JPH10314600A - Oxide photocatalyst film and product provided with the same - Google Patents
Oxide photocatalyst film and product provided with the sameInfo
- Publication number
- JPH10314600A JPH10314600A JP9129299A JP12929997A JPH10314600A JP H10314600 A JPH10314600 A JP H10314600A JP 9129299 A JP9129299 A JP 9129299A JP 12929997 A JP12929997 A JP 12929997A JP H10314600 A JPH10314600 A JP H10314600A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- thin film
- film
- fine particles
- dispersed
- 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
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 239000010419 fine particle Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 67
- 239000010408 film Substances 0.000 claims description 64
- 239000010409 thin film Substances 0.000 claims description 63
- 230000001699 photocatalysis Effects 0.000 claims description 41
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 40
- 238000000354 decomposition reaction Methods 0.000 claims description 29
- 239000004065 semiconductor Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 230000004888 barrier function Effects 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 38
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 18
- 229920002799 BoPET Polymers 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 239000002985 plastic film Substances 0.000 abstract description 3
- 229920006255 plastic film Polymers 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract 4
- 239000000377 silicon dioxide Substances 0.000 abstract 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract 4
- 229910052682 stishovite Inorganic materials 0.000 abstract 4
- 229910052905 tridymite Inorganic materials 0.000 abstract 4
- 239000000243 solution Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910019899 RuO Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- -1 Silicon alkoxides Chemical class 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005416 organic matter Substances 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化物光触媒薄
膜、及びそれを備えた物品に係わり、特にわずかな光で
有機物を分解する能力に優れるため、各種フィルター，
空調機，掃除機，空気洗浄機，洗濯機，換気扇に適用す
ることが可能な酸化物光触媒薄膜、及びそれを備えた物
品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxide photocatalytic thin film and an article provided with the same. Particularly, the present invention relates to various filters,
The present invention relates to an oxide photocatalytic thin film applicable to an air conditioner, a vacuum cleaner, an air washing machine, a washing machine, a ventilation fan, and an article provided with the thin film.
【０００２】[0002]
【従来の技術】近年、ＴｉＯ2 光触媒を用いた有機物の
分解及び抗菌防臭材が注目を集めている。これは、例え
ばニューセラミックス（1996)No.2,55に記載されている
ような半導体光触媒の酸化還元反応を用いたもので、基
板上に膜として形成されるのが一般的である。 2. Description of the Related Art In recent years, attention has been paid to organic substance decomposition and antibacterial deodorants using a TiO 2 photocatalyst. This uses an oxidation-reduction reaction of a semiconductor photocatalyst as described in New Ceramics (1996) No. 2, 55, for example, and is generally formed as a film on a substrate.
【０００３】成膜法としては、基板上にスパッタリング
のような物理的方法によるものとゾルゲル法のような塗
布法などの化学的な方法によるものとが知られている。
前者は真空装置等を用いて低い温度で成膜が可能であ
る。後者はスピンコート，スプレーなど簡単な装置で基
板上に塗布し、通常数百℃の温度で処理することによっ
て膜を得ることができる。抗菌防臭用の材料であるＴｉ
Ｏ2 はアナターゼ型の結晶のものが有効であり、機能発
現には結晶化が有効であることが報告されている(Paten
t No.(PCT)WO 94／11092,(PCT)WO95／15816)。As a film forming method, a method using a physical method such as sputtering on a substrate and a method using a chemical method such as a coating method such as a sol-gel method are known.
The former can form a film at a low temperature using a vacuum device or the like. The latter can be applied to a substrate by a simple device such as spin coating or spraying, and usually processed at a temperature of several hundred degrees Celsius to obtain a film. Ti, an antibacterial and deodorant material
It has been reported that O 2 is an anatase-type crystal effective, and crystallization is effective for function expression (Paten
t No. (PCT) WO 94/11092, (PCT) WO 95/15816).
【０００４】またＴｉＯ2 にＶ，Ｆｅ等を添加して高性
能化したものが報告されている(W.Choi,A.Termin,M.R.H
offmann,J.Phys.Chem.,98,13669-13679(1994))。[0004] V to TiO 2, is obtained by high performance by adding Fe or the like have been reported (W.Choi, A.Termin, MRH
offmann, J. Phys. Chem., 98, 13669-13679 (1994)).
【０００５】また、特開平8−66635号公報には、ＴｉＯ
2 膜を形成するための高温焼成時に低下した光活性を回
復するため、Ｃｕ，Ａｇ，Ｆｅ、Ｃｏ，Ｐｔ，Ｎｉ，Ｐ
ｄ等の金属を膜中に固定することが開示されている。ま
た、この発明では、従来、触媒の光活性を低下させるア
ルカリ金属，アルカリ土類金属のＴｉＯ2 への付着によ
る光活性の低下を回復させる効果があることも記載され
ている。Japanese Patent Application Laid-Open No. 8-66635 discloses that TiO
In order to recover the reduced photoactivity during high-temperature firing for forming the two films, Cu, Ag, Fe, Co, Pt, Ni, P
It is disclosed that a metal such as d is fixed in the film. In addition, this invention also describes that there is an effect of restoring a decrease in photoactivity due to the attachment of an alkali metal or an alkaline earth metal to TiO 2 that reduces the photoactivity of the catalyst.
【０００６】[0006]
【発明が解決しようとする課題】従来の技術で用いられ
ていた光触媒性を有する酸化チタン粒子を無機物薄膜中
に分散したものでは、酸化チタンのみから構成される光
触媒膜に比べて、酸化チタンの占有面積が小さい分、性
能が低下するという問題があった。そのため、従来の技
術で述べたように酸化チタン粒子を含む無機薄膜を数百
℃で焼成し、酸化チタンの結晶性を向上させる方法，
Ｖ，Ｆｅ等を添加して高性能化する方法などがとられて
いた。しかし、前者の方法では、数百℃で焼成する必要
があるため、耐熱温度が３００℃以下の有機高分子から
なる基材表面に設けることはできなかった。また、Ｖ，
Ｆｅ等を添加して高性能化する方法では酸化チタンに
Ｖ，Ｆｅ等の金属が拡散，固溶していないと性能が発揮
できない。すなわち、酸化チタンの粒子の前処理が必要
なので、製造プロセスが増えるという問題があった。In the case where the titanium oxide particles having photocatalytic properties used in the prior art are dispersed in an inorganic thin film, the titanium oxide particles of titanium oxide have a smaller particle size than the photocatalyst film composed of titanium oxide alone. There is a problem that the performance is deteriorated as the occupied area is small. Therefore, as described in the prior art, a method of firing an inorganic thin film containing titanium oxide particles at several hundred degrees Celsius to improve the crystallinity of titanium oxide,
A method of improving performance by adding V, Fe, or the like has been adopted. However, in the former method, since it is necessary to bake at several hundred degrees Celsius, it cannot be provided on the surface of a base material made of an organic polymer having a heat resistant temperature of 300 ° C. or less. V,
In the method of adding high performance by adding Fe or the like, the performance cannot be exhibited unless metals such as V and Fe are diffused and dissolved in titanium oxide. That is, since the pretreatment of the titanium oxide particles is required, there is a problem that the number of manufacturing processes increases.
【０００７】本発明の目的は、酸化チタンの触媒活性を
高める成分を添加することで、酸化チタンの結晶性が低
くてもわずかな光量（照度×照射時間）でも十分実用に
耐え得る光触媒活性を呈する酸化チタン粒子分散型の光
触媒膜、及びその膜を有する物品を提供することにあ
る。An object of the present invention is to add a component that enhances the catalytic activity of titanium oxide to provide a photocatalytic activity that can sufficiently withstand practical use even when the crystallinity of titanium oxide is low even with a small amount of light (illuminance × irradiation time). An object of the present invention is to provide a titanium oxide particle-dispersed photocatalytic film and an article having the film.
【０００８】別言すれば、本発明の目的は、高温で焼成
することを不要にでき、また酸化チタン粒子の前処理等
も不要な酸化チタン粒子分散型光触媒膜を提供すること
にある。In other words, an object of the present invention is to provide a titanium oxide particle-dispersed photocatalyst film which does not require firing at a high temperature and does not require pretreatment of the titanium oxide particles.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
の本発明の第１の発明の構成は、ＴｉＯ2 微粒子が無機
物薄膜中に分散している酸化物光触媒薄膜において、前
記無機物薄膜中に、電気陰性度が１.６より小さく、か
つイオン半径が０.２ｎｍより小さい元素であって、原
子価が２以下の金属元素が含有されていることを特徴と
する酸化物光触媒薄膜である。Means for Solving the Problems To achieve the above object, a first aspect of the present invention is directed to an oxide photocatalytic thin film in which TiO 2 fine particles are dispersed in an inorganic thin film; An oxide photocatalytic thin film characterized by containing a metal element having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm and a valence of 2 or less.
【００１０】無機物薄膜とは、例えば酸化珪素，酸化ジ
ルコニウム，酸化アルミニウム等の金属酸化物を主体と
する膜から構成されるものである。含有される金属元素
は、上記無機物薄膜中に均一に分散されていることが好
ましい。また、金属元素は、無機物薄膜中でイオンの形
態で分散されていることが好ましい。これらの元素は、
硝酸塩，炭酸塩，水酸化物等の塩の形で添加されること
によって、無機物薄膜中でイオンの形で存在させること
ができる。上記におけるイオン半径とは、化学便覧基礎
編II，改訂２版（昭和５４年３月２０日第４刷，１４０
７頁）に記載のイオン半径の表に基づいている。また、
電気陰性度は、ポーリングの電気陰性度の表に記載され
た数値に基づいている。The inorganic thin film is a film mainly composed of a metal oxide such as silicon oxide, zirconium oxide and aluminum oxide. It is preferable that the contained metal element is uniformly dispersed in the inorganic thin film. Preferably, the metal element is dispersed in the form of ions in the inorganic thin film. These elements are
By being added in the form of a salt such as nitrate, carbonate, hydroxide, etc., it can be present in the form of ions in the inorganic thin film. The ionic radius in the above is defined as Chemical Handbook Basic Edition II, 2nd revised edition (March 20, 1979, 4th printing, 140th edition).
Page 7)). Also,
The electronegativity is based on the values listed in Pauling's electronegativity table.
【００１１】ＴｉＯ2 は光触媒としての機能を有してお
り、有機物の分解及び抗菌防臭作用を持つ。その機能は
半導体であるＴｉＯ2 が光特に紫外線を照射すると生じ
る電子とホールに起因する。半導体であるＴｉＯ2 はバ
ンドギャップ以上のエネルギーを持つ光を照射すると、
電子とホールを生成する。生成した電子とホールはＴｉ
Ｏ2 表面に吸着した水を分解してＨラジカルとＯＨラジ
カルを生成する。このＯＨラジカルが有機物と反応する
ことにより、有機物を分解することができる。この様な
機構で光触媒は有機物等を分解しているが、さらに反応
速度を大きくするには以下の二つの手段がある。第１は
一つの活性点の仕事量を多くすることで、第２は活性点
の数を多くすることである。活性点の数を多くするに
は、表面積を大きくすること、すなわちＴｉＯ2 を微粒
子化することにより達成できる。また、活性点の仕事量
を多くするためには、ＴｉＯ2 （アナターゼ）の結晶化
を良くすることと、電子とホールの再結合を防止するこ
とである。以上を満足することにより反応速度を大きく
することができる。しかし、ＴｉＯ2（アナターゼ)の結
晶化を良くすることと表面積を大きくすることは相反す
ることであり、両立は困難である。すなわち、結晶性を
向上することは粒子径の増加を招き、表面積は低下して
しまう。従って、結晶性を向上させる方向と表面積を大
きくさせる方向との間に、最適域が存在する。その領域
は本発明の多くの実験結果より５〜２０ｎｍであること
を見出した。ＴｉＯ2 微粒子を分散させる場合に無機バ
インダーとして使用する酸化物の種類を変えてもこの粒
子径の範囲で分解速度が大きくなった。TiO 2 has a function as a photocatalyst, and has a function of decomposing organic substances and an antibacterial and deodorizing effect. Its function is caused by electrons and holes generated when TiO 2 as a semiconductor is irradiated with light, particularly ultraviolet light. When TiO 2, which is a semiconductor, is irradiated with light having energy equal to or greater than the band gap,
Generates electrons and holes. The generated electrons and holes are Ti
The water adsorbed on the O 2 surface is decomposed to generate H radicals and OH radicals. By reacting the OH radical with an organic substance, the organic substance can be decomposed. Although the photocatalyst decomposes organic substances and the like by such a mechanism, there are the following two means to further increase the reaction rate. The first is to increase the workload of one active point, and the second is to increase the number of active points. Increasing the number of active sites can be achieved by increasing the surface area, that is, by making TiO 2 finer. Further, in order to increase the work of the active site, it is necessary to improve the crystallization of TiO 2 (anatase) and to prevent recombination of electrons and holes. By satisfying the above, the reaction rate can be increased. However, improving the crystallization of TiO 2 (anatase) and increasing the surface area are contradictory, and it is difficult to achieve both. That is, improving the crystallinity leads to an increase in the particle diameter and a decrease in the surface area. Therefore, there is an optimum range between the direction in which the crystallinity is improved and the direction in which the surface area is increased. The region was found to be 5-20 nm from many experimental results of the present invention. Even when the type of the oxide used as the inorganic binder was changed when the TiO 2 fine particles were dispersed, the decomposition rate was increased within the range of the particle diameter.
【００１２】電子とホールの再結合を防止することによ
り反応速度を向上させるには、電子とホールの分離効率
をあげることにより達成される。ＴｉＯ2 表面にはＴｉ
欠陥が存在する。この欠陥は電子とホールの再結合点と
なり、反応を阻害する。ここに、イオン半径がＴｉと同
程度のイオンが添加されると表面のＴｉ欠陥に侵入し、
欠陥が消滅し再結合点が減少する。さらに、正イオンで
存在するため、電子を引き付けホールと分離でき、有機
物の酸化反応を促進することができる。本発明は、この
ような効果を有する添加剤の条件が電気陰性度が１.６
より小さく、イオン半径が０.２ｎｍ より小さいものが
有効であることを見出した。電気陰性度が１.６より小
さく、イオン半径が０.２ｎｍより小さい代表的なもの
としてアルカリ金属元素がある。これらの元素は従来の
文献、例えば１９９６年７月５日（金）に中央大学駿河
台記念館で行われた「光触媒の開発と最新技術」と題す
る講習会でのテキスト第３４頁下から５行目〜に、チタ
ン膜にアルカリ成分が拡散することにより触媒活性が低
下することが記載されているように、従来は光活性を低
下させるものとして認識されていた。本発明者らは酸化
チタンの光触媒活性を向上させる方法を鋭意検討した結
果、従来光触媒を低下させるものと認識されていたアル
カリ金属等が、逆に触媒活性を向上させるという新しい
発見に基づいてなされたものである。この場合、添加さ
れる金属元素は、酸化チタン格子中に拡散しているより
は、酸化チタン粒子の周りにある無機物薄膜中に金属イ
オンとして存在する方が高活性を示す。従って、高温で
焼成するよりは、２００℃以下の低温で焼成されるか、
または紫外線を照射するのみでまったく焼成しない方
が、高活性の触媒膜が得られる。The improvement of the reaction rate by preventing the recombination of electrons and holes can be achieved by increasing the efficiency of separating electrons and holes. Ti on the TiO 2 surface
There are defects. This defect becomes a recombination point of electrons and holes, and inhibits the reaction. Here, when ions having an ionic radius similar to that of Ti are added, they penetrate into Ti defects on the surface,
Defects disappear and recombination points decrease. Furthermore, since it exists as a positive ion, the electron can be attracted and separated from the hole, and the oxidation reaction of the organic substance can be promoted. According to the present invention, the condition of the additive having such an effect is that the electronegativity is 1.6.
It has been found that those having a smaller ionic radius than 0.2 nm are effective. As a typical electronegativity smaller than 1.6 and an ionic radius smaller than 0.2 nm, there is an alkali metal element. These elements are described in the conventional literature, for example, the text from the bottom of page 34 at the textbook "Development and Latest Technology of Photocatalyst" held at Chuo University Surugadai Memorial Hall on July 5, 1996 (Fri). As described above, it has been conventionally recognized that the photoactivity is reduced as described in that the catalytic activity is reduced by the diffusion of the alkali component into the titanium film. The present inventors have conducted intensive studies on a method for improving the photocatalytic activity of titanium oxide, and as a result, based on a new discovery that alkali metals and the like, which were conventionally recognized as reducing the photocatalyst, conversely improve the catalytic activity. It is a thing. In this case, the added metal element exhibits higher activity when it is present as a metal ion in the inorganic thin film around the titanium oxide particles than when it is diffused into the titanium oxide lattice. Therefore, rather than firing at a high temperature, firing at a low temperature of 200 ° C. or less,
Alternatively, a catalyst film with high activity can be obtained by irradiating only ultraviolet rays and not firing at all.
【００１３】上記構成により、製造時に焼成等をしなく
とも、十分な性能の光活性を呈する光触媒薄膜が製造で
きるため、低コストな光触媒薄膜が提供できる。すなわ
ち、十分な光活性を維持しながら、かつ耐熱性の低い有
機高分子化合物表面にも設けることが可能な光触媒薄膜
が提供できる。According to the above configuration, a photocatalytic thin film exhibiting sufficient photoactivity can be produced without firing or the like at the time of production, so that a low-cost photocatalytic thin film can be provided. That is, it is possible to provide a photocatalytic thin film that can be provided on the surface of an organic polymer compound having low heat resistance while maintaining sufficient photoactivity.
【００１４】焼成しないで酸化チタン膜を作製する場合
は、生成した酸化チタン膜は、結晶性が低い。これをＸ
線回折するとブロードなピークが現れる。このような結
晶性の低い酸化チタン粒子は、光触媒活性が低いが、Ｌ
ｉが添加されることによって、触媒活性を向上させてい
るので、トータルの光触媒性能は、数百度で焼成した酸
化チタン粒子分散型光触媒膜と同等またはそれ以上であ
る。When a titanium oxide film is formed without firing, the resulting titanium oxide film has low crystallinity. This is X
A broad peak appears upon line diffraction. Such titanium oxide particles having low crystallinity have low photocatalytic activity,
Since the catalytic activity is improved by the addition of i, the total photocatalytic performance is equal to or higher than the titanium oxide particle-dispersed photocatalyst film fired at several hundred degrees.
【００１５】第１の発明において、上記金属が、Ｎａ，
Ｌｉ，Ｋ，Ｍｇ，Ｃａ，Ｓｒ，Ｚｎの中から選ばれた少
なくとも一種の金属であることが好ましい。特に本発明
者らの実験によれば、Ｌｉ，Ｎａ，Ｍｇ，Ｃａ，Ｚｎの
順で光活性が高いことを確認している。このことから電
気陰性度が１.６より小さく、イオン半径が０.２ｎｍよ
り小さいものの中でも原子番号の小さい金属元素が有効
であると思われる。In the first invention, the metal is Na,
It is preferably at least one metal selected from Li, K, Mg, Ca, Sr, and Zn. In particular, according to the experiments of the present inventors, it has been confirmed that the photoactivity is higher in the order of Li, Na, Mg, Ca, and Zn. From this, it is considered that a metal element having a small atomic number is effective among those having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm.
【００１６】また、第１の発明においてＴｉＯ2 微粒子
の大きさが５〜２０ｎｍであることが好ましい。酸化チ
タン粒子の径が大きくなると光触媒薄膜の光透過性が低
下する。また、粒子径が小さい方が触媒粒子の表面積が
大きいため、触媒性能が向上する。しかし、粒子径が小
さすぎても逆に触媒性能が低下することから、望ましい
酸化チタンの粒子径としては５〜２０ｎｍが良い。In the first invention, the size of the TiO 2 fine particles is preferably 5 to 20 nm. As the diameter of the titanium oxide particles increases, the light transmittance of the photocatalytic thin film decreases. In addition, the smaller the particle size, the larger the surface area of the catalyst particles, so that the catalyst performance is improved. However, even if the particle diameter is too small, the catalytic performance is conversely reduced. Therefore, the desirable particle diameter of titanium oxide is preferably 5 to 20 nm.
【００１７】第１の発明において金属元素の量が酸化物
光触媒薄膜全体に対して２〜５０ｗｔ％、より好ましく
は５〜２０ｗｔ％であることが望ましい。図５にリチウ
ム添加量と触媒活性（一定時間後の有機物の分解率）の
関係を示す。リチウム無添加のものに比べて、リチウム
添加量が２重量％以上になると触媒活性が向上している
ことがわかる。In the first invention, it is desirable that the amount of the metal element is 2 to 50% by weight, more preferably 5 to 20% by weight based on the whole oxide photocatalytic thin film. FIG. 5 shows the relationship between the amount of lithium added and the catalytic activity (the decomposition rate of organic substances after a certain time). It can be seen that the catalytic activity is improved when the added amount of lithium is 2% by weight or more as compared with the case where no lithium is added.
【００１８】何故このような関係となるのかは現在のと
ころ明確には解っていない。特にリチウムの場合、１ｗ
ｔ％の添加で触媒活性が２割ほど低下しているがこの原
因については今後の研究を待たねばならない。The reason why such a relationship is established is not clearly understood at present. Especially for lithium, 1w
The catalyst activity is reduced by about 20% with the addition of t%, but the cause of this must be further studied.
【００１９】第１の発明において、無機物薄膜が、Ｓｉ
Ｏ2 を主成分とするものであっても良い。無機薄膜をゾ
ルゲル法で作製する場合、金属アルコシキド水溶液を用
いる。珪素のアルコキシドは他の物に比べて価格が安
く、また低温で酸化物が形成されるため、酸化チタンの
粒子を分散させるための無機薄膜として好適である。In the first invention, the inorganic thin film is made of Si
O 2 may be the main component. When preparing an inorganic thin film by a sol-gel method, an aqueous solution of metal alkoxide is used. Silicon alkoxides are inexpensive compared to other materials, and oxides are formed at low temperatures, so that they are suitable as inorganic thin films for dispersing titanium oxide particles.
【００２０】また、酸化物光触媒薄膜中のＴｉＯ2／Ｓ
ｉＯ2比が重量で９〜５であることが好ましい。Further, TiO 2 / S in the oxide photocatalytic thin film
It is preferable iO 2 ratio of 9 to 5 by weight.
【００２１】第１の発明において無機物薄膜中に、更に
Ｐｔ，Ｒｈ，Ｐｄ，Ａｇ，Ｃｕ，Ｎｉの中から選ばれた
少なくとも一種の金属元素が含まれていることが好まし
い。これら元素は、従来の技術においても触媒活性の向
上効果があるものとされていたもので、本発明に適用す
ることが可能である。また、これらの元素は導電性を有
しているため、光触媒薄膜の帯電を防止でき、空気中の
塵埃の付着を抑制することができるという効果も得られ
る。In the first invention, the inorganic thin film preferably further contains at least one metal element selected from Pt, Rh, Pd, Ag, Cu, and Ni. These elements are said to have the effect of improving the catalytic activity even in the prior art, and can be applied to the present invention. In addition, since these elements have conductivity, it is possible to prevent the photocatalytic thin film from being charged and to suppress the adhesion of dust in the air.
【００２２】第１の発明において、酸化物薄膜中に、更
に電子親和力が１.２ 以上の金属元素から構成される酸
化物半導体微粒子が分散していることが好ましい。In the first invention, it is preferable that fine particles of an oxide semiconductor composed of a metal element having an electron affinity of 1.2 or more are further dispersed in the oxide thin film.
【００２３】これはキャリア濃度の小さいＴｉＯ2 にキ
ャリア濃度の大きな酸化物半導体より、キャリアを注入
することにより達成される。従って、酸化物半導体から
TiO2にキャリアが流れやすいようにする必要がある。酸
化物半導体の電子親和力がＴｉ以下であるとショットキ
ーバリアが形成される。そこで、添加する材料は電子親
和力が１.２ｅＶ 以上である必要がある。This is achieved by injecting carriers from an oxide semiconductor having a high carrier concentration into TiO 2 having a low carrier concentration. Therefore, from the oxide semiconductor
It is necessary to make it easy for carriers to flow into TiO 2 . When the electron affinity of the oxide semiconductor is less than or equal to Ti, a Schottky barrier is formed. Therefore, the material to be added needs to have an electron affinity of 1.2 eV or more.
【００２４】上記において、前記酸化物半導体粒子が分
散している層を、前記ＴｉＯ2 微粒子が分散している層
とは別に設けられていることが好ましい。特に、表面よ
り数えて第１層にＳｉＯ2 中にＴｉＯ2 微粒子が分散し
てあり、電気陰性度が１.６より小さく、イオン半径が
０.２ｎｍ より小さい元素であって、原子価が２以下の
イオンを添加してある酸化物光触媒薄膜が形成してあっ
て、表面より数えて第２層には、少なくとも電子親和力
が１.２ 以上の金属元素から構成される酸化物半導体を
主体とする酸化物微粒子が分散している酸化物薄膜を形
成し、積層構造とすることが好ましい。In the above, it is preferable that the layer in which the oxide semiconductor particles are dispersed is provided separately from the layer in which the TiO 2 particles are dispersed. In particular, TiO 2 fine particles are dispersed in SiO 2 in the first layer counted from the surface, the electronegativity is smaller than 1.6, the ionic radius is smaller than 0.2 nm, and the valence is 2 An oxide photocatalytic thin film to which the following ions are added is formed, and the second layer counted from the surface mainly includes an oxide semiconductor composed of a metal element having an electron affinity of at least 1.2 or more. It is preferable to form an oxide thin film in which oxide particles to be dispersed are dispersed to form a laminated structure.
【００２５】上記酸化物半導体微粒子としてはＳｎ，Ｆ
ｅ，Ｃｒの中から選ばれた少なくとも一種の酸化物から
なることが好ましい。As the oxide semiconductor fine particles, Sn, F
It is preferable to be made of at least one oxide selected from e and Cr.
【００２６】また、上記酸化物半導体微粒子がＡＴＯ
（アンチモン添加酸化スズ）であることも好ましい。The above oxide semiconductor fine particles may be made of ATO.
(Tin oxide-added tin oxide) is also preferable.
【００２７】ＡＴＯなどの導電性微粒子を添加した場合
及び積層した場合は、光触媒の性能を向上すると共に、
帯電防止機能が付与されることによって、有機物の分解
だけでなく、空気中に浮遊している埃などの無機物の付
着を防ぎ、より高性能な防汚機能を提供できる。When conductive fine particles such as ATO or the like are added and when they are laminated, the performance of the photocatalyst is improved and
By providing the antistatic function, not only decomposition of organic substances but also prevention of adhesion of inorganic substances such as dust floating in the air can be prevented, and a higher performance antifouling function can be provided.
【００２８】上記した酸化物半導体微粒子の含有量が２
〜５０ｗｔ％であることが好ましい。When the content of the oxide semiconductor fine particles is 2
It is preferably about 50% by weight.
【００２９】更に、本発明の目的を達成するために本発
明の第２の発明では、ＴｉＯ2 微粒子が無機物薄膜中に
分散している酸化物光触媒薄膜において、前記無機物薄
膜中に、電子親和力が１.２ 以上の金属元素から構成さ
れる酸化物半導体微粒子が分散していることを特徴とす
る酸化物光触媒薄膜の構成を用いる。Further, in order to achieve the object of the present invention, in the second invention of the present invention, in the oxide photocatalytic thin film in which TiO 2 fine particles are dispersed in the inorganic thin film, the inorganic thin film has an electron affinity. Use is made of a structure of an oxide photocatalytic thin film in which oxide semiconductor fine particles composed of 1.2 or more metal elements are dispersed.
【００３０】本発明の第３の発明は、上記した酸化物光
触媒薄膜を基材表面に備えたことを特徴とする物品にあ
る。A third invention of the present invention is an article characterized in that the above-mentioned oxide photocatalyst thin film is provided on a substrate surface.
【００３１】第３の発明では酸化物光触媒薄膜の膜厚が
１００〜５００ｎｍであることが好ましい。In the third invention, the thickness of the oxide photocatalyst thin film is preferably from 100 to 500 nm.
【００３２】更に第３の発明では、酸化物光触媒薄膜
と、前記物品の基材表面との間に、無機物からなるバリ
ア層を設けることもできる。Further, in the third invention, a barrier layer made of an inorganic substance may be provided between the oxide photocatalyst thin film and the substrate surface of the article.
【００３３】バリア層としては、特にＡｌ，Ｚｒ，Ｆｅ
より選ばれた少なくとも一種の金属元素を含む金属酸化
物の膜であることが好ましい。As the barrier layer, Al, Zr, Fe
It is preferable that the film be a metal oxide film containing at least one metal element selected from the above.
【００３４】本発明者らはＦｅ，Ａｌ，Ｚｒを添加する
とＴｉＯ2 の光触媒が失われることを見出した。有機物
を主体とする基板材料を用いた場合、光触媒作用により
基板を自己破壊するという問題がある。そこで、本発明
は基板と光触媒の間にバリア層を形成するが、このバリ
ア層にＦｅ，Ａｌ，Ｚｒを添加することで、完全に自己
破壊を抑制することができる。さらに、高性能なバリア
層であるため、膜厚を十分薄くすることが可能となる。The present inventors have found that the addition of Fe, Al and Zr results in loss of the TiO 2 photocatalyst. When a substrate material mainly composed of an organic substance is used, there is a problem that the substrate is self-destructed by photocatalysis. Therefore, in the present invention, a barrier layer is formed between the substrate and the photocatalyst. By adding Fe, Al, and Zr to the barrier layer, self-destruction can be completely suppressed. Further, since the barrier layer is a high-performance barrier layer, the film thickness can be sufficiently reduced.
【００３５】すなわち、上記物品の基材が、分解開始温
度３００℃以下の有機物高分子化合物からなることが好
ましい。That is, it is preferable that the substrate of the article is made of an organic polymer compound having a decomposition start temperature of 300 ° C. or less.
【００３６】また、本発明の第４の発明では、有機物高
分子化合物を主体とする基材と、該機材の表面に設けら
れた、無機物からなるバリア層と、該バリア層の表面に
設けられた、有機物の分解反応を触媒する酸化物触媒層
からなる物品との構成が用いられる。In the fourth invention of the present invention, a base material mainly composed of an organic polymer compound, a barrier layer made of an inorganic substance provided on the surface of the equipment, and a base material provided on the surface of the barrier layer Further, a configuration with an article comprising an oxide catalyst layer that catalyzes a decomposition reaction of an organic substance is used.
【００３７】[0037]
（実施例１）ＳｉＯ2 ゾル中にＴｉＯ2 微粒子を分散さ
せた溶液を作製した。この溶液を用いてＰＥＴフィルム
上にＴｉＯ2 膜を形成し、図１のＰＥＴフィルムを作製
した。以下にその手順を示した。(Example 1) A solution in which TiO 2 fine particles were dispersed in a SiO 2 sol was prepared. Using this solution, a TiO 2 film was formed on a PET film to produce the PET film shown in FIG. The procedure is shown below.
【００３８】まず、ＳｉＯ2 ゾルの作製法について説明
する。５ｇのテトラエトキシシランを１００ｍｌの水−
エタノール−プロパノール（３：２７：７０）混合溶液
中に溶解し、４０℃で５時間程度撹伴した。得られた溶
液は室温で２週間放置してＳｉＯ2 ゾルとした。First, a method for producing a SiO 2 sol will be described. 5 g of tetraethoxysilane is added to 100 ml of water-
It was dissolved in a mixed solution of ethanol and propanol (3:27:70) and stirred at 40 ° C. for about 5 hours. The obtained solution was left at room temperature for 2 weeks to form a SiO 2 sol.
【００３９】次にＳｉＯ2ゾル中にＴｉＯ2微粒子を分散
させた溶液の作製法について説明する。先に作製したＳ
ｉＯ2ゾル中にＴｉＯ2微粒子を重量比でＴｉＯ2 ／Ｓｉ
Ｏ2を９として添加した。また、固形分濃度は４ｗｔ％
とし、必要量水を加えて調整した。その後５mmφのジル
コニアボールを用いてＳｉＯ2 ゾル中にＴｉＯ2 微粒子
を分散させるために２４ｈｒボールミルで処理し、Ｓｉ
Ｏ2 ゾル中にＴｉＯ2微粒子を分散させた溶液を作製し
た。Next, a method for preparing a solution in which TiO 2 fine particles are dispersed in a SiO 2 sol will be described. S made earlier
TiO 2 fine particles in a weight ratio of TiO 2 / Si in TiO 2 sol
O 2 was added as 9. The solid concentration is 4wt%
And adjusted by adding necessary amount of water. Then, a zirconia ball having a diameter of 5 mm was used to disperse the TiO 2 fine particles in the SiO 2 sol with a ball mill for 24 hours.
A solution in which TiO 2 fine particles were dispersed in an O 2 sol was prepared.
【００４０】ＰＥＴフィルム１に作製したＴｉＯ2 微粒
子分散ＳｉＯ2 ゾルをコートして、１２０℃で低圧水銀
ランプ(強度：１５ｍＷ／cm2）を照射しながら５分間処
理してＳｉＯ2 膜２中にＴｉＯ2 微粒子３が分散したＴ
ｉＯ2 分散ＳｉＯ2 膜４をコートしたプラスチックフィ
ルムを形成した。ＰＥＴフィルム上に得られた薄膜は、
膜質及び強度共に良好であり、膜厚は３００ｎｍであっ
た。[0040] by coating the TiO 2 fine particle dispersion SiO 2 sol prepared on a PET film 1, a low pressure mercury lamp (intensity: 15 mW / cm 2) at 120 ° C. in for 5 minutes SiO 2 film 2 while irradiating T in which TiO 2 fine particles 3 are dispersed
A plastic film coated with the iO 2 dispersed SiO 2 film 4 was formed. The thin film obtained on PET film is
Both the film quality and strength were good, and the film thickness was 300 nm.
【００４１】酸化チタンは近年、光触媒機能による有機
物の分解活性に優れるとされることより有機物の分解活
性を評価した。なお、活性試験は薄膜に赤紫系の有機色
素をコートして２５４ｎｍで１ｍＷ／cm2 の光を照射し
て行った。分解速度は初期の色素の透過率からの変化量
より求めた。図２にその結果を示した。In recent years, titanium oxide was considered to have excellent activity of decomposing organic substances by a photocatalytic function, and thus the activity of decomposing organic substances was evaluated. The activity test was performed by coating the thin film with a red-purple organic dye and irradiating it with 254 nm light of 1 mW / cm 2 . The decomposition rate was determined from the amount of change from the initial transmittance of the dye. FIG. 2 shows the result.
【００４２】図には比較のためにＴｉＯ2 分散ＳｉＯ2
膜付きの他、膜なしとＳｉＯ2 膜の結果も示した。Ｔｉ
Ｏ2 分散ＳｉＯ2 膜なし及びＳｉＯ2 膜ではほとんど色
素量に変化はないが、ＴｉＯ2 分散ＳｉＯ2 膜ありの場
合は３０分後に４５％分解したという結果が得られた。In the figure, TiO 2 dispersed SiO 2 is shown for comparison.
The results with and without the film and with the SiO 2 film are also shown. Ti
There was almost no change in the pigment amount without the O 2 -dispersed SiO 2 film and with the SiO 2 film, but in the case of the TiO 2 -dispersed SiO 2 film, a result of 45% decomposition was obtained after 30 minutes.
【００４３】この様に、光触媒機能を有したＴｉＯ2 分
散ＳｉＯ2 膜付きＰＥＴフィルムを作製することができ
た。本発明の成膜法は、１２０℃程度で作製が可能であ
り、パイレックスガラス基板以外にプラスチック材料へ
の応用が可能である。通常のゾルゲル法では、４００℃
程度の温度が必要であるためプラスチック製品への応用
が困難であったり、ＴｉＯ2 の結晶化に１０分以上の時
間が必要である。一方、本発明の作製法は低温で成膜が
可能であるため、使用できる基材が豊富で、どの様な表
面にも光触媒を成膜できる。また、数分間という短時間
処理が可能で生産コストの大幅な低下が可能である。Thus, a PET film with a TiO 2 dispersed SiO 2 film having a photocatalytic function was produced. The film formation method of the present invention can be manufactured at about 120 ° C., and can be applied to plastic materials other than Pyrex glass substrates. 400 ° C. in a normal sol-gel method
Since a temperature of the order is required, application to plastic products is difficult, and crystallization of TiO 2 requires a time of 10 minutes or more. On the other hand, since the film formation method of the present invention can form a film at a low temperature, a variety of substrates can be used, and a photocatalyst can be formed on any surface. In addition, the processing can be performed for a short time of several minutes, and the production cost can be significantly reduced.
【００４４】次に、光触媒の性能向上のために、助触媒
添加を行った。先に作製したＳiＯ2ゾル中にＴｉＯ2 微
粒子を分散させた溶液中に各種硝酸塩を添加して、ＰＥ
Ｔフィルム上に成膜し、色素の分解反応を行った。結果
は表１に示した。Next, a cocatalyst was added to improve the performance of the photocatalyst. Various nitrates are added to a solution in which TiO 2 fine particles are dispersed in the previously prepared SiO 2 sol, and PE
A film was formed on a T film, and a decomposition reaction of the dye was performed. The results are shown in Table 1.
【００４５】[0045]
【表１】 [Table 1]
【００４６】Ｎａ，Ｌｉ，Ｋ，Ｍｇ，Ｃａ，Ｓｒ，Ｚｎ
添加の光触媒が有効であり、Ｆｅ，Ａｌは失活剤となる
ことがわかった。Na, Li, K, Mg, Ca, Sr, Zn
It was found that the added photocatalyst was effective, and Fe and Al became deactivators.
【００４７】図３に電気陰性度に対し助触媒の添加効果
をプロットした結果を示した。電気陰性度は小さいもの
ほど効果があるようだが、特にＬｉ，Ｎａ，Ｍｇが有効
であることから、電気陰性度だけでなくイオン半径も重
要であることがわかった。図４には電気陰性度とイオン
半径そして添加効果の関係を示した。このように、電気
陰性度が１.６より小さく、イオン半径が０.２ｎｍより
小さい元素でその価数が２以下のイオンを添加すること
が有効であることがわかった。FIG. 3 shows the results of plotting the effect of adding a cocatalyst on the electronegativity. The smaller the electronegativity seems to be, the more effective it is. Particularly, since Li, Na, and Mg are effective, it was found that not only the electronegativity but also the ionic radius is important. FIG. 4 shows the relationship between the electronegativity, the ionic radius and the effect of addition. As described above, it was found that it is effective to add an ion having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm and having a valence of 2 or less.
【００４８】（実施例２）ＳｉＯ2 ゾル中に粒子径の異
なるＴｉＯ2 微粒子を分散させた溶液を数種類作製し
た。なお、ＴｉＯ2／ＳｉＯ2比は重量比で９とし、Ｌｉ
添加量は５ｗｔ％とし、実施例１同様な操作でＴｉＯ2
分散ＳｉＯ2 膜をＰＥＴフィルム上に形成し、有機色素
を用いて１０分後の分解率を調べた。(Example 2) Several kinds of solutions were prepared by dispersing TiO 2 fine particles having different particle diameters in a SiO 2 sol. The TiO 2 / SiO 2 ratio was set to 9 by weight, and Li
The addition amount was 5 wt%, and TiO 2
A dispersed SiO 2 film was formed on a PET film, and the decomposition rate after 10 minutes was examined using an organic dye.
【００４９】[0049]
【表２】 [Table 2]
【００５０】表２に作製した試料の各条件と試験結果を
示した。これらの結果より、分散したＴｉＯ2 粒子の大
きさは、８〜１０ｎｍが最も有効であることが分かっ
た。このように、粒子径により分解速度が変化してお
り、さらにＴｉＯ2／ＳｉＯ2比を小さくするとＴｉＯ2
微粒子の最適粒子径は変化したが、５〜２０ｎｍの範囲
であれば分解速度は良好であった。従って、Ｌｉ添加触
媒のＴｉＯ2 粒子径は５〜２０ｎｍであれば良いことが
分かった。また、以上の結果はＬｉ以外のＮａ，Ｋ，Ｍ
ｇ，Ｃａ，Ｓｒ，Ｚｎについても同様であった。Table 2 shows the conditions and test results of the prepared samples. From these results, it was found that the most effective size of the dispersed TiO 2 particles was 8 to 10 nm. As described above, the decomposition rate changes depending on the particle size, and when the TiO 2 / SiO 2 ratio is further reduced, the TiO 2
Although the optimum particle diameter of the fine particles changed, the decomposition rate was good in the range of 5 to 20 nm. Therefore, it was found that the TiO 2 particle diameter of the Li-added catalyst should be 5 to 20 nm. The above results indicate that Na, K, M other than Li
The same applies to g, Ca, Sr, and Zn.
【００５１】（実施例３）表３にＬｉ添加量，ＴｉＯ2
／ＳｉＯ2を変化させた場合の色素分解率及び膜強度に
ついて調べた結果を示した。なお溶液の作製及び成膜法
は実施例１同様に行った。これらの結果より分解率と強
度ともに有効である条件は、Ｌｉ添加量が０.５〜２０
ｗｔ％で、ＴｉＯ2／ＳｉＯ2が９〜５であることが分か
った。Example 3 Table 3 shows the amounts of Li added and TiO 2
The results of examining the dye decomposition rate and the film strength when changing the ratio of / SiO 2 are shown. The preparation of the solution and the film formation method were performed in the same manner as in Example 1. From these results, the conditions under which both the decomposition rate and the strength are effective are that the Li content is 0.5 to 20.
In wt%, TiO 2 / SiO 2 was found to be 9-5.
【００５２】[0052]
【表３】 [Table 3]
【００５３】表４にはＴｉＯ2／ＳｉＯ2及び膜厚を変化
させた場合の色素分解率及び膜質について調べた結果を
示した。なお溶液の作製及び成膜法は実施例１同様に行
ったが、膜厚は溶液の固形分濃度を０.５〜８ｗｔ％ま
で変化させて調節した。Table 4 shows the results of examining the dye decomposition rate and film quality when TiO 2 / SiO 2 and the film thickness were changed. The solution preparation and film formation were performed in the same manner as in Example 1, but the film thickness was adjusted by changing the solid content of the solution from 0.5 to 8 wt%.
【００５４】結果は膜厚が１００〜５００ｎｍであれば
ＴｉＯ2／ＳｉＯ2比の影響を受けずに分解率，膜質とも
良好であることが分かった。As a result, it was found that if the film thickness was 100 to 500 nm, the decomposition rate and the film quality were good without being affected by the TiO 2 / SiO 2 ratio.
【００５５】以上の結果はＬｉ以外のＮａ，Ｋ，Ｍｇ，
Ｃａ，Ｓｒ，Ｚｎについても同様であった。The above results indicate that Na, K, Mg,
The same applies to Ca, Sr, and Zn.
【００５６】[0056]
【表４】 [Table 4]
【００５７】（実施例４）表５にはＴｉＯ2 以外の酸化
物半導体であるＡＴＯ,ＩＴＯ,ＺｎＯ,Ｆｅ2Ｏ3,Ｃｒ2
Ｏ3微粒子を添加した場合の色素分解率を調べた結果を
示した。結果はATO,Ｆｅ2Ｏ3，Ｃｒ2Ｏ3微粒子添加が有
効であり、添加量はいずれの場合も添加すれば有効であ
り、特に１０〜２０ｗｔ％が最も有効であった。ここ
で、各酸化物の構成元素の電子親和力を見ると以下のよ
うになり、１.２ｅＶ 以上の電子親和力を有する構成元
素を用いた酸化物半導体を用いると有効であることが分
かった。Example 4 Table 5 shows that oxide semiconductors other than TiO 2 , such as ATO, ITO, ZnO, Fe 2 O 3 , and Cr 2
The results of examining the dye decomposition rate when O 3 fine particles were added were shown. As a result, the addition of fine particles of ATO, Fe 2 O 3 , and Cr 2 O 3 was effective, and the addition amount was effective in any case, especially 10 to 20 wt% was most effective. Here, the electron affinity of the constituent elements of each oxide is as follows, and it has been found that it is effective to use an oxide semiconductor using a constituent element having an electron affinity of 1.2 eV or more.
【００５８】[0058]
【表５】 [Table 5]
【００５９】 構成元素 Ｔｉ Ｓｎ Ｉｎ Ｚｎ Ｆｅ Ｃｒ 電子親和力(ｅＶ) 1.25 1.2 0.2 −1.2 3.16 3.54 酸化物半導体の電子親和力がＴｉのそれより小さい場合
は、微粒子の粒子界面にはショットキーバリアが形成さ
れ、添加した酸化物半導体のキャリアがＴiＯ2中に注入
できず効果が現れない。これに対して酸化物半導体の電
子親和力がＴｉのそれより小さい場合は、微粒子の粒子
界面にはショットキーバリアが形成されず、オーミック
接合となり、容易に酸化物半導体のキャリアがＴｉＯ2
中に注入され、有効に機能する。特に有効であったＡＴ
Ｏは、電子親和力はＴｉより若干小さいが、その差はほ
とんどないため性能向上が見られた。これは導電性酸化
物であるＡＴＯはキャリア濃度が高く、ＡＴＯの大量の
キャリアがＴｉＯ2 中に注入され、光触媒の活性が向上
した。さらに、このような酸化物半導体添加時において
も、Ｌｉの添加効果が大きいということもわかった。Constituent elements Ti Sn In Zn Fe Cr Electron affinity (eV) 1.25 1.2 0.2 -1.2 3.16 3.54 When the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles. In addition, carriers of the added oxide semiconductor cannot be injected into TiO 2 , and the effect is not exhibited. If the electron affinity of the oxide semiconductor contrast is smaller than that of Ti, the grain boundaries of the particles is not Schottky barrier formation becomes an ohmic junction, readily oxide semiconductor carriers TiO 2
It is injected during and works effectively. AT that was particularly effective
O has a slightly smaller electron affinity than Ti, but there is almost no difference, so that an improvement in performance was observed. This is because ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of ATO is injected into TiO 2 to improve the activity of the photocatalyst. Further, it was also found that the effect of adding Li was large even when such an oxide semiconductor was added.
【００６０】また、酸化物半導体の持つキャリアを有効
に利用する方法としては、微粒子添加ばかりではなく積
層化によっても可能である。表６にはＴｉＯ2／ＳｉＯ2
膜とＡＴＯ膜を積層した場合の結果を示した。結果は積
層することが有効で、さらに、Ｌｉを両方に添加するこ
とで、更に性能が向上することがわかった。また、多数
回交互に積層することも有効であることが分かった。As a method of effectively utilizing the carriers of the oxide semiconductor, not only addition of fine particles but also lamination can be used. Table 6 shows TiO 2 / SiO 2
The results when the film and the ATO film are stacked are shown. As a result, it was found that lamination was effective, and that the performance was further improved by adding Li to both. It has also been found that it is effective to alternately laminate a large number of times.
【００６１】[0061]
【表６】 [Table 6]
【００６２】また、図５には同様の試験方法を用いて第
１層のＬｉ添加量を５ｗｔ％以下の範囲でも実施した結
果を示す。この図より、Ｌｉの添加量が２ｗｔ％以下の
範囲では、Ｌｉを添加することによって、Ｌｉ無添加の
ものの有機物分解率よりも有機物分解率が低下している
ことがわかる。この原因については、現在のところよく
わかっていない。FIG. 5 shows the results of the same test method performed when the amount of Li added to the first layer was in the range of 5 wt% or less. From this figure, it can be seen that in the range where the amount of Li added is 2 wt% or less, the addition of Li lowers the organic substance decomposition rate lower than the organic substance decomposition rate of the case where Li is not added. The cause is currently unknown.
【００６３】（実施例６）ＳｉＯ2ゾル中に粒子径５ｎ
ｍのＴｉＯ2微粒子を分散させた溶液を作製し、これに
Ａｇ，Ｐｔ，Ｐｄ，Ｒｈ，Ｎｉ，Ｃｕ，ＲｕＯ2 微粒子
をそれぞれＴｉＯ2に対して２ｗｔ％添加した。なお、
ＴｉＯ2／ＳｉＯ2比は重量比で９とした。作製したＡ
ｇ，ＲｕＯ2 微粒子添加ＴｉＯ2分散ＳｉＯ2ゾルを用い
て、実施例１と同様な操作でＡｇ，Ｐｔ，Ｐｄ，Ｒｈ，
Ｎｉ，Ｃｕ，ＲｕＯ2 微粒子を添加したＴｉＯ2分散Ｓ
ｉＯ2膜をＰＥＴフィルム上に形成し、有機色素の分解
特性を調べた。結果は表７に示したようにＡｇ，Ｐｔ，
Ｐｄ，Ｒｈ，Ｎｉ，Ｃｕ，ＲｕＯ2微粒子添加により分
解速度が大きくなっていることが分かった。Example 6 Particle Size 5n in SiO 2 Sol
A solution in which m TiO 2 fine particles were dispersed was prepared, and Ag, Pt, Pd, Rh, Ni, Cu, and RuO 2 fine particles were each added to the solution at 2 wt% with respect to TiO 2 . In addition,
The TiO 2 / SiO 2 ratio was 9 by weight. A made
g, RuO 2 fine particles added TiO 2 dispersed SiO 2 sol, and Ag, Pt, Pd, Rh,
TiO 2 dispersion S to which Ni, Cu, RuO 2 fine particles are added
An iO 2 film was formed on a PET film, and the decomposition characteristics of the organic dye were examined. As shown in Table 7, the results were Ag, Pt,
It was found that the decomposition rate was increased by the addition of Pd, Rh, Ni, Cu, and RuO 2 fine particles.
【００６４】[0064]
【表７】 [Table 7]
【００６５】（実施例７）実施例１で作製したＬｉ添加
光触媒とＬｉ無添加光触媒について、蛍光灯，太陽光，
白熱ランプ，水銀灯を用いて、タバコのヤニ，アセトア
ルデキド，尿素，大腸菌の分解特性を比較した。その結
果表８に示したようにＬｉ添加光触媒はいずれのランプ
を用いても、タバコのヤニ，アセトアルデキド，尿素，
大腸菌の分解特性が、Ｌｉ無添加光触媒の３〜５倍の効
果があることが分かった。このようにＬｉ添加触媒は、
紫外線ランプばかりでなく、生活環境下で使用するラン
プで十分な効果が得られることが分かった。また、Ｌｉ
以外のＮａ，Ｋ，Ｍｇ，Ｃａ，Ｓｒ，Ｚｎを添加した場
合の同様の効果が得られた。(Example 7) The Li-added photocatalyst and the Li-free photocatalyst prepared in Example 1 were analyzed using a fluorescent lamp, sunlight,
Using an incandescent lamp and a mercury lamp, the decomposition characteristics of cigarette tar, acetoaldehyde, urea and Escherichia coli were compared. As a result, as shown in Table 8, the Li-added photocatalyst was used for any of the lamps, regardless of the type of tobacco tar, acetoaldehyde, urea,
It was found that the decomposition characteristics of Escherichia coli were three to five times as effective as the Li-free photocatalyst. Thus, the Li-added catalyst is
It has been found that a sufficient effect can be obtained not only with an ultraviolet lamp but also with a lamp used in a living environment. Also, Li
Similar effects were obtained when other Na, K, Mg, Ca, Sr, and Zn were added.
【００６６】[0066]
【表８】 [Table 8]
【００６７】（実施例８）実施例１で作製したＬｉ添加
ＴｉＯ2 分散ＳｉＯ2 膜は、ＰＥＴフィルム上に直接成
膜すると、光触媒作用により基材のＰＥＴフィルムにダ
メージを与えてしまう。そこで、実施例１で作製したＬ
ｉ添加ＴｉＯ2 分散ＳｉＯ2 膜をコートする際、ＰＥＴ
フィルムとの間にＳｉＯ2 膜を１層設けたフィルムを作
製した。さらに、ＳｉＯ2 膜中に光触媒作用を失活させ
る成分となる、Ａｌ，Ｆｅ，Ｚｒの各硝酸塩を添加した
試料あるいはＬｉ添加ＴｉＯ2 分散ＳｉＯ2 膜中にＡＴ
Ｏを添加した試料を作製し、各種試験を行った。その結
果は表９に示した。Example 8 When the Li-added TiO 2 -dispersed SiO 2 film produced in Example 1 is formed directly on a PET film, the PET film as a substrate is damaged by a photocatalytic action. Thus, the L produced in Example 1
When coating i-added TiO 2 dispersed SiO 2 film, PET
A film having one layer of SiO 2 film between the film and the film was produced. Furthermore, AT in the SiO 2 film becomes component to deactivate the photocatalytic action, Al, Fe, a sample or Li added TiO 2 dispersed SiO 2 film with the addition of nitrates of Zr
Samples to which O was added were prepared, and various tests were performed. The results are shown in Table 9.
【００６８】[0068]
【表９】 [Table 9]
【００６９】結果はＬｉ添加ＴｉＯ2 分散ＳｉＯ2 膜と
ＰＥＴフィルムの間に、バリア層としてＳｉＯ2 膜を１
層設けることで長期間使用しても膜剥がれを防ぐことが
できた。さらに、Ａｌ，Ｆｅ，Ｚｒを添加することで光
触媒活性を完全に失活させることができ、接着強度を維
持できることが分かった。また、ＡＴＯ添加膜では帯電
防止効果が加味され埃等の付着も抑制でき、有機物の分
解だけでなく、無機物の付着も防ぐことができ、より優
れた防汚効果を有したフィルムを作製できた。The results show that a SiO 2 film was formed as a barrier layer between the Li-added TiO 2 dispersed SiO 2 film and the PET film.
By providing a layer, film peeling could be prevented even after long-term use. Furthermore, it was found that by adding Al, Fe, and Zr, the photocatalytic activity could be completely deactivated and the adhesive strength could be maintained. In addition, the ATO-added film added an antistatic effect to suppress the adhesion of dust and the like, was able to prevent not only the decomposition of organic substances but also the adhesion of inorganic substances, and produced a film having a better antifouling effect. .
【００７０】[0070]
【発明の効果】耐熱性のない基材上に高活性な光触媒を
形成し、抗菌，防汚効果の優れた物品を提供することが
できる。According to the present invention, a highly active photocatalyst is formed on a substrate having no heat resistance, and an article having excellent antibacterial and antifouling effects can be provided.
【図１】プラスチックフィルム上に形成したＴｉＯ2 分
散ＳｉＯ2 積層膜の構造。FIG. 1 shows the structure of a TiO 2 dispersed SiO 2 laminated film formed on a plastic film.
【図２】有機色素の分解試験結果を示す図。FIG. 2 is a diagram showing a decomposition test result of an organic dye.
【図３】電気陰性度と分解率の関係を示す図。FIG. 3 is a diagram showing a relationship between electronegativity and decomposition rate.
【図４】電気陰性度とイオン半径の関係を示す図。FIG. 4 is a diagram showing the relationship between electronegativity and ionic radius.
【図５】リチウム添加量と有機物分解率の関係を示す
図。FIG. 5 is a graph showing the relationship between the amount of lithium added and the organic matter decomposition rate.
１…ＰＥＴフィルム，２…ＳｉＯ2 膜，３…ＴｉＯ2 微
粒子、４…ＴｉＯ2 分散ＳｉＯ2 膜。1 ... PET film, 2 ... SiO 2 film, 3 ... TiO 2 fine particles, 4 ... TiO 2 dispersed SiO 2 film.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 23/14 Ｂ０１Ｊ 23/14 Ａ 23/18 23/18 Ａ 23/26 23/26 Ａ 23/38 23/38 Ａ 23/74 23/74 Ａ (72)発明者 高橋 研 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 23/14 B01J 23/14 A 23/18 23/18 A 23/26 23/26 A 23/38 23/38 A 23/74 23 / 74 A (72) Inventor Ken Takahashi 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd.
Claims (19)
いる酸化物光触媒薄膜において、 前記無機物薄膜中に、電気陰性度が１.６より小さく、
かつイオン半径が０.２ｎｍより小さい元素であって、
原子価が２以下の金属元素が含有されていることを特徴
とする酸化物光触媒薄膜。1. An oxide photocatalytic thin film in which TiO 2 fine particles are dispersed in an inorganic thin film, wherein the inorganic thin film has an electronegativity of less than 1.6,
And an element having an ionic radius smaller than 0.2 nm,
An oxide photocatalytic thin film comprising a metal element having a valence of 2 or less.
Ｍｇ，Ｃａ，Ｓｒ，Ｚｎの中から選ばれた少なくとも一
種の金属であることを特徴とする酸化物光触媒薄膜。2. The method according to claim 1, wherein the metal is Na, Li, K,
An oxide photocatalytic thin film comprising at least one metal selected from Mg, Ca, Sr, and Zn.
５〜２０ｎｍであることを特徴とする酸化物光触媒薄
膜。3. The oxide photocatalytic thin film according to claim 1, wherein the TiO 2 fine particles have a size of 5 to 20 nm.
媒薄膜全体に対して０.５ 〜２０ｗｔ％であることを特
徴とする酸化物光触媒薄膜。4. The oxide photocatalyst thin film according to claim 1, wherein the amount of the metal element is 0.5 to 20 wt% based on the whole oxide photocatalyst thin film.
主成分とするものであることを特徴とする酸化物光触媒
薄膜。5. The oxide photocatalytic thin film according to claim 1, wherein the inorganic thin film is mainly composed of SiO 2 .
Ｏ2／ＳｉＯ2比が重量で９〜５であることを特徴とする
酸化物光触媒薄膜。6. Ti in the oxide photocatalytic thin film according to claim 5.
An oxide photocatalytic thin film having an O 2 / SiO 2 ratio of 9 to 5 by weight.
ｔ，Ｒｈ，Ｐｄ，Ａｇ，Ｃｕ，Ｎｉの中から選ばれた少
なくとも一種の金属元素が含まれていることを特徴とす
る酸化物光触媒薄膜。7. The oxide thin film according to claim 1, further comprising P
An oxide photocatalytic thin film comprising at least one metal element selected from t, Rh, Pd, Ag, Cu, and Ni.
親和力が１.２ 以上の金属元素から構成される酸化物半
導体微粒子が分散していることを特徴とする酸化物光触
媒薄膜。8. An oxide photocatalytic thin film, wherein oxide semiconductor fine particles composed of a metal element having an electron affinity of 1.2 or more are dispersed in the oxide thin film according to claim 1.
が分散している層を、前記ＴｉＯ2微粒子が分散してい
る層とは別に設けられていることを特徴とする酸化物光
触媒薄膜。9. The oxide photocatalytic thin film according to claim 8, wherein the layer in which the oxide semiconductor particles are dispersed is provided separately from the layer in which the TiO 2 fine particles are dispersed.
ｎ，Ｆｅ，Ｃｒの中から選ばれた少なくとも一種の酸化
物からなることを特徴とする酸化物光触媒薄膜。10. The oxide semiconductor fine particles according to claim 8, wherein
An oxide photocatalytic thin film comprising at least one oxide selected from n, Fe, and Cr.
ＴＯ（アンチモン添加酸化スズ）であることを特徴とす
る酸化物光触媒薄膜。11. The oxide semiconductor fine particles according to claim 8, wherein
An oxide photocatalytic thin film comprising TO (antimony-added tin oxide).
物半導体微粒子の含有量が２〜５０ｗｔ％であることを
特徴とする酸化物光触媒薄膜。12. An oxide photocatalytic thin film, wherein the content of the oxide semiconductor fine particles according to claim 8 is 2 to 50 wt%.
ている酸化物光触媒薄膜において、前記無機物薄膜中
に、電子親和力が１.２ 以上の金属元素から構成される
酸化物半導体微粒子が分散していることを特徴とする酸
化物光触媒薄膜。13. An oxide photocatalytic thin film in which TiO 2 fine particles are dispersed in an inorganic thin film, wherein oxide semiconductor fine particles composed of a metal element having an electron affinity of 1.2 or more are dispersed in the inorganic thin film. An oxide photocatalytic thin film characterized by the following.
物光触媒薄膜を基材表面に備えたことを特徴とする物
品。14. An article provided with the oxide photocatalyst thin film according to claim 1 on a substrate surface.
厚が１００〜５００ｎｍであることを特徴とする物品。15. An article characterized in that the oxide photocatalyst thin film according to claim 14 has a thickness of 100 to 500 nm.
前記物品の基材表面との間に、無機物からなるバリア層
を有することを特徴とする物品。16. An oxide photocatalyst thin film according to claim 14,
An article comprising a barrier layer made of an inorganic material between the article and a substrate surface of the article.
ｒ，Ｆｅより選ばれた少なくとも一種の金属元素を含む
金属酸化物の膜であることを特徴とする物品。17. The method according to claim 16, wherein the barrier layer is made of Al, Z.
An article characterized by being a metal oxide film containing at least one metal element selected from r and Fe.
材が、分解開始温度３００℃以下の有機物高分子化合物
からなることを特徴とする物品。18. An article, characterized in that the substrate according to any one of claims 14 to 17 is made of an organic polymer compound having a decomposition start temperature of 300 ° C. or lower.
と、該機材の表面に設けられた、無機物からなるバリア
層と、該バリア層の表面に設けられた、有機物の分解反
応を触媒する酸化物触媒層からなる物品。19. A substrate mainly composed of an organic polymer compound, a barrier layer made of an inorganic substance provided on the surface of the equipment, and catalyzes a decomposition reaction of an organic substance provided on the surface of the barrier layer. An article comprising an oxide catalyst layer.
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| JP12929997A JP3518251B2 (en) | 1997-05-20 | 1997-05-20 | Oxide photocatalytic thin film and article provided with the same |
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| JP12929997A JP3518251B2 (en) | 1997-05-20 | 1997-05-20 | Oxide photocatalytic thin film and article provided with the same |
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|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000033977A1 (en) * | 1998-12-07 | 2000-06-15 | Tao Inc. | Coating liquid for photocatalyst-containing coating film comprising organic coloring matter |
| WO2000046165A1 (en) * | 1999-02-05 | 2000-08-10 | Toto Ltd. | Cement-based joint body and joint material therefor |
| JP2001025437A (en) * | 1999-07-13 | 2001-01-30 | Tiger Vacuum Bottle Co Ltd | Heat insulating container |
| JP2002186860A (en) * | 2000-12-20 | 2002-07-02 | Nihon Tetra Pak Kk | Photocatalyst material |
| JP2003305371A (en) * | 1996-09-20 | 2003-10-28 | Hitachi Ltd | Photocatalyst thin film and article equipped therewith |
| WO2017082201A1 (en) * | 2015-11-09 | 2017-05-18 | 大阪ガスケミカル株式会社 | Microorganism-controlling agent and miticidal composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH08182934A (en) * | 1994-12-29 | 1996-07-16 | Ishihara Sangyo Kaisha Ltd | Photocatalyst and its production |
| JPH09227156A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Material expressing hydrophilic properties depending on optical excitation of optical semiconductor |
-
1997
- 1997-05-20 JP JP12929997A patent/JP3518251B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH08182934A (en) * | 1994-12-29 | 1996-07-16 | Ishihara Sangyo Kaisha Ltd | Photocatalyst and its production |
| JPH09227156A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Material expressing hydrophilic properties depending on optical excitation of optical semiconductor |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003305371A (en) * | 1996-09-20 | 2003-10-28 | Hitachi Ltd | Photocatalyst thin film and article equipped therewith |
| WO2000033977A1 (en) * | 1998-12-07 | 2000-06-15 | Tao Inc. | Coating liquid for photocatalyst-containing coating film comprising organic coloring matter |
| WO2000046165A1 (en) * | 1999-02-05 | 2000-08-10 | Toto Ltd. | Cement-based joint body and joint material therefor |
| JP2001025437A (en) * | 1999-07-13 | 2001-01-30 | Tiger Vacuum Bottle Co Ltd | Heat insulating container |
| JP2002186860A (en) * | 2000-12-20 | 2002-07-02 | Nihon Tetra Pak Kk | Photocatalyst material |
| WO2017082201A1 (en) * | 2015-11-09 | 2017-05-18 | 大阪ガスケミカル株式会社 | Microorganism-controlling agent and miticidal composition |
| JPWO2017082201A1 (en) * | 2015-11-09 | 2018-01-11 | 大阪ガスケミカル株式会社 | Microbicide control agent and acaricide composition |
| JP2018087201A (en) * | 2015-11-09 | 2018-06-07 | 大阪ガスケミカル株式会社 | Microorganism-controlling agent |
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| Publication number | Publication date |
|---|---|
| JP3518251B2 (en) | 2004-04-12 |
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