型結晶構造である。また、光触媒物質層１４と
酸化チタン結晶層１６は図５では積層構造を図示してい
るが、両者の界面は明確でなくてもよい。つまり、基材
１１に近いほど窒素またはイオウが増加していく構造で
もよい。透光性かつ蓄水物質層１５は、ＳｉＯ2、Ｓｉ
Ｏ、Ｔａ2Ｏ5等の可視光または紫外光が一部透過し、水
の吸着性材料である。構造は結晶性でも無定型でもかま
わない。また、禁制帯幅がチタニアの３．２ｅＶより小
さくても大きくてもかまわない。ただし、透光性である
必要はある。これは、光触媒物質層１４において可視光
を吸収し、ＴｉＯ2結晶層１６で触媒反応をおこすため
である。また、この透光性かつ蓄水物質層１５の層厚
は、光触媒物質層１４において生成した電子と正孔が移
動できる距離と関係する。すなわち、２ｎｍ以上かつ１
００ｎｍ以下が好適である。The titanium oxide crystal layer 16 has an anatase or rutile type crystal structure. Although the photocatalyst material layer 14 and the titanium oxide crystal layer 16 have a stacked structure in FIG. 5, the interface between them may not be clear. That is, a structure in which nitrogen or sulfur increases as the position is closer to the base material 11 may be employed. The translucent and water storage material layer 15 is made of SiO 2 , Si
It is a water-absorbing material that partially transmits visible light or ultraviolet light such as O and Ta 2 O 5 . The structure may be crystalline or amorphous. Further, the forbidden band width may be smaller or larger than 3.2 eV of titania. However, it needs to be translucent. This is because the photocatalytic substance layer 14 absorbs visible light and causes a catalytic reaction in the TiO 2 crystal layer 16. The thickness of the light-transmitting and water-storing substance layer 15 is related to the distance over which electrons and holes generated in the photocatalytic substance layer 14 can move. That is, 2 nm or more and 1
00 nm or less is suitable.
【００４１】「実施形態６」図６は、実施形態６の構成
を示す図である。この実施形態６では、実施形態５の構
成において、Ｐｔ、Ｐｄ、Ｎｉ、ＲｕＯx、ＮｉＯx、Ｓ
ｎＯxのいずれか一種類以上の助触媒１３を光触媒物質
層１４上に坦持した構成を示す図である。助触媒１３に
より、紫外光だけでなく可視光に対する光触媒活性が向
上する。[Sixth Embodiment] FIG. 6 is a diagram showing a configuration of the sixth embodiment. In the sixth embodiment, in the configuration of the fifth embodiment, Pt, Pd, Ni, RuO x , NiO x , S
FIG. 3 is a view showing a configuration in which any one or more types of promoters 13 of nO x are supported on a photocatalytic substance layer 14. The cocatalyst 13 improves the photocatalytic activity not only for ultraviolet light but also for visible light.
【００４２】「実施形態７」実施形態７は、実施形態１
〜６の構成において、可視光域において光触媒作用を発
現する光触媒物質をＭ1−Ｍ2−Ｏ−ＮまたはＭ1−Ｍ2−
Ｏ−Ｓ（Ｍ1＝Ｔｉ，Ｚｎ，Ｓｎ；Ｍ2＝Ｖ，Ｃｒ，Ｍ
ｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｒｕ，Ｒｈ，Ｒ
ｅ，Ｏｓ，Ｉｒ，Ｐｔ，Ｐｄ）結晶層とすることによっ
て、さらに、可視光吸収領域を長波長化し、光触媒特性
を向上させた親水性材料である。[Embodiment 7] Embodiment 7 corresponds to Embodiment 1.
In the constitutions of Nos. 1 to 6, the photocatalytic substance exhibiting a photocatalytic action in the visible light range is M 1 -M 2 -ON or M 1 -M 2-.
OS (M 1 = Ti, Zn, Sn; M 2 = V, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ru, Rh, R
(e, Os, Ir, Pt, Pd) is a hydrophilic material having a visible light absorption region of a longer wavelength and improved photocatalytic properties by forming a crystal layer.
【００４３】ここで、Ｍ1−Ｍ2−Ｏ−ＮまたはＭ1−Ｍ2
−Ｏ−Ｓ構造は、基本的にＭ1−Ｏの結晶構造におい
て、Ｍ1のサイトの一部がＭ2原子に、また酸素原子サイ
トの一部が窒素またはイオウで置換された構造である。
このように、カチオンの一部がＭ2に、また酸素格子の
一部が窒素原子またはイオウに置換されることにより、
両者の複合相互作用により、結晶構造が安定化し、さら
に６００ｎｍ程度の波長までの可視光が吸収できるバン
ド構造となる。Here, M 1 -M 2 -ON or M 1 -M 2
The -OS structure is basically a crystal structure of M 1 -O in which a part of the M 1 site is replaced by an M 2 atom and a part of the oxygen atom site is replaced by nitrogen or sulfur. .
Thus, by replacing part of the cation with M 2 and part of the oxygen lattice with a nitrogen atom or sulfur,
Due to the complex interaction between the two, the crystal structure is stabilized, and a band structure capable of absorbing visible light up to a wavelength of about 600 nm is obtained.
【００４４】Ｍ2の添加量は、０＜Ｍ2＜５％である。ま
た、ＮまたはＳの添加量は、０＜（ＮまたはＳ）＜１３
％である。The addition amount of M 2 is 0 <M 2 <5%. The amount of N or S added is 0 <(N or S) <13
%.
【００４５】[0045]
【実施例】「実施例１」実施例１は実施形態１に対応す
る親水性材料である。ソーダ石灰ガラス基板上に、光触
媒物質と、蓄水性のＳｉＯ2とを複合した複合層を形成
する。ここで、光触媒物質は、酸化チタン結晶の酸素の
サイトの一部を窒素で置換したＴｉ−Ｏ−Ｎ構成を有
し、可視光域において光触媒作用を発現する。EXAMPLES Example 1 Example 1 is a hydrophilic material corresponding to the first embodiment. On a soda-lime glass substrate, a composite layer is formed in which a photocatalytic substance and water storage SiO 2 are composited. Here, the photocatalytic substance has a Ti-ON configuration in which part of the oxygen sites of the titanium oxide crystal has been replaced with nitrogen, and exhibits a photocatalytic action in the visible light region.
【００４６】以下にその製造方法の一例を示す。ソーダ
石灰ガラス板を基材として用意し、通常の水洗浄、有機
洗浄を行った。一方、市販品のアナターゼ型結晶性酸化
チタン粉末をアンモニア雰囲気７００℃で熱処理し、窒
素を含有させた酸化チタン粉末を作製した。この粉末を
例えば無機バインダとしてコロイダルシリカを用い、溶
媒として水とエタノールを用いて塗布溶液とした。この
塗布溶液を、前記基材に塗布し、乾燥させ１５０℃の空
気中熱処理を実施した。塗布方法としてスプレー法また
はディッピングコート法を用いた。膜厚として、２００
〜４００ｎｍ塗布した。An example of the manufacturing method will be described below. A soda-lime glass plate was prepared as a base material and subjected to ordinary water washing and organic washing. On the other hand, a commercially available anatase-type crystalline titanium oxide powder was heat-treated at 700 ° C. in an ammonia atmosphere to prepare a titanium oxide powder containing nitrogen. This powder was used as a coating solution using, for example, colloidal silica as an inorganic binder and water and ethanol as solvents. This coating solution was applied to the substrate, dried, and heat-treated at 150 ° C. in air. A spray method or a dipping coat method was used as a coating method. 200 as the film thickness
４００400 nm was applied.
【００４７】次に、本実施例の親水性能および耐摩耗性
の特性について、比較例とともに評価した。すなわち、
実施例１−１〜１−３として光触媒物質であるＴｉ−Ｏ
−Ｎ（ＴｉＯＮ）と蓄水物質であるＳｉＯ2（ＳｉＯ
２）の割合を変更したものを試験し、実施例１−４（実
施形態２に対応する）では、助触媒Ｐｔを加え可視光の
照射量を他の１／２にした。また、比較例１−Ａは、Ｔ
ｉＯ2とＳｉＯ2の複合層であり、その他の条件は実施例
１−１〜１−３と同一とした。Next, the hydrophilic performance and abrasion resistance characteristics of this example were evaluated together with comparative examples. That is,
In Examples 1-1 to 1-3, a photocatalytic substance, Ti-O
-N (TiON) and water storage substance SiO 2 (SiO 2
Tests were conducted by changing the ratio of 2), and in Examples 1-4 (corresponding to Embodiment 2), the irradiation amount of visible light was reduced to another half by adding a promoter Pt. Comparative Example 1-A shows T
This was a composite layer of iO 2 and SiO 2 , and the other conditions were the same as in Examples 1-1 to 1-3.
【００４８】表１には、それぞれの実施例の親水性能
（接触角）および耐摩耗性を示す。ここで、親水性能
は、親水性材料を作製後、室内にて蛍光灯（ただし、波
長４００ｎｍ以下の光をカット）にあてながら２０日経
過した後の水の接触角値で評価した。また、耐摩耗性は
２００ｇ荷重のテーバー摩耗試験１０００回を行い、そ
の後の曇化値が５％以下かつ、親水の劣化がない場合を
○とし、それ以外を×とした。Table 1 shows the hydrophilic performance (contact angle) and abrasion resistance of each example. Here, the hydrophilic performance was evaluated by a contact angle value of water after 20 days passed after producing a hydrophilic material and illuminating the room with a fluorescent lamp (cutting light having a wavelength of 400 nm or less). The abrasion resistance was evaluated by performing a Taber abrasion test 1000 times under a load of 200 g 1,000 times, and when the haze value was 5% or less and there was no deterioration in hydrophilicity, the result was evaluated as ○, and the others were evaluated as ×.
【００４９】[0049]
【表１】 この表１からも明らかなように、実施例１−１〜１−３
においては、十分な親水性能が可視光照射のもとで維持
され、かつ耐摩耗性も有している。これに対し、比較例
の従来のアナターゼチタニア（ＴｉＯ2）とＳｉＯ2の組
み合わせでは親水性能が維持されず、耐摩耗性について
も、満足しなかった。[Table 1] As is clear from Table 1, Examples 1-1 to 1-3 were used.
Has sufficient hydrophilic performance under visible light irradiation, and also has abrasion resistance. On the other hand, the hydrophilic performance was not maintained by the conventional combination of anatase titania (TiO 2 ) and SiO 2 of the comparative example, and the abrasion resistance was not satisfactory.
【００５０】さらに、Ｐｔ膜厚にして０．２ｎｍ坦持
し、Ｔｉ−Ｏ−Ｎが５０％、ＳｉＯ2が５０％とした実
施例１−４の親水性材料では、可視光の照射光量が実施
例１−１の１／２でも、実施例１−１〜１−３と同様の
親水および耐摩耗性能を示した。Further, in the hydrophilic material of Example 1-4 in which the Pt film thickness was 0.2 nm and the Ti—O—N was 50% and the SiO 2 was 50%, the amount of visible light irradiation was small. Also in １ ／ of Example 1-1, the same hydrophilicity and abrasion resistance as in Examples 1-1 to 1-3 were exhibited.
【００５１】「実施例２」実施例２は実施形態３に対応
する親水性材料である。ＳｉＯ2ガラスまたはホウケイ
酸ガラス基材上に、Ｔｉ−Ｏ−Ｎ構成を有し、可視光域
において光触媒作用を発現する光触媒物質層を形成し、
さらにその上に透光性でかつ蓄水性のＳｉＯ2またはＳ
ｉＯ層を形成した親水性材料である。Example 2 Example 2 is a hydrophilic material corresponding to Embodiment 3. On a SiO 2 glass or borosilicate glass substrate, a photocatalytic substance layer having a Ti—O—N configuration and exhibiting a photocatalytic action in a visible light region is formed,
Further, light-transmitting and water-retentive SiO 2 or S
It is a hydrophilic material on which an iO layer is formed.
【００５２】以下に、その製造方法の一例について説明
する。本例では、マルチターゲットスパッタリング装置
を用いて作製した例を示す。An example of the manufacturing method will be described below. In this example, an example is described in which a multi-target sputtering apparatus is used.
【００５３】図７には、スパッタリング装置の概略図を
示す。２１はチェンバ本体、２２は基板ホルダ、２３は
基材、２４はＴｉＯ2ターゲット、２５はＳｉＯ2ターゲ
ット、２６および２７はターゲットシャッタ、２８、２
９および３０はＡｒ等の不活性ガス、窒素ガスおよび酸
素ガスのバリアブルリークバルブ、３１はＡｒなどの不
活性ガスボンベ、３２は窒素ガスボンベ、３３は酸素ガ
スボンベ、３６は真空排気口、３４および３５はマッチ
ングボックス、ＲＦ電源である。FIG. 7 is a schematic diagram of a sputtering apparatus. 21 is a chamber body, 22 is a substrate holder, 23 is a base material, 24 is a TiO 2 target, 25 is a SiO 2 target, 26 and 27 are target shutters,
9 and 30 are variable leak valves of an inert gas such as Ar, nitrogen gas and oxygen gas, 31 is an inert gas cylinder such as Ar, 32 is a nitrogen gas cylinder, 33 is an oxygen gas cylinder, 36 is a vacuum exhaust port, and 34 and 35 are Matching box, RF power supply.
【００５４】ＳｉＯ2ガラスまたはホウケイ酸ガラス基
板を表面洗浄し、基材とした。まず、基板ホルダ２２に
基材をセットし、１０-5Ｐａ台までチェンバ本体２１を
３６の真空排気口を通して真空排気した。ボンベ３１、
３２からバリアブルリークバルブ２８および２９を介し
てチェンバ本体２１にＡｒと窒素ガスを導入した。この
時の窒素の比率は４０％で、５ｘ１０-1Ｐａの圧力まで
導入した。そこで、ＴｉＯ2ターゲット２４にマッチン
グボックス３４を介してＲＦ電源３５からＲＦ電力を供
給し、ＲＦ放電させた。規定の時間シャッタ２６を開け
てＴｉ−Ｏ−Ｎ層をスパッタ成膜し、放電を止め、Ａｒ
と窒素の混合ガスを排気した。The surface of the SiO 2 glass or borosilicate glass substrate was washed to obtain a substrate. First, the base material was set on the substrate holder 22, and the chamber main body 21 was evacuated to a level of 10 −5 Pa through 36 evacuation ports. Cylinder 31,
Ar and nitrogen gas were introduced into chamber body 21 from 32 through variable leak valves 28 and 29. At this time, the ratio of nitrogen was 40%, and the pressure was introduced up to a pressure of 5 × 10 -1 Pa. Then, RF power was supplied from the RF power supply 35 to the TiO 2 target 24 via the matching box 34, and RF discharge was performed. The shutter 26 is opened for a specified time, a Ti-ON layer is formed by sputtering, discharge is stopped, and Ar
And a nitrogen gas mixture was exhausted.
【００５５】その後、基材を５５０℃の温度で熱処理
し、Ｔｉ−Ｏ−Ｎ層を結晶化させた。次に、３１および
３３のボンベからバリアブルリークバルブ２８および３
０を介してチェンバ本体２１にＡｒと酸素を導入した。
この時の酸素の比率は５％で、５ｘ１０-1Ｐａの圧力ま
で導入した。そこで、ＳｉＯ2ターゲット２５にマッチ
ングボックス３４を介してＲＦ電源３５からＲＦ電力を
供給し、ＲＦ放電させた。規定の時間シャッタ２７を開
けてＳｉＯ2層をスパッタ成膜し、放電を止め、Ａｒと
酸素の混合ガスを排気した。Thereafter, the substrate was heat-treated at a temperature of 550 ° C. to crystallize the Ti—O—N layer. Next, the variable leak valves 28 and 3 are removed from the cylinders 31 and 33.
Ar and oxygen were introduced into the chamber main body 21 through the chamber.
At this time, the ratio of oxygen was 5%, and the pressure was introduced up to a pressure of 5 × 10 -1 Pa. Therefore, RF power was supplied from the RF power supply 35 to the SiO 2 target 25 via the matching box 34 to perform RF discharge. The shutter 27 was opened for a specified time, a SiO 2 layer was formed by sputtering, the discharge was stopped, and a mixed gas of Ar and oxygen was exhausted.
【００５６】Ｔｉ−Ｏ−Ｎ層の組成はＴｉ31Ｏ67Ｎ2、
膜厚１００ｎｍで、ＳｉＯ2層の膜厚は２０ｎｍとし
た。なお、ＳｉＯ層を形成する場合は、ＳｉＯ2ターゲ
ットの代わりにＳｉＯターゲットを設置して行った。The composition of the Ti—O—N layer is Ti 31 O 67 N 2 ,
The film thickness was 100 nm, and the film thickness of the SiO 2 layer was 20 nm. When forming the SiO layer, an SiO target was provided instead of the SiO 2 target.
【００５７】次に、本実施例２−１〜２−４の親水性能
および耐摩耗性の特性について、比較例とともに評価し
た。なお、実施例２−１〜２−３では蓄水物質層である
ＳｉＯ2（ＳｉＯ２）層の厚みを変更したものを試験
し、実施例１−４（実施形態２に対応する）では、助触
媒Ｐｔを加え可視光の照射量を他の１／２にした。ま
た、比較例２−ＡではＴｉ−Ｏ−Ｎ層に代えＴｉＯ2層
を採用した。Next, the hydrophilicity and abrasion resistance of Examples 2-1 to 2-4 were evaluated together with Comparative Examples. In addition, in Examples 2-1 to 2-3, those in which the thickness of the SiO 2 (SiO 2 ) layer as the water storage material layer was changed were tested, and in Examples 1-4 (corresponding to Embodiment 2), The irradiation amount of visible light was reduced to another half by adding the catalyst Pt. In Comparative Example 2-A, a TiO 2 layer was used instead of the Ti-ON layer.
【００５８】表２には、親水性能（接触角）および耐摩
耗性を示す。ここで、親水性能は、親水材料を作製後、
室内にて蛍光灯（ただし、波長４００ｎｍ以下をカッ
ト）にあてながら２０日経過した後の水の接触角値で評
価した。また、耐摩耗性は２００ｇ荷重のテーバー摩耗
試験１０００回を行い、その後の曇化値が５％以下か
つ、親水の劣化がない場合を○とし、それ以外を×とし
た。Table 2 shows hydrophilic performance (contact angle) and abrasion resistance. Here, the hydrophilic performance, after producing a hydrophilic material,
The evaluation was made based on the contact angle value of water after 20 days while being exposed to a fluorescent lamp (however, a wavelength of 400 nm or less was cut) indoors. The abrasion resistance was evaluated by performing a Taber abrasion test 1000 times under a load of 200 g 1,000 times, and when the haze value was 5% or less and there was no deterioration in hydrophilicity, the result was evaluated as ○, and the others were evaluated as ×.
【００５９】[0059]
【表２】 表２からも明らかなように、実施例２−１〜２−４にお
いては、十分な親水性能が、可視光照射のもとでは維持
されるのに対し、比較例の従来のアナターゼチタニアと
ＳｉＯ2の組み合わせでは親水性能が維持されない。耐
摩耗性については、試験を満足した。[Table 2] As is clear from Table 2, in Examples 2-1 to 2-4, sufficient hydrophilic performance was maintained under irradiation with visible light, whereas the conventional anatase titania and SiO 2 of the comparative example were maintained. With the combination of 2 , hydrophilic performance is not maintained. The test satisfied the abrasion resistance.
【００６０】また、Ｔｉ−Ｏ−Ｎ層上に、Ｐｔ膜厚にし
て０．２ｎｍ坦持し、さらにＳｉＯ層２０ｎｍ形成した
実施例２−４の親水性材料では、可視光の照射光量が実
施例２−１の１／２でも、同様の親水性能を示した。In the hydrophilic material of Example 2-4 in which a Pt film thickness of 0.2 nm was supported on the Ti—O—N layer and a SiO layer was formed to a thickness of 20 nm, the amount of visible light irradiation was limited. The same hydrophilic performance was shown in １ ／ of Example 2-1.
【００６１】本実施例では酸素過剰のＴｉ31Ｏ67Ｎ2の
組成比を挙げたが組成比はこれに限らない。すなわちＴ
ｉ37Ｏ67Ｎ2のように還元組成であっても本発明の可視
光動作が実現できる。In the present embodiment, the composition ratio of oxygen-excess Ti 31 O 67 N 2 is mentioned, but the composition ratio is not limited to this. That is, T
The visible light operation of the present invention can be realized even with a reduced composition such as i 37 O 67 N 2 .
【００６２】「実施例３」実施例３は、図５に示した実
施形態５に対応する親水材料である。セラミックス基板
上に、Ｔｉ−Ｏ−Ｓ層、酸化チタン層を順次を形成し、
さらにその上に透光性でかつ蓄水性のＳｉＯ2層を形成
した親水性材料である。層の厚さはそれぞれ、２００ｎ
ｍ、５０ｎｍ、２０ｎｍである。実施例３では、４００
ｎｍ以上の可視光を１時間照射し、その後、暗所に１０
日以上放置しても、水の接触角５度以下の親水性を保持
した。一方、従来の酸化チタン、ＳｉＯ2の積層体では
２０度以上となった。Example 3 Example 3 is a hydrophilic material corresponding to Embodiment 5 shown in FIG. A Ti-OS layer and a titanium oxide layer are sequentially formed on a ceramic substrate,
Further, it is a hydrophilic material on which a translucent and water storage SiO 2 layer is formed. The thickness of each layer is 200n
m, 50 nm, and 20 nm. In the third embodiment, 400
irradiate visible light of 1 nm or more for 1 hour, and then
Even if left for more than a day, the hydrophilicity of the contact angle of water of 5 degrees or less was maintained. On the other hand, in the case of the conventional laminate of titanium oxide and SiO 2 , the temperature was 20 ° or more.
【００６３】「実施例４」実施例４は、実施形態７に対
応するものであり、シリカガラス板上に、Ｔｉ−Ｃｒ−
Ｏ−Ｎ層を形成し、さらにその上にＳｉＯ2層を形成し
た。層の厚さは、それぞれ２００ｎｍ、２０ｎｍであ
る。また、Ｔｉ−Ｃｒ−Ｏ−Ｎ層の組成は、Ｃｒ３ａｔ
％、Ｎ１．５ａｔ％である。本実施例では、４５０ｎｍ
以上の可視光によっても接触角５度以下の親水性を維持
した。Example 4 Example 4 corresponds to Embodiment 7, and a Ti—Cr—
O-N layer is formed, SiO 2 layer was formed to further thereon. The thickness of the layers is 200 nm and 20 nm, respectively. The composition of the Ti—Cr—ON layer is Cr 3 at.
% And N 1.5 at%. In this embodiment, 450 nm
Even with the above visible light, hydrophilicity with a contact angle of 5 degrees or less was maintained.
【００６４】[0064]
【発明の効果】以上説明したように、本発明の親水性材
料は、可視光によっても応答し、光触媒機能を呈し、表
面を親水化する。したがって、屋外だけでなく、紫外光
の少ないまたはない室内や車内においても、蛍光灯やラ
ンプ等の可視光によって親水性を発現する。その結果、
汚れ防止および防曇性を安定に呈することができる。ま
た、Ｔｉ−Ｏ−ＮまたはＴｉ−Ｏ−Ｓ系はＴｉＯ2ベー
スであるので、化学的に安定であり、他の光触媒半導体
材料（ＣｄＳ，ＷＯ3，Ｆｅ2Ｏ3，ＺｎＯ等）のよう
に、酸アルカリによって溶出することもなく、長期間安
定に使用できる。As described above, the hydrophilic material of the present invention responds to visible light, exhibits a photocatalytic function, and renders the surface hydrophilic. Therefore, not only outdoors, but also indoors and vehicles where there is little or no ultraviolet light, hydrophilicity is exhibited by visible light such as fluorescent lamps and lamps. as a result,
Stain prevention and antifogging properties can be exhibited stably. Further, since the TiO-N or TiO-S system is a TiO 2 basis, it is chemically stable, like other photocatalytic semiconductor material (CdS, WO 3, Fe 2 O 3, ZnO , etc.) In addition, it can be used stably for a long time without being eluted by acid or alkali.
【００６５】また、蓄水性の材料ＳｉＯ2やＳｉＯ等は
硬度的にも硬く、層自体の耐摩耗性等の機械的強度も向
上する。Further, the water storage materials SiO 2 and SiO are also hard in hardness, and the mechanical strength such as the wear resistance of the layer itself is improved.
【図１】 実施形態１の構成を示す図である。FIG. 1 is a diagram showing a configuration of a first embodiment.
【図２】 実施形態２の構成を示す図である。FIG. 2 is a diagram illustrating a configuration of a second embodiment.
【図３】 実施形態３の構成を示す図である。FIG. 3 is a diagram illustrating a configuration of a third embodiment.
【図４】 実施形態４の構成を示す図である。FIG. 4 is a diagram showing a configuration of a fourth embodiment.
【図５】 実施形態５の構成を示す図である。FIG. 5 is a diagram showing a configuration of a fifth embodiment.
【図６】 実施形態６の構成を示す図である。FIG. 6 is a diagram showing a configuration of a sixth embodiment.
【図７】 スパッタリング装置の構成を示す図である。FIG. 7 is a diagram illustrating a configuration of a sputtering apparatus.
【符号の説明】 １１ 基材、１２ 複合層、１３ 助触媒、１４ 光触
媒物質層、１５ 蓄水物質層、１６ ＴｉＯ2結晶層。[Description of Signs] 11 base material, 12 composite layer, 13 co-catalyst, 14 photocatalytic substance layer, 15 water storage substance layer, 16 TiO 2 crystal layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 旭 良司 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 志賀 孝広 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 多賀 康訓 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 Ｆターム(参考） 4G069 AA03 BA02A BA02B BA04A BA04B BA13B BA48A BB02A BB04A BB06A BB20A BB20B BC22A BC31A BC35A BC50A BC50B BC54A BC58A BC62A BC64A BC66A BC68A BC70A BC71A BC72A BC73A BC74A BC75A BD02A BD02B BD06A BD06B BD08A BD08B EA07 EB15Y EC28 ED02 EE06 4J038 AA011 HA066 HA211 HA216 HA441 KA04 NA06 PA07 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ryoji Asahi 41-cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Institute, Inc. (72) Inventor Takahiro Shiga Nagakute-cho, Aichi-gun, Aichi Prefecture No. 41, Yokomichi, Toyota Central Research Laboratory Co., Ltd. (72) Inventor Yasunori Taga, No. 41, Chukumi Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture F-term in Toyota Central Research Laboratory Co., Ltd. 4G069 AA03 BA02A BA02B BA04A BA04B BA13B BA48A BB02A BB04A BB06A BB20A BB20B BC22A BC31A BC35A BC50A BC50B BC54A BC58A BC62A BC64A BC66A BC68A BC70A BC71A BC72A BC73A BC74A BC75A HA02 HA07B02B08B08A08
Claims (9)
素原子で置換、酸化チタン結晶の格子間に窒素原子をド
ーピング、あるいは酸化チタン結晶の多結晶集合体の粒
界に窒素原子を配してなる光触媒物質と、 蓄水性を有する蓄水性物質と、 を含み、 基板上に層を形成し得る親水性材料。1. A method for disposing a part of an oxygen site of a titanium oxide crystal with a nitrogen atom, doping a nitrogen atom between lattices of the titanium oxide crystal, or disposing a nitrogen atom at a grain boundary of a polycrystalline aggregate of the titanium oxide crystal. A hydrophilic material, comprising: a photocatalytic substance comprising: a photocatalytic substance; and a water storage substance having a water storage property, and capable of forming a layer on a substrate.
オウ原子で置換、酸化チタン結晶の格子間にイオウ原子
をドーピング、あるいは酸化チタン結晶の多結晶集合体
の粒界にイオウ原子を配してなる光触媒物質と、 蓄水性を有する蓄水性物質と、 を含み、 基板上に層を形成し得る親水性材料。2. A method according to claim 1, wherein a part of an oxygen site of the titanium oxide crystal is replaced by a sulfur atom, a sulfur atom is doped between lattices of the titanium oxide crystal, or a sulfur atom is arranged at a grain boundary of a polycrystalline aggregate of the titanium oxide crystal. A hydrophilic material, comprising: a photocatalytic substance comprising: a photocatalytic substance; and a water storage substance having a water storage property, and capable of forming a layer on a substrate.
おいて、 前記蓄水性物質は、少なくとも酸化シリコンを含む親水
性材料。3. The hydrophilic material according to claim 1, wherein the water storage material contains at least silicon oxide.
おいて、 前記光触媒物質と蓄水性物質とは複合されて１つの複合
層に形成されている親水性材料。4. The hydrophilic material according to claim 1, wherein the photocatalytic substance and the water storage substance are composited to form a single composite layer.
ＯX、ＮｉＯx、ＳｎＯxのうちの少なくとも１種の助触
媒物質を担持させた親水性材料。5. The hydrophilic material according to claim 4, wherein Pt, Pd, Ni, and Ru are provided near the surface of the composite layer.
A hydrophilic material carrying at least one co-catalyst substance of O x , NiO x , and SnO x .
おいて、 光触媒物質と蓄水性物質とは、それぞれ層状に形成さ
れ、これらが積層されている親水性材料。6. The hydrophilic material according to claim 1, wherein the photocatalytic substance and the water storage substance are formed in layers, respectively, and are laminated.
ｄ、Ｎｉ、ＲｕＯX、ＮｉＯx、ＳｎＯxのうちの少なく
とも１種の助触媒物質を担持させた親水性材料。7. The hydrophilic material according to claim 6, wherein Pt, P is added to a boundary region between the photocatalytic substance layer and the water storage substance layer.
d, a hydrophilic material carrying at least one co-catalyst substance of Ni, RuO x , NiO x , and SnO x .
からなる層を有する親水性材料。8. The hydrophilic material according to claim 6, further comprising a layer made of titanium oxide between the photocatalytic substance layer and the water storage substance layer.
種選択された第１物質と、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｒｕ、Ｒｈ、Ｒｅ、Ｏｓ、Ｉ
ｒ、Ｐｔ、Ｐｄの中から少なくとも１種選択された第２
物質と、これらの複合酸化物の酸素サイトの一部を窒素
原子またはイオウ原子で置換、複合酸化物の格子間に窒
素原子またはイオウ原子をドーピング、あるいは複合酸
化物の多結晶集合体の粒界に窒素原子またはイオウ原子
を配してなる光触媒物質と、 蓄水性を有する蓄水性物質と、 を含み、 基板上に層を形成し得る親水性材料。9. At least one of Ti, Zn, and Sn
V, Cr, Mn, Fe, C
o, Ni, Cu, Zn, Ru, Rh, Re, Os, I
a second selected from at least one of r, Pt, and Pd
Substitute some nitrogen atoms or sulfur atoms for substances and oxygen sites of these composite oxides, dope nitrogen or sulfur atoms between lattices of composite oxides, or grain boundaries of polycrystalline aggregates of composite oxides A hydrophilic material capable of forming a layer on a substrate, comprising: a photocatalytic substance having a nitrogen atom or a sulfur atom disposed therein; and a water storage substance having a water storage property.
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|---|---|---|---|
| JP2000017634A JP5252757B2 (en) | 2000-01-26 | 2000-01-26 | Hydrophilic material |
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