JP5919019B2 - Visible light responsive photocatalyst member and apparatus - Google Patents
Visible light responsive photocatalyst member and apparatus Download PDFInfo
- Publication number
- JP5919019B2 JP5919019B2 JP2012029728A JP2012029728A JP5919019B2 JP 5919019 B2 JP5919019 B2 JP 5919019B2 JP 2012029728 A JP2012029728 A JP 2012029728A JP 2012029728 A JP2012029728 A JP 2012029728A JP 5919019 B2 JP5919019 B2 JP 5919019B2
- Authority
- JP
- Japan
- Prior art keywords
- visible light
- responsive photocatalyst
- light responsive
- titanium oxide
- optical fiber
- 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.)
- Expired - Fee Related
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 120
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 87
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- 239000011162 core material Substances 0.000 claims description 28
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- 239000011248 coating agent Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 25
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Description
本発明は、可視光応答型の光触媒を用いた可視光応答型光触媒部材及び可視光応答型光触媒装置に関する。 The present invention relates to a visible light responsive photocatalyst member and a visible light responsive photocatalyst device using a visible light responsive photocatalyst.
酸化チタン等の光触媒は紫外線等の光を吸収すると強い酸化作用を発揮するため、自動車の排気ガス等から排出される窒素酸化物や硫黄酸化物等の環境汚染物質の除去による大気浄化、アンモニア、アセトアルデヒド、硫化水素、メチルメルカプタン等の悪臭物質の除去による脱臭、テトラクロロエチレンやトリハロメタン等の有機塩素化合物の分解除去による浄水、殺菌、抗菌、油分の分解による防汚など様々な用途に利用されている。 Photocatalysts such as titanium oxide exhibit a strong oxidizing action when absorbing light such as ultraviolet rays, so air purification by removing environmental pollutants such as nitrogen oxides and sulfur oxides emitted from automobile exhaust gases, ammonia, It is used for various purposes such as deodorization by removing malodorous substances such as acetaldehyde, hydrogen sulfide and methyl mercaptan, water purification by disassembly and removal of organic chlorine compounds such as tetrachloroethylene and trihalomethane, sterilization, antibacterial, and antifouling by decomposition of oil.
従来、光ファイバーの表面に光触媒粒子を担持させた光触媒担持部材が知られている（特許文献１、２）。しかし、これらの文献で具体的に示されているのは、光として紫外線を用い、光ファイバーとして石英ガラス製の光ファイバー用いたもののみである。しかし、石英ガラス製の光ファイバーは高価なため、特殊な用途にしか利用できず、汎用性に乏しい。 Conventionally, a photocatalyst carrying member in which photocatalyst particles are carried on the surface of an optical fiber is known (Patent Documents 1 and 2). However, these documents specifically show only an optical fiber made of quartz glass as an optical fiber using ultraviolet light as light. However, the optical fiber made of quartz glass is expensive, so it can be used only for special purposes and is not versatile.
一方、酸化チタン等の光触媒粒子を建築用木材、集成合板、石膏ボード、ガラス、タイル、プラスチックフィルム等の表面に塗布し、外部から、太陽光、紫外線ランプを照射して、光触媒機能を発現させる方法が知られている（特許文献３）。しかし、このような方法では、照射光エネルギーを光触媒機能発現に効率よく利用できない。 On the other hand, photocatalyst particles such as titanium oxide are applied to the surface of building wood, laminated plywood, gypsum board, glass, tile, plastic film, etc., and exposed to sunlight and ultraviolet lamps from outside to develop the photocatalytic function. A method is known (Patent Document 3). However, in such a method, the irradiation light energy cannot be efficiently used for the expression of the photocatalytic function.
従って、本発明の目的は、可視光を極めて効率よく光触媒機能発現に利用でき、しかも汎用性が高く、コストも低減できる可視光応答型光触媒部材及び装置を提供することにある。 Accordingly, an object of the present invention is to provide a visible light responsive photocatalyst member and apparatus that can use visible light for the expression of a photocatalytic function very efficiently, have high versatility, and can reduce costs.
本発明者は、上記目的を達成するため鋭意検討した結果、導光体の表面に可視光応答型光触媒粒子を担持し、導光体に導かれた光が導光体表面から可視光応答型光触媒粒子に照射されるようにすると、可視光が導光体の内部から可視光応答型光触媒を照射するので、可視光を極めて効率よく光触媒機能発現に利用できるとともに、導光体の素材として有機高分子をも利用できため、汎用性に優れ、しかも安価に製造できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventor carried visible light responsive photocatalyst particles on the surface of the light guide, and the light guided to the light guide from the surface of the light guide to the visible light responsive type. By irradiating the photocatalyst particles, visible light irradiates the visible light responsive photocatalyst from the inside of the light guide, so that the visible light can be used for the photocatalyst function very efficiently, and the light guide material is organic Since a polymer can also be used, it was found that it was excellent in versatility and could be produced at low cost, and the present invention was completed.
すなわち、本発明は、導光体表面に可視光応答型光触媒粒子が担持された構造を有しており、前記導光体に導かれた光が該導光体表面から前記可視光応答型光触媒粒子に照射されることにより光触媒機能が発現する可視光応答型光触媒部材を提供する。 That is, the present invention has a structure in which visible light responsive photocatalyst particles are supported on the surface of a light guide, and light guided to the light guide is transmitted from the surface of the light guide to the visible light responsive photocatalyst. Provided is a visible light responsive photocatalyst member that develops a photocatalytic function when irradiated with particles.
前記導光体としては光ファイバーが好ましい。 The light guide is preferably an optical fiber.
前記光ファイバーが光の透過するコアのみで形成され、該コアの屈折率が可視光応答型光触媒粒子の屈折率の９９％以下であってもよい。 The optical fiber may be formed of only a core through which light passes, and the refractive index of the core may be 99% or less of the refractive index of the visible light responsive photocatalyst particles.
前記光ファイバーが、光の透過するコアが該コアの屈折率よりも低い屈折率を有するクラッドで被覆された構造を有し、且つ可視光応答型光触媒を担持する部位のクラッド表面を粗すことによりコア内部を通る光がクラッド表面から漏れ出す構造をしているのも好ましい。 The optical fiber has a structure in which a core through which light passes is coated with a clad having a refractive index lower than the refractive index of the core, and roughens the clad surface of a portion carrying a visible light responsive photocatalyst It is also preferable that the light passing through the core leaks from the cladding surface.
前記光ファイバーは、１０ｃｍ長での光透過率（λ＝４５５ｎｍ）が５０％以上であるコアを有していてもよい。 The optical fiber may have a core having a light transmittance (λ = 455 nm) at a length of 10 cm of 50% or more.
前記光ファイバーが有機高分子で形成されていてもよい。 The optical fiber may be formed of an organic polymer.
前記可視光応答型光触媒は、鉄化合物が酸化面に選択的に担持されたルチル型又はアナターゼ型酸化チタンであるのが好ましい。 The visible light responsive photocatalyst is preferably a rutile type or anatase type titanium oxide in which an iron compound is selectively supported on an oxidized surface.
前記可視光応答型光触媒部材においては、導光体が光ファイバーであり、且つ複数の可視光応答型光触媒部材が束ねられた構造を有していてもよい。 The visible light responsive photocatalyst member may have a structure in which the light guide is an optical fiber and a plurality of visible light responsive photocatalyst members are bundled.
本発明は、また、上記の導光体が光ファイバーであり、且つ複数の可視光応答型光触媒部材が束ねられた構造を有する前記可視光応答型光触媒部材と、束ねられた可視光応答型光触媒部材の一端面に配設された可視光光源とを有する可視光応答型光触媒装置を提供する。 The present invention also provides the visible light responsive photocatalyst member having a structure in which the light guide is an optical fiber and a plurality of visible light responsive photocatalyst members are bundled, and the bundled visible light responsive photocatalyst members. A visible light responsive photocatalyst device having a visible light source disposed on one end face of the same.
前記可視光光源として、青色ＬＥＤを使用できる。 A blue LED can be used as the visible light source.
本発明によれば、可視光が導光体の内部から導光体表面に担持された可視光応答型光触媒に照射されるので、可視光を極めて効率よく光触媒機能発現に利用できる。また、導光体の素材として有機高分子をも利用できため、汎用性に優れ、安価に製造可能である。 According to the present invention, visible light is irradiated from the inside of the light guide to the visible light responsive photocatalyst carried on the surface of the light guide, so that the visible light can be used for the photocatalytic function expression very efficiently. Moreover, since an organic polymer can also be used as a light guide material, it is excellent in versatility and can be manufactured at low cost.
［可視光応答型光触媒部材］
本発明の可視光応答型光触媒部材は、導光体表面に可視光応答型光触媒粒子が担持された構造を有しており、前記導光体に導かれた光が該導光体表面から前記可視光応答型光触媒粒子に照射されることにより光触媒機能が発現するものである。
[Visible light-responsive photocatalyst member]
The visible light responsive photocatalyst member of the present invention has a structure in which visible light responsive photocatalyst particles are supported on the surface of the light guide, and the light guided to the light guide from the surface of the light guide The photocatalytic function is exhibited by irradiating the visible light responsive photocatalyst particles.
図１は本発明の可視光応答型光触媒部材の例を示す横断面図である。この例は、導光体として光ファイバーを用いた例であり、図１の（ａ）はコア（ｃｏｒｅ）のみを有しクラッド（ｃｌａｄ）を有しない光ファイバーを用いた例であり、（ｂ）はコアの外側にクラッドを有する光ファイバーを用いた例である。図１（ａ）の例では、可視光応答型光触媒部材１は、光ファイバーのコア２の表面に可視光応答型光触媒層４が設けられている。図１（ｂ）の例では、可視光応答型光触媒部材１は、光ファイバーのクラッド３の表面に可視光応答型光触媒層４が設けられている。 FIG. 1 is a cross-sectional view showing an example of the visible light responsive photocatalyst member of the present invention. In this example, an optical fiber is used as a light guide, FIG. 1A is an example using an optical fiber having only a core and not a clad, and FIG. This is an example using an optical fiber having a cladding outside the core. In the example of FIG. 1A, the visible light responsive photocatalyst member 1 is provided with a visible light responsive photocatalyst layer 4 on the surface of an optical fiber core 2. In the example of FIG. 1B, the visible light responsive photocatalyst member 1 is provided with a visible light responsive photocatalyst layer 4 on the surface of a clad 3 of an optical fiber.
図１（ａ）の場合には、コア２内部を通る光が導光体からより多く漏れ出て、可視光応答型光触媒層４内の可視光応答型光触媒粒子に効率よく照射するように、コア２の屈折率を可視光応答型光触媒粒子の屈折率よりも低くするのが好ましい。例えば、コア２の屈折率は、可視光応答型光触媒粒子の屈折率の９９％以下が好ましく、より好ましくは９８％以下、特に好ましくは９７％以下である。図１（ｂ）の場合には、コア２内部を通る光が導光体外部に漏れ出るように、クラッド３表面を粗面化するのが好ましい。粗面化の方法としては、特に制限はなく、研磨剤などで研磨することにより行うことができる。 In the case of FIG. 1 (a), more light that passes through the core 2 leaks from the light guide, and the visible light responsive photocatalyst particles in the visible light responsive photocatalyst layer 4 are efficiently irradiated. It is preferable to make the refractive index of the core 2 lower than that of the visible light responsive photocatalyst particles. For example, the refractive index of the core 2 is preferably 99% or less, more preferably 98% or less, and particularly preferably 97% or less of the refractive index of the visible light responsive photocatalyst particles. In the case of FIG. 1B, the surface of the cladding 3 is preferably roughened so that light passing through the core 2 leaks out of the light guide. There is no restriction | limiting in particular as a roughening method, It can carry out by grind | polishing with an abrasive | polishing agent etc.
光ファイバーの材質は、ポリメチルメタクリレート（ＰＭＭＡ）、完全フッ素化ポリマー、ポリカーボネート、ポリエステル、ポリスチレン等の有機高分子、石英ガラス等のガラス、セラミックなどのいずれであってもよいが、安価に入手できる点から、有機高分子が好ましく、特に、可視光の透過性に優れるポリメチルメタクリレート（ＰＭＭＡ）が好ましい。コア２とクラッド３を有する光ファイバーの場合、全反射や屈折によりできる限り光を中心部のコア２にだけ伝播させるため、クラッド材料の屈折率はコア材料の屈折率よりも低くしている。ガラス製の光ファイバーでは、コア材料、クラッド材料ともに石英ガラスが用いられることが多く、添加剤により屈折率を調整している。有機高分子製（或いはプラスチック製）の光ファイバーでは、コア材料として前記の有機高分子が用いられ、クラッド材料として、低屈折率のフッ素系ポリマーが用いられることが多い。本発明においては、光ファイバーの材質は安価で入手容易な有機高分子が好ましく、特に、コア材料としてはポリメチルメタクリレート（ＰＭＭＡ）が好ましい。本発明では、光として可視光を用いるため、有機高分子であっても光損失が小さい。 The material of the optical fiber may be any of polymethyl methacrylate (PMMA), fully fluorinated polymer, organic polymer such as polycarbonate, polyester, polystyrene, glass such as quartz glass, ceramic, etc. Therefore, an organic polymer is preferable, and polymethyl methacrylate (PMMA) excellent in visible light transmission is particularly preferable. In the case of the optical fiber having the core 2 and the clad 3, the refractive index of the clad material is set lower than the refractive index of the core material so that light is propagated only to the core 2 at the central part as much as possible by total reflection and refraction. In the optical fiber made of glass, quartz glass is often used for both the core material and the clad material, and the refractive index is adjusted by an additive. In an organic polymer (or plastic) optical fiber, the organic polymer is often used as a core material, and a low refractive index fluoropolymer is often used as a cladding material. In the present invention, the material of the optical fiber is preferably an organic polymer that is inexpensive and easily available, and in particular, polymethyl methacrylate (PMMA) is preferable as the core material. In the present invention, since visible light is used as light, light loss is small even with organic polymers.
光ファイバーとしては、可視光線に対する透過性に優れるものが好ましい。光ファイバーの１０ｃｍ長での波長４５５ｎｍにおける光透過率は、好ましくは５０％以上であり、より好ましくは６０％以上、さらに好ましくは７０％以上、特に好ましくは８０％以上である。 As the optical fiber, one having excellent transparency to visible light is preferable. The light transmittance at a wavelength of 455 nm at a length of 10 cm of the optical fiber is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and particularly preferably 80% or more.
光ファイバーの径としては、例えば０．１〜５ｍｍ、好ましくは０．２〜３ｍｍ、さらに好ましくは０．３〜１ｍｍである。 The diameter of the optical fiber is, for example, 0.1 to 5 mm, preferably 0.2 to 3 mm, and more preferably 0.3 to 1 mm.
なお、上記の例では導光体として光ファイバーを用いているが、光ファイバーに限らず、円柱状、角柱状、シート状、球状等の導光体を用いることもできる。光の損失を低減でき、且つ湾曲化が可能な点などから、導光体としては光ファイバーが特に好ましい。 In the above example, an optical fiber is used as the light guide. However, the light guide is not limited to an optical fiber, and a cylindrical, prismatic, sheet, or spherical light guide can also be used. An optical fiber is particularly preferable as the light guide because it can reduce light loss and bend.
前記可視光応答型光触媒層４には可視光応答型光触媒粒子が含まれている。 The visible light responsive photocatalyst layer 4 contains visible light responsive photocatalyst particles.
可視光応答型光触媒粒子としては、可視光に対して応答性を有する光触媒粒子であれば特に限定されず、例えば、酸化チタン（ＴｉＯ2）、酸化タングステン（ＷＯ3）、酸化亜鉛（ＺｎＯ）等の公知の可視光応答型光触媒の粒子を使用できる。これらのうち、高い酸化力を有し、安価で且つ無害である点で、酸化チタン粒子が特に好ましい。 The visible light responsive photocatalyst particles are not particularly limited as long as they are responsive to visible light. For example, titanium oxide (TiO 2 ), tungsten oxide (WO 3 ), zinc oxide (ZnO), etc. The known visible light responsive photocatalyst particles can be used. Of these, titanium oxide particles are particularly preferred because they have high oxidizing power, are inexpensive and harmless.
酸化チタン粒子としては、ルチル型、アナターゼ型、ブルッカイト型酸化チタン粒子のいずれも使用できる。これらを組み合わせて用いることもできる。これらの中でも、ルチル型又はアナターゼ型酸化チタン粒子が好ましく、特に、アスペクト比が大きい形状を有する点でルチル型酸化チタン粒子が好ましい。 As the titanium oxide particles, any of rutile type, anatase type and brookite type titanium oxide particles can be used. A combination of these can also be used. Among these, rutile type or anatase type titanium oxide particles are preferable, and rutile type titanium oxide particles are particularly preferable in that they have a shape with a large aspect ratio.
酸化チタン粒子の形状としては、棒状或いは針状形状を有しているのが好ましい。棒状或いは針状形状の酸化チタン粒子は、酸化チタン粒子を含む塗膜を形成した場合に塗膜表面への光触媒の露出量が多いため、可視光線域において高い触媒活性を発揮する。棒状或いは針状形状の酸化チタン粒子のアスペクト比［長辺／短辺（長さ）の比率］としては、例えば１．５以上、好ましくは１．５〜１００程度、特に好ましくは２．０〜２０程度、最も好ましくは５．０〜１５程度である。酸化チタン粒子のアスペクト比は、例えば、ＳＥＭ写真から求めることができる。 The shape of the titanium oxide particles is preferably a rod shape or a needle shape. The rod-like or needle-like titanium oxide particles exhibit a high catalytic activity in the visible light region because the amount of photocatalyst exposed to the surface of the coating film is large when a coating film containing titanium oxide particles is formed. The aspect ratio [long side / short side (length) ratio] of the rod-like or needle-like titanium oxide particles is, for example, 1.5 or more, preferably about 1.5 to 100, particularly preferably 2.0 to. About 20, most preferably about 5.0-15. The aspect ratio of the titanium oxide particles can be determined from, for example, an SEM photograph.
酸化チタン粒子として、例えば、（００１）（１１０）（１１１）面を有するルチル型酸化チタン粒子は、チタン化合物を、必要に応じて、構造制御剤としての親水性ポリマー（例えば、ポリビニルピロリドン、ポリビニルアルコール）の存在下、水性媒体（例えば、水又は水と水溶性有機溶媒との混合液）中で水熱処理［例えば、１００〜２００℃、３〜４８時間（好ましくは６〜１２時間）］することにより合成することができる。 As the titanium oxide particles, for example, rutile-type titanium oxide particles having (001) (110) (111) planes, a titanium compound and, if necessary, a hydrophilic polymer (for example, polyvinylpyrrolidone, polyvinyl Hydrothermal treatment [for example, 100 to 200 ° C., 3 to 48 hours (preferably 6 to 12 hours)] in an aqueous medium (for example, water or a mixed solution of water and a water-soluble organic solvent) in the presence of alcohol) Can be synthesized.
前記チタン化合物としては、３価のチタン化合物、４価のチタン化合物を挙げることができる。３価のチタン化合物としては、例えば、三塩化チタンや三臭化チタン等のトリハロゲン化チタン等を挙げることができる。３価のチタン化合物としては、なかでも安価で、入手が容易な点で三塩化チタン（ＴｉＣｌ3）が好ましい。 Examples of the titanium compound include a trivalent titanium compound and a tetravalent titanium compound. Examples of the trivalent titanium compound include titanium trihalides such as titanium trichloride and titanium tribromide. As the trivalent titanium compound, titanium trichloride (TiCl 3 ) is preferable because it is inexpensive and easily available.
また、４価のチタン化合物は、例えば、下記式（１）で表される化合物等を挙げることができる。
Ｔｉ（ＯＲ）tＸ4-t （１）
（式中、Ｒは炭化水素基を示し、Ｘはハロゲン原子を示す。ｔは０〜３の整数を示す）
Examples of the tetravalent titanium compound include a compound represented by the following formula (1).
Ti (OR) t X 4-t (1)
(In the formula, R represents a hydrocarbon group, X represents a halogen atom, and t represents an integer of 0 to 3).
Ｒにおける炭化水素基としては、例えば、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、sec−ブチル、tert−ブチル等のＣ1-4脂肪族炭化水素基等を挙げることができる。Ｘにおけるハロゲン原子としては、塩素、臭素、ヨウ素等を挙げることができる。 Examples of the hydrocarbon group for R include C 1-4 aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Examples of the halogen atom for X include chlorine, bromine, iodine and the like.
このような４価のチタン化合物としては、例えば、ＴｉＣｌ4、ＴｉＢｒ4、ＴｉＩ4等のテトラハロゲン化チタン；Ｔｉ（ＯＣＨ3）Ｃｌ3、Ｔｉ（ＯＣ2Ｈ5）Ｃｌ3、Ｔｉ（ＯＣ4Ｈ9）Ｃｌ3、Ｔｉ（ＯＣ2Ｈ5）Ｂｒ3、Ｔｉ（ＯＣ4Ｈ9）Ｂｒ3等のトリハロゲン化アルコキシチタン；Ｔｉ（ＯＣＨ3）2Ｃｌ2、Ｔｉ（ＯＣ2Ｈ5）2Ｃｌ2、Ｔｉ（ＯＣ4Ｈ9）2Ｃｌ2、Ｔｉ（ＯＣ2Ｈ5）2Ｂｒ2等のジハロゲン化ジアルコキシチタン；Ｔｉ（ＯＣＨ3）3Ｃｌ、Ｔｉ（ＯＣ2Ｈ5）3Ｃｌ、Ｔｉ（ＯＣ4Ｈ9）3Ｃｌ、Ｔｉ（ＯＣ2Ｈ5）3Ｂｒ等のモノハロゲン化トリアルコキシチタン等を挙げることができる。４価のチタン化合物としては、なかでも安価で、入手が容易な点で、テトラハロゲン化チタンが好ましく、特に四塩化チタン（ＴｉＣｌ4）が好ましい。 Examples of such tetravalent titanium compounds include titanium tetrahalides such as TiCl 4 , TiBr 4 , and TiI 4 ; Ti (OCH 3 ) Cl 3 , Ti (OC 2 H 5 ) Cl 3 , and Ti (OC 4). H 9) Cl 3, Ti ( OC 2 H 5) Br 3, Ti (OC 4 H 9) trihalide alkoxy titanium Br 3 such; Ti (OCH 3) 2 Cl 2, Ti (OC 2 H 5) 2 Dihalogenated dialkoxytitanium such as Cl 2 , Ti (OC 4 H 9 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Br 2 ; Ti (OCH 3 ) 3 Cl, Ti (OC 2 H 5 ) 3 Cl, Examples thereof include monohalogenated trialkoxytitanium such as Ti (OC 4 H 9 ) 3 Cl and Ti (OC 2 H 5 ) 3 Br. As the tetravalent titanium compound, titanium tetrahalide is preferable, and titanium tetrachloride (TiCl 4 ) is particularly preferable because it is inexpensive and easily available.
特に、前記チタン化合物として４価のチタン化合物を使用する場合は、構造制御剤として親水性ポリマーを添加しなくとも、反応温度１１０〜２２０℃（好ましくは１５０℃〜２２０℃）、その反応温度における飽和蒸気圧以上の圧力下、水性媒体中で２時間以上（好ましくは５〜１５時間）水熱処理を施すことにより、（００１）（１１０）（１１１）面を有するルチル型酸化チタン粒子を合成することができる。 In particular, when a tetravalent titanium compound is used as the titanium compound, the reaction temperature is 110 to 220 ° C. (preferably 150 to 220 ° C.) without adding a hydrophilic polymer as a structure control agent. Rutile titanium oxide particles having (001) (110) (111) faces are synthesized by hydrothermal treatment in an aqueous medium under a pressure equal to or higher than the saturated vapor pressure for 2 hours or more (preferably 5 to 15 hours). be able to.
その他、（００１）（１１０）（１１１）面を有するルチル型酸化チタンは、（１１０）（１１１）面を有するルチル型酸化チタン粒子を硫酸（好ましくは、５０重量％以上の高濃度の硫酸、特に好ましくは濃硫酸）中に投入し、加熱下で撹拌することにより、酸化チタン粒子の稜又は頂点の部位を浸食（溶解）して合成することもできる。（１１０）（１１１）面を有するルチル型酸化チタン粒子は、チタン化合物を水性媒体（例えば、水又は水と水溶性有機溶媒との混合液）中で水熱処理［例えば、１００〜２００℃、３〜４８時間（好ましくは６〜１２時間）］することにより合成することができる。水熱処理の際には、ハロゲン化物を添加することが、得られる粒子のサイズ及び表面積を調整することができる点で好ましい。 In addition, the rutile-type titanium oxide having (001) (110) (111) face is obtained by converting rutile-type titanium oxide particles having (110) (111) face into sulfuric acid (preferably sulfuric acid having a high concentration of 50% by weight or more, In particular, it is also possible to synthesize (dissolve) the ridges or apexes of the titanium oxide particles by adding them into concentrated sulfuric acid) and stirring them under heating. The rutile-type titanium oxide particles having (110) (111) faces are obtained by hydrothermal treatment of a titanium compound in an aqueous medium (for example, water or a mixture of water and a water-soluble organic solvent) [for example, 100 to 200 ° C., 3 To 48 hours (preferably 6 to 12 hours)]. In the hydrothermal treatment, it is preferable to add a halide because the size and surface area of the obtained particles can be adjusted.
酸化チタン粒子の比表面積としては、例えば、２０〜１００ｍ2／ｇ、好ましくは４０〜９０ｍ2／ｇ、特に好ましくは５０〜８５ｍ2／ｇである。酸化チタン粒子の比表面積が上記範囲を下回ると、反応物質の吸着能力が低下して光触媒能が低下する傾向があり、一方、酸化チタン粒子の比表面積が上記範囲を上回ると、励起電子とホールの分離性が低下し、光触媒能が低下する傾向がある。 As a specific surface area of a titanium oxide particle, it is 20-100 m < 2 > / g, for example, Preferably it is 40-90 m < 2 > / g, Most preferably, it is 50-85 m < 2 > / g. When the specific surface area of the titanium oxide particles is below the above range, the adsorption capacity of the reactants tends to be reduced and the photocatalytic performance tends to be reduced. On the other hand, when the specific surface area of the titanium oxide particles exceeds the above range, excited electrons and holes There is a tendency that the separability of the photocatalyst decreases and the photocatalytic ability decreases.
酸化チタン粒子としては、可視光線域で高い触媒活性を発揮させるため、遷移金属化合物を担持した酸化チタン粒子（遷移金属化合物担持酸化チタン粒子）を使用することが好ましい。 As the titanium oxide particles, it is preferable to use titanium oxide particles carrying transition metal compounds (transition metal compound-carrying titanium oxide particles) in order to exhibit high catalytic activity in the visible light region.
また、前記遷移金属化合物は、酸化チタン粒子の露出結晶面における酸化反応面又は還元反応面のうち一方の面（特に、酸化反応面）に選択的に担持されていることが、酸化反応と還元反応の反応場を空間的により大きく引き離すことができ、それにより励起電子とホールの分離性を高め、励起電子とホールの再結合及び逆反応の進行を極めて低いレベルにまで抑制することができ、より高い光触媒活性を発揮することができる点で好ましい。 The transition metal compound is selectively supported on one of the oxidation reaction surface and the reduction reaction surface (particularly the oxidation reaction surface) of the exposed crystal surface of the titanium oxide particles. The reaction field of the reaction can be separated more spatially, thereby increasing the separation of excited electrons and holes, and suppressing the recombination of excited electrons and holes and the progress of reverse reaction to a very low level, It is preferable at the point which can exhibit higher photocatalytic activity.
遷移金属化合物としては、可視光領域に吸収スペクトルを有し、励起状態で伝導帯に電子を注入することができるものであればよく、例えば、周期表第３〜第１１族元素化合物、なかでも周期表第８〜第１１族元素化合物が好ましく、特に、三価の鉄化合物が好ましい。鉄化合物の酸化チタン粒子への担持においては、三価の鉄化合物は吸着しやすく、二価の鉄化合物は吸着しにくい特性を有するため、その特性を利用することにより容易に面選択性を付与することができるからである。 Any transition metal compound may be used as long as it has an absorption spectrum in the visible light region and can inject electrons into the conduction band in an excited state, for example, a periodic table group 3 to 11 element compound, Periodic table Group 8 to Group 11 element compounds are preferred, and trivalent iron compounds are particularly preferred. In supporting iron compounds on titanium oxide particles, trivalent iron compounds are easily adsorbed, and divalent iron compounds are difficult to adsorb. Therefore, surface selectivity can be easily provided by using these properties. Because it can be done.
ルチル型酸化チタン粒子の主な露出結晶面としては、例えば、（１１０）（００１）（１１１）（０１１）面等を挙げることができる。好ましいルチル型酸化チタン粒子として、例えば、（１１０）（１１１）面を有するルチル型酸化チタン粒子、（１１０）（０１１）面を有するルチル型酸化チタン粒子、（００１）（１１０）（１１１）面を有するルチル型酸化チタン粒子等を挙げることができる。これらのなかでも、酸化反応と還元反応の反応場を空間的により大きく引き離すことができ、励起電子とホールとの再結合及び逆反応の進行を抑制することができる点で、（００１）（１１０）（１１１）面を有するルチル型酸化チタン粒子が好ましい。（００１）（１１０）（１１１）面を有するルチル型酸化チタンの酸化反応面は、（１１１）面と（００１）面である。 Examples of main exposed crystal planes of rutile-type titanium oxide particles include (110) (001) (111) (011) planes. As preferable rutile type titanium oxide particles, for example, rutile type titanium oxide particles having a (110) (111) plane, rutile type titanium oxide particles having a (110) (011) plane, (001) (110) (111) plane And rutile-type titanium oxide particles having Among these, (001) (110) in that the reaction field of the oxidation reaction and the reduction reaction can be separated more spatially, and the recombination of excited electrons and holes and the progress of the reverse reaction can be suppressed. ) Rutile type titanium oxide particles having a (111) plane are preferred. The oxidation reaction surfaces of rutile type titanium oxide having (001) (110) (111) planes are (111) plane and (001) plane.
従って、遷移金属化合物担持酸化チタン粒子としては、なかでも、（００１）（１１０）（１１１）面を有するルチル型酸化チタン粒子の酸化面（００１）（１１１）面に遷移金属化合物が選択的に担持されているもの、及び（１１０）（１１１）面を有するルチル型酸化チタン粒子の酸化面（１１１）面に遷移金属化合物が選択的に担持されているものが好ましい。 Therefore, as the transition metal compound-carrying titanium oxide particles, the transition metal compound is selectively formed on the oxidized surface (001) (111) surface of the rutile type titanium oxide particles having (001) (110) (111) surface. Those that are supported and those in which a transition metal compound is selectively supported on the oxidized surface (111) of rutile-type titanium oxide particles having (110) (111) surfaces are preferred.
本発明では、酸化チタン粒子の中でも、遷移金属化合物、特に鉄化合物が、酸化面に選択的に担持されたルチル型又はアナターゼ型酸化チタンが好ましい。 In the present invention, among the titanium oxide particles, a rutile type or anatase type titanium oxide in which a transition metal compound, particularly an iron compound is selectively supported on an oxidized surface is preferable.
なお、「遷移金属化合物が選択的に担持」とは、露出結晶面を有する酸化チタン粒子に担持する遷移金属化合物の５０％を超える量（好ましくは７０％以上、特に好ましくは８０％以上）が２面以上の露出結晶面のうち、全ての面ではなく、特定の面（例えば、特定の１面又は２面等）に担持されていることをいう。遷移金属化合物の担持は、透過型電子顕微鏡（ＴＥＭ）やエネルギー分散型蛍光Ｘ線分析装置（ＥＤＸ）を使用し、露出結晶面上の遷移金属化合物由来のシグナルを確認することで判定できる。 Note that “the transition metal compound is selectively supported” means that the amount of transition metal compound supported on the titanium oxide particles having an exposed crystal plane exceeds 50% (preferably 70% or more, particularly preferably 80% or more). It means that it is supported on a specific surface (for example, specific one surface or two surfaces) among all the exposed crystal surfaces of two or more surfaces. The loading of the transition metal compound can be determined by confirming a signal derived from the transition metal compound on the exposed crystal plane using a transmission electron microscope (TEM) or an energy dispersive X-ray fluorescence spectrometer (EDX).
遷移金属化合物の酸化チタン粒子への担持は、酸化チタン粒子に遷移金属化合物を含浸する含浸法により行うことができる。この場合、合成した酸化チタン粒子は乾燥固化することなく湿状態のまま遷移金属化合物の担持を行うのが好ましい。この方法を採用することにより、水分蒸発にかかるエネルギーを低減できるとともに、酸化チタンの凝集を回避でき、酸化チタンの分散性を高めることができる。 The transition metal compound can be supported on the titanium oxide particles by an impregnation method in which the titanium oxide particles are impregnated with the transition metal compound. In this case, the synthesized titanium oxide particles are preferably supported on the transition metal compound in a wet state without being dried and solidified. By adopting this method, energy required for water evaporation can be reduced, aggregation of titanium oxide can be avoided, and dispersibility of titanium oxide can be enhanced.
含浸は、具体的には、酸化チタン粒子を水溶液中に分散して浸漬し、撹拌しながら、遷移金属化合物を添加することにより行うことができ、例えば、遷移金属化合物として三価の鉄化合物を使用する場合は、鉄化合物（例えば、硝酸鉄（III）、硫酸鉄（III）、塩化鉄（III）等）を添加することにより行うことができる。 Specifically, the impregnation can be performed by dispersing and immersing titanium oxide particles in an aqueous solution and adding a transition metal compound while stirring. For example, a trivalent iron compound is used as the transition metal compound. When using, it can carry out by adding an iron compound (For example, iron nitrate (III), iron sulfate (III), iron chloride (III), etc.).
鉄化合物を担持する場合、鉄化合物を添加する際の酸化チタンの水分散液のｐＨを０から７の範囲で調整することにより、所望量（例えば、０〜２０００ｐｐｍ程度）の鉄化合物を担持した鉄化合物担持酸化チタンを容易に製造することができる。ｐＨが上記範囲を外れると、効率的な酸化チタンへの鉄化合物の担持が困難となり、得られる鉄化合物担持酸化チタンの可視光応答性が著しく低下する場合がある。また、鉄化合物の担持量が上記範囲を上回ると、励起電子が有効に作用せず、光触媒能が低下する傾向がある。特に、鉄化合物担持量が多く（例えば、１０〜１５００ｐｐｍ程度、好ましくは４０〜１２００ｐｐｍ程度、特に好ましくは１５０〜１０００ｐｐｍ程度、最も好ましくは１８０〜５００ｐｐｍ程度）、優れた可視光応答性、及び光触媒能を有する鉄化合物担持酸化チタンを製造する場合は、鉄化合物を添加する際の酸化チタンの水分散液のｐＨを、例えば、１．０から６．０（好ましくは２．０から５．０、特に好ましくは２．１から４．５、最も好ましくは２．５から４．０）の範囲で調整することが好ましい。 When loading an iron compound, a desired amount (for example, about 0 to 2000 ppm) of the iron compound was loaded by adjusting the pH of the aqueous dispersion of titanium oxide in the range of 0 to 7 when adding the iron compound. An iron compound-supported titanium oxide can be easily produced. When the pH is out of the above range, it is difficult to efficiently support the iron compound on the titanium oxide, and the visible light responsiveness of the obtained iron compound-supporting titanium oxide may be significantly lowered. On the other hand, if the amount of the iron compound supported exceeds the above range, the excited electrons do not act effectively and the photocatalytic ability tends to decrease. In particular, the amount of iron compound supported is large (for example, about 10 to 1500 ppm, preferably about 40 to 1200 ppm, particularly preferably about 150 to 1000 ppm, most preferably about 180 to 500 ppm), excellent visible light responsiveness, and photocatalytic ability. In the case of producing an iron compound-supported titanium oxide having a pH of 1.0 to 6.0 (preferably 2.0 to 5.0, preferably 1.0 to 6.0), for example, the aqueous dispersion of titanium oxide when the iron compound is added. It is particularly preferable to adjust in the range of 2.1 to 4.5, most preferably 2.5 to 4.0.
遷移金属化合物の添加量としては、例えば、酸化チタン粒子に対して０．０１〜３．０重量％程度、好ましくは０．０５〜１．０重量％程度である。遷移金属化合物の添加量が上記範囲を下回ると、酸化チタン粒子表面における遷移金属化合物の担持量が低下し、光触媒活性が低下する傾向があり、一方、遷移金属化合物の添加量が上記範囲を上回ると、注入電子の逆電子移動等により励起電子が有効に作用せず、光触媒活性が低下する傾向がある。浸漬時間としては、例えば、３０分から２４時間程度、好ましくは１〜１０時間程度である。 The addition amount of the transition metal compound is, for example, about 0.01 to 3.0% by weight, preferably about 0.05 to 1.0% by weight with respect to the titanium oxide particles. When the addition amount of the transition metal compound is below the above range, the amount of the transition metal compound supported on the surface of the titanium oxide particles tends to decrease, and the photocatalytic activity tends to decrease, while the addition amount of the transition metal compound exceeds the above range. Then, the excited electrons do not act effectively due to reverse electron transfer of the injected electrons, and the photocatalytic activity tends to decrease. The immersion time is, for example, about 30 minutes to 24 hours, preferably about 1 to 10 hours.
酸化チタン粒子に遷移金属化合物を含浸する際には励起光を照射することが好ましい。励起光を照射すると、酸化チタン粒子の価電子帯の電子が伝導帯に励起し、価電子帯にホール、伝導帯に励起電子が生成し、これらは粒子表面へ拡散し、各露出結晶面の特性に従って励起電子とホールとが分離されて酸化反応面と還元反応面とを形成する。この状態で遷移金属化合物として、例えば三価の鉄化合物の含浸を行うと、三価の鉄化合物は酸化反応面には吸着するが、還元反応面では三価の鉄化合物は二価の鉄化合物に還元され、二価の鉄化合物は吸着しにくい特性を有するため、溶液中に溶出し、結果として酸化反応面にのみ鉄化合物が担持された金属化合物担持酸化チタン粒子を得ることができる。 When impregnating the titanium oxide particles with the transition metal compound, it is preferable to irradiate excitation light. When irradiated with excitation light, the electrons in the valence band of the titanium oxide particles are excited in the conduction band, holes are generated in the valence band, and excited electrons are generated in the conduction band, which are diffused to the particle surface. Excited electrons and holes are separated according to the characteristics to form an oxidation reaction surface and a reduction reaction surface. When a trivalent iron compound is impregnated as a transition metal compound in this state, for example, the trivalent iron compound is adsorbed on the oxidation reaction surface, but on the reduction reaction surface, the trivalent iron compound is a divalent iron compound. Since the divalent iron compound has a characteristic that it is difficult to adsorb, it is eluted in the solution, and as a result, metal compound-supported titanium oxide particles in which the iron compound is supported only on the oxidation reaction surface can be obtained.
励起光の照射方法としては、バンドギャップエネルギー以上のエネルギーを有する光を照射することができればよく、例えば、紫外線を照射することにより行うことができる。紫外線照射手段としては、例えば、中・高圧水銀灯、ＵＶレーザー、ＵＶ−ＬＥＤ、ブラックライト等の紫外線を効率よく生成する光源を使用した紫外線露光装置等を使用することができる。励起光の照射量としては、例えば、０．１〜３００ｍＷ／ｃｍ2程度、好ましくは１〜５ｍＷ／ｃｍ2程度である。 As a method for irradiating the excitation light, it is only necessary to irradiate light having energy equal to or higher than the band gap energy. As the ultraviolet irradiation means, for example, an ultraviolet exposure apparatus using a light source that efficiently generates ultraviolet rays such as a medium / high pressure mercury lamp, a UV laser, a UV-LED, and a black light can be used. The irradiation amount of the excitation light is, for example, about 0.1 to 300 mW / cm 2 , preferably about 1 to 5 mW / cm 2 .
さらに、含浸の際に犠牲剤を添加してもよい。犠牲剤を添加することにより、酸化チタン粒子表面において、特定の露出結晶面により高い選択率で遷移金属化合物を担持させることができる。犠牲剤としては、それ自体が電子を放出しやすい有機化合物を使用することが好ましく、例えば、メタノール、エタノール等のアルコール；酢酸等のカルボン酸；エチレンジアミン四酢酸（ＥＤＴＡ）、トリエタノールアミン（ＴＥＡ）等のアミン等を挙げることができる。 Further, a sacrificial agent may be added during the impregnation. By adding the sacrificial agent, the transition metal compound can be supported on the surface of the titanium oxide particles with a higher selectivity on the specific exposed crystal plane. As the sacrificial agent, it is preferable to use an organic compound that easily emits electrons. For example, alcohols such as methanol and ethanol; carboxylic acids such as acetic acid; ethylenediaminetetraacetic acid (EDTA) and triethanolamine (TEA) And the like.
犠牲剤の添加量としては、適宜調整することができ、例えば、酸化チタン溶液の０．５〜５．０vol％程度、好ましくは１．０〜２．０vol％程度である。犠牲剤は過剰量を使用してもよい。 The addition amount of the sacrificial agent can be adjusted as appropriate, and is, for example, about 0.5 to 5.0 vol%, preferably about 1.0 to 2.0 vol% of the titanium oxide solution. An excessive amount of the sacrificial agent may be used.
上記方法により得られた金属化合物担持酸化チタン粒子は、例えば、濾過、遠心分離、濃縮、乾燥等の手段により分離精製できる。 The metal compound-supported titanium oxide particles obtained by the above method can be separated and purified by means such as filtration, centrifugation, concentration, and drying.
なお、酸化チタン粒子に遷移金属化合物を担持させる方法としては、含浸法のほか、光析出法、化学析出法、同時沈殿法、混練法、振り混ぜ法、金属粉添加法、スパッタ法などの公知の方法を使用することができる。 As a method for supporting the transition metal compound on the titanium oxide particles, in addition to the impregnation method, a photoprecipitation method, a chemical precipitation method, a simultaneous precipitation method, a kneading method, a shaking method, a metal powder addition method, a sputtering method, and the like are known. Can be used.
酸化チタン粒子等の可視光応答型光触媒粒子の平均粒径としては、例えば１ｎｍ〜１０μｍであり、上限は、好ましくは２μｍ、より好ましくは５００ｎｍであり、下限は、好ましくは１０ｎｍ、より好ましくは５０ｎｍである。 The average particle diameter of visible light responsive photocatalyst particles such as titanium oxide particles is, for example, 1 nm to 10 μm, the upper limit is preferably 2 μm, more preferably 500 nm, and the lower limit is preferably 10 nm, more preferably 50 nm. It is.
本発明において、光ファイバー等の導光体表面への可視光応答型光触媒粒子の担持形態としては、導光体表面の全面或いは一部に担持されていればよく、薄膜状であっても粒子が凝集した形態であってもよい。また、必ずしも導光体表面の全体が可視光応答型光触媒粒子で覆われている必要はなく、島状或いは筋状に可視光応答型光触媒粒子が担持され、導光体が露出している部分があってもよい。導光体表面における可視光応答型光触媒粒子による被覆率（面積）は、酸化効率等の点から、好ましくは５０％以上、より好ましくは８０％以上、さらに好ましくは９２％以上である。 In the present invention, the visible light responsive photocatalyst particles are supported on the surface of the light guide such as an optical fiber as long as it is supported on the entire surface or part of the surface of the light guide. It may be in an aggregated form. Further, it is not always necessary that the entire surface of the light guide is covered with visible light responsive photocatalyst particles. The portion where the visible light responsive photocatalyst particles are supported in the shape of islands or streaks and the light guide is exposed. There may be. The coverage (area) with visible light responsive photocatalyst particles on the surface of the light guide is preferably 50% or more, more preferably 80% or more, and still more preferably 92% or more from the viewpoint of oxidation efficiency and the like.
光ファイバー等の導光体表面への可視光応答型光触媒粒子の担持法としては、ゾルゲル法、熱分解法、パイロゾル法、ＣＶＤ法、真空蒸着法、スパッタ法、化合物プレーティング法、金属酸化法などの公知の方法を用いることができる。また、可視光応答型光触媒粒子とバインダー成分とを含む塗布液（塗料）を光ファイバー等の導光体表面に塗布し、可視光応答型光触媒層を形成することで、可視光応答型光触媒粒子を導光体表面に担持してもよい。可視光応答型光触媒粒子とバインダー成分とを含む塗布液を導光体表面に塗布することにより可視光応答型光触媒粒子を導光体表面に担持する方法が、製造効率、コスト等の点で好ましい。 Examples of methods for supporting visible light responsive photocatalyst particles on the surface of a light guide such as an optical fiber include a sol-gel method, a thermal decomposition method, a pyrosol method, a CVD method, a vacuum deposition method, a sputtering method, a compound plating method, and a metal oxidation method. These known methods can be used. In addition, a visible light responsive photocatalyst particle is formed by applying a coating liquid (paint) containing visible light responsive photocatalyst particles and a binder component to the surface of a light guide such as an optical fiber to form a visible light responsive photocatalyst layer. You may carry | support on the light guide surface. A method of supporting the visible light responsive photocatalyst particles on the surface of the light guide by applying a coating liquid containing visible light responsive photocatalyst particles and a binder component to the surface of the light guide is preferable in terms of production efficiency, cost, and the like. .
前記バインダー成分は、上記可視光応答型光触媒粒子を導光体表面に固定する働きを有するものであり、例えば、過酸化チタン、ケイ素系化合物、フッ素系樹脂等を挙げることができる。 The binder component has a function of fixing the visible light responsive photocatalyst particles to the surface of the light guide, and examples thereof include titanium peroxide, silicon compounds, and fluorine resins.
ケイ素系化合物としては、例えば、テトラブロモシラン、テトラクロロシラン、トリブロモシラン、トリクロロシラン、ジブロモシラン、ジクロロシラン、モノブロモシラン、モノクロロシラン、ジクロロジメチルシラン、ジクロロジエチルシラン、ジクロロメチルシラン、ジクロロエチルシラン、クロロトリメチルシラン、クロロトリエチルシラン、クロロジメチルシラン、クロロジエチルシラン、クロロメチルシラン、クロロエチルシラン、ｔ−ブチルクロロジメチルシラン、ｔ−ブチルクロロジエチルシラン等のハロゲン化シラン化合物；テトラメトキシシラン、テトラエトキシシラン、トリメトキシシラン、トリエトキシシラン、ジメトキシシラン、ジエトキシシラン、メトキシシラン、エトキシシラン、ジメトキシメチルシラン、ジエトキシメチルシラン、ジメトキシエチルシラン、ジエトキシエチルシラン、メトキシジメチルシラン、エトキシジメチルシラン、メトキシジエチルシラン、エトキシジエチルシラン等のアルコキシシラン化合物等を挙げることができる。 Examples of silicon compounds include tetrabromosilane, tetrachlorosilane, tribromosilane, trichlorosilane, dibromosilane, dichlorosilane, monobromosilane, monochlorosilane, dichlorodimethylsilane, dichlorodiethylsilane, dichloromethylsilane, and dichloroethylsilane. , Halogenated silane compounds such as chlorotrimethylsilane, chlorotriethylsilane, chlorodimethylsilane, chlorodiethylsilane, chloromethylsilane, chloroethylsilane, t-butylchlorodimethylsilane, t-butylchlorodiethylsilane; tetramethoxysilane, tetra Ethoxysilane, trimethoxysilane, triethoxysilane, dimethoxysilane, diethoxysilane, methoxysilane, ethoxysilane, dimethoxymethylsilane, Ethoxymethyl silane, dimethoxy ethyl silane, diethoxy ethyl silane, methoxy dimethylsilane, ethoxy dimethyl silane, methoxy diethyl silane, can be mentioned alkoxysilane compounds such as ethoxy diethyl silane.
フッ素系樹脂としては、例えば、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリクロロトリフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレンコポリマー、エチレン−テトラフルオロエチレンコポリマー、エチレン−クロロトリフルオロエチレンコポリマー、テトラフルオロエチレン−パーフルオロアルキルビニルエーテルコポリマー、パーフルオロシクロポリマー、ビニルエーテル−フルオロオレフィンコポリマー、ビニルエステル−フルオロオレフィンコポリマー、テトラフルオロエチレン−ビニルエーテルコポリマー、クロロトリフルオロエチレン−ビニルエーテルコポリマー、テトラフルオロエチレンウレタン架橋体、テトラフルオロエチレンエポキシ架橋体、テトラフルオロエチレンアクリル架橋体、テトラフルオロエチレンメラミン架橋体等を挙げることができる。 Examples of the fluorine-based resin include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. , Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, tetrafluoroethylene-vinyl ether copolymer, chlorotrifluoroethylene-vinyl ether copolymer, tetrafluoroethylene urethane crosslinked product , Tetrafluoroethylene epoxy crosslinked product, tetrafluoro Chiren'akuriru crosslinked, mention may be made of tetrafluoroethylene melamine crosslinked body and the like.
前記バインダー成分としては、少なくとも過酸化チタン（ペルオキソチタン酸）を用いることが好ましい。過酸化チタンは単独で使用してもよく、過酸化チタンとケイ素系化合物若しくはフッ素系樹脂を併用して使用してもよい。過酸化チタンは、成膜性が高く、塗布、乾燥することにより、優れた接着性を有する塗膜を速やかに形成することができ、しかも、酸化チタン粒子の光触媒作用によっても分解されることがないため、耐久性に優れ、長期に亘って、被着体表面に酸化チタン粒子を固定することができる。 It is preferable to use at least titanium peroxide (peroxotitanic acid) as the binder component. Titanium peroxide may be used alone or in combination with titanium peroxide and a silicon-based compound or fluorine-based resin. Titanium peroxide has high film-forming properties, and can be rapidly formed by coating and drying, and can be decomposed by the photocatalytic action of titanium oxide particles. Therefore, it is excellent in durability, and the titanium oxide particles can be fixed on the adherend surface over a long period of time.
過酸化チタン（ペルオキソチタン酸）は、例えば、塩基性物質（例えば、アンモニア水、水酸化ナトリウム等）の存在下で、ＴｉＣｌ4等のチタン化合物の水溶液に過酸化水素水を添加することにより合成することができる。 Titanium peroxide (peroxotitanic acid) is synthesized, for example, by adding hydrogen peroxide to an aqueous solution of a titanium compound such as TiCl 4 in the presence of a basic substance (eg, ammonia water, sodium hydroxide, etc.). can do.
過酸化チタン（ペルオキソチタン酸）は、下記式（２）で表される二核錯体であると考えられる。
Ｔｉ2Ｏ5（ＯＨ）x (2-x) （２）
（式中、ｘは１〜６の整数を示す）
Titanium peroxide (peroxotitanic acid) is considered to be a binuclear complex represented by the following formula (2).
Ti 2 O 5 (OH) x (2-x) (2)
(Wherein x represents an integer of 1 to 6)
前記可視光応答型光触媒粒子とバインダー成分とを含む塗布液の調製方法としては、特に限定されることはなく、酸化チタン粒子等の可視光応答型光触媒粒子とバインダー成分とを混合すればよい。例えば、可視光応答型光触媒粒子とバインダー成分とを分散媒中で混合してもよく、可視光応答型光触媒粒子とバインダー成分とをそれぞれ別個に分散媒と混合してゾル状態とし、ゾル状態の可視光応答型光触媒粒子とゾル状態のバインダー成分とを混合してもよい。例えば、酸化チタンゾルは、湿式媒体撹拌ミル等の周知慣用の分散装置を使用して、酸化チタン粒子を分散媒（例えば、水、エタノール等）に分散させることにより調製することができる。酸化チタンゾル中の酸化チタン粒子含有量としては、例えば、１．０〜１０．０重量％程度である。また、過酸化チタンゾル中の過酸化チタン含有量としては、例えば、１．４０〜１．６０重量％程度である。過酸化チタンゾルとしては、例えば、商品名「ティオスカイコートＣ」（株式会社ティオテクノ製）等の市販品を使用してもよい。 The method for preparing the coating liquid containing the visible light responsive photocatalyst particles and the binder component is not particularly limited, and the visible light responsive photocatalyst particles such as titanium oxide particles and the binder component may be mixed. For example, the visible light responsive photocatalyst particles and the binder component may be mixed in a dispersion medium, and the visible light responsive photocatalyst particles and the binder component are separately mixed with the dispersion medium to form a sol state. Visible light-responsive photocatalyst particles and a sol-state binder component may be mixed. For example, the titanium oxide sol can be prepared by dispersing titanium oxide particles in a dispersion medium (for example, water, ethanol, etc.) using a well-known and common dispersing apparatus such as a wet medium stirring mill. The titanium oxide particle content in the titanium oxide sol is, for example, about 1.0 to 10.0% by weight. Moreover, as titanium peroxide content in titanium peroxide sol, it is about 1.40-1.60 weight%, for example. As the titanium peroxide sol, for example, a commercial product such as a trade name “Tio Sky Coat C” (manufactured by Tio Techno Co., Ltd.) may be used.
前記塗布液中における酸化チタン粒子等の可視光応答型光触媒粒子とバインダー成分の配合は、例えば、可視光応答型光触媒粒子とバインダー成分の配合比率［前者：後者（重量比）］が、１：６〜３０：１程度、好ましくは、１：１〜１５：１、特に好ましくは１．５：１〜１３：１となるように配合することが好ましい。可視光応答型光触媒粒子の配合量が上記範囲を下回ると、光触媒能が低下する傾向があり、一方、可視光応答型光触媒粒子の配合量が上記範囲を上回ると、導光体に対する接着性、被着体の劣化防止性が低下する傾向がある。 The blending of visible light responsive photocatalyst particles such as titanium oxide particles and the binder component in the coating liquid is, for example, a blending ratio of the visible light responsive photocatalyst particles and the binder component [the former: the latter (weight ratio)] is 1: It is preferable to blend so as to be about 6 to 30: 1, preferably 1: 1 to 15: 1, particularly preferably 1.5: 1 to 13: 1. When the blending amount of the visible light responsive photocatalyst particles is below the above range, the photocatalytic activity tends to decrease, whereas when the blending amount of the visible light responsive photocatalyst particles exceeds the above range, the adhesion to the light guide, There exists a tendency for the deterioration prevention property of a to-be-adhered body to fall.
また、前記塗布液には、上記酸化チタン粒子等の可視光応答型光触媒粒子、バインダー成分、及び分散媒以外にも、他の成分として通常光触媒塗料に配合される化合物を必要に応じて適宜配合することができる、他の成分としては、例えば、塗布助剤等を挙げることができる。他の成分の配合量としては、本発明の効果を損なわない範囲内であればよく、例えば、前記塗料全量（１００重量％）に対して、１０重量％以下程度（例えば、０．０１〜１０重量％程度）である。 In addition to the visible light responsive photocatalyst particles such as the titanium oxide particles, the binder component, and the dispersion medium, the coating liquid is appropriately mixed with a compound that is usually blended in the photocatalyst paint as necessary. Examples of other components that can be used include coating aids. The blending amount of the other components may be within a range that does not impair the effects of the present invention. For example, it is about 10% by weight or less (for example, 0.01 to 10%) with respect to the total amount of the paint (100% by weight) Weight percent).
前記塗布液の導光体表面への塗布は、例えば、スプレー、刷毛、ローラー、グラビア印刷等により行うことができる。導光体表面に塗布した後は、乾燥（分散媒を蒸発）させることよって、速やかに塗膜を形成することができる。乾燥方法としては、室温で乾燥させてもよく、加熱して乾燥させてもよい。 Application | coating to the light guide surface of the said coating liquid can be performed by spray, a brush, a roller, gravure printing etc., for example. After coating on the surface of the light guide, the coating film can be quickly formed by drying (evaporating the dispersion medium). As a drying method, it may be dried at room temperature or may be dried by heating.
前記塗布液の塗布量は、可視光応答型光触媒粒子（特に、棒状又は針状の可視光応答型光触媒粒子）の含有量が０．５ｇ／ｍ2以上（例えば、０．５〜１０．０ｇ／ｍ2程度、好ましくは０．５〜８．０ｇ／ｍ2程度）となるような塗布量が好ましい。このような塗布量で塗布すると、バインダー成分と混合した場合の充填率が低く、空隙率が大きい光触媒塗膜を形成することができ、結果として、著しく表面積が広く光触媒が塗膜表面に多く露出した構造を有し、極めて優れた光触媒能を発揮することができる。こうして得られる塗膜（可視光応答型光触媒層）においては、単位体積（厚さ１μｍ×１ｍ2）当たりの可視光応答型光触媒粒子（特に、棒状又は針状の可視光応答型光触媒粒子）の含有量は３．０ｇ未満であるのが好ましい。 The coating amount of the coating liquid is such that the content of visible light responsive photocatalyst particles (particularly rod-like or needle-like visible light responsive photocatalyst particles) is 0.5 g / m 2 or more (for example, 0.5 to 10.0 g). / M 2 , preferably about 0.5 to 8.0 g / m 2 ). When applied in such a coating amount, a photocatalyst coating film having a low filling rate when mixed with a binder component and a large porosity can be formed, and as a result, the photocatalyst film has a significantly large surface area and a large amount of photocatalyst is exposed on the coating film surface. It has such a structure and can exhibit extremely excellent photocatalytic activity. In the coating film (visible light responsive photocatalyst layer) obtained in this way, visible light responsive photocatalyst particles (particularly rod-like or needle-like visible light responsive photocatalyst particles) per unit volume (thickness 1 μm × 1 m 2 ). The content is preferably less than 3.0 g.
可視光応答型光触媒層の厚みは、例えば、１ｎｍ〜１００μｍであり、上限は、好ましくは５０μｍ、より好ましくは１０μｍであり、下限は、好ましくは１０ｎｍ、より好ましくは５０ｎｍである。 The thickness of the visible light responsive photocatalyst layer is, for example, 1 nm to 100 μm, the upper limit is preferably 50 μm, more preferably 10 μm, and the lower limit is preferably 10 nm, more preferably 50 nm.
なお、前記塗布液を塗布する前に、予め、導光体表面にバインダー成分（特に、過酸化チタン）を含むコーティング剤を塗布することにより下塗り層を設け、その上に前記塗布液を塗布してもよい。 Before applying the coating solution, an undercoat layer is provided on the surface of the light guide in advance by applying a coating agent containing a binder component (particularly titanium peroxide), and the coating solution is applied thereon. May be.
本発明の可視光応答型光触媒部材では、導光体に導かれた可視光が該導光体表面から可視光応答型光触媒粒子に照射され、可視光応答型光触媒粒子において光触媒機能が発現する。特に、導光体がファイバー状である場合には、柱状導光体の内部から光が照射されるので、平面の場合よりも照射面積を増やすことができ、光触媒への照射量を増加できので、光の有効利用が可能となる。本発明の可視光応答型光触媒部材は、室内外の空気の浄化、汚染物質の分解、悪臭物質の脱臭等に極めて有用である。 In the visible light responsive photocatalyst member of the present invention, visible light guided to the light guide is irradiated to the visible light responsive photocatalyst particles from the surface of the light guide, and the photocatalytic function is expressed in the visible light responsive photocatalyst particles. In particular, when the light guide is in the form of a fiber, light is irradiated from the inside of the columnar light guide, so that the irradiation area can be increased and the amount of irradiation to the photocatalyst can be increased compared to the case of a flat surface. Effective use of light becomes possible. The visible light responsive photocatalyst member of the present invention is extremely useful for purifying indoor and outdoor air, decomposing pollutants, deodorizing malodorous substances, and the like.
上記可視光応答型光触媒部材は複数個（特に、１０個以上）が束ねられた構造を有していてもよい。例えば、導光体が光ファイバーである可視光応答型光触媒部材においては、複数本を結束バンド等で束ねて使用することができる。また、複数個の可視光応答型光触媒部材を用いて、網目状、布状、シート状等にしたり、さらに、これらの形状のものを積層したり、渦巻状に巻回することもできる。 The visible light responsive photocatalyst member may have a structure in which a plurality (particularly, 10 or more) are bundled. For example, in a visible light responsive photocatalyst member in which the light guide is an optical fiber, a plurality of light guides can be bundled with a binding band or the like. Further, a plurality of visible light responsive photocatalyst members may be used to form a mesh, cloth, sheet, or the like, or those having these shapes may be laminated or spirally wound.
［可視光応答型光触媒装置］
本発明の可視光応答型光触媒装置は、前記本発明の可視光応答型光触媒部材のうち、導光体が光ファイバーであり、且つ複数の可視光応答型光触媒部材が束ねられた構造を有している可視光応答型光触媒部材と、束ねられた可視光応答型光触媒部材の一端面に配設された可視光光源とを有している。
[Visible light responsive photocatalytic device]
The visible light responsive photocatalyst device of the present invention has a structure in which, among the visible light responsive photocatalyst members of the present invention, the light guide is an optical fiber, and a plurality of visible light responsive photocatalyst members are bundled. A visible light responsive photocatalyst member, and a visible light source disposed on one end surface of the bundled visible light responsive photocatalyst member.
図２は本発明の可視光応答型光触媒装置の一例を示す概略斜視図である。図２において、１は可視光応答型光触媒部材、５は複数の可視光応答型光触媒部材を束ねるための結束バンド、６は光源装置、７は台である。 FIG. 2 is a schematic perspective view showing an example of the visible light responsive photocatalyst device of the present invention. In FIG. 2, 1 is a visible light responsive photocatalyst member, 5 is a binding band for bundling a plurality of visible light responsive photocatalyst members, 6 is a light source device, and 7 is a table.
この例では、導光体として光ファイバーが用いられており、多数本（例えば、１０本以上）のファイバー状の可視光応答型光触媒部材１を束ね、一方の端部を揃えてエポキシ系接着剤等の接着剤などで固定し、残りの部分は結束バンド５でシート状に束ねてファイバー束とし、このファイバー束の一端面（接着剤で固定した方の端面）を光源装置６に近接させ、光源装置からの光を可視光応答型光触媒部材１の光ファイバー内へ導入している。なお、多数本のファイバー状の可視光応答型光触媒部材１の接着剤などで固定した一方の端部以外の部分は、必ずしも結束バンドで束ねなくてもよく、例えば他方の端部にかけて扇状に開いた形状をしていてもよい。 In this example, an optical fiber is used as the light guide, and a large number (for example, 10 or more) of fiber-like visible light responsive photocatalyst members 1 are bundled, and one end is aligned to form an epoxy adhesive or the like. The remaining part is bundled in a sheet shape with a binding band 5 to form a fiber bundle, and one end face (the end face fixed with the adhesive) of this fiber bundle is brought close to the light source device 6, Light from the apparatus is introduced into the optical fiber of the visible light responsive photocatalytic member 1. It should be noted that a portion other than one end portion fixed with an adhesive or the like of a large number of fiber-like visible light responsive photocatalyst members 1 does not necessarily have to be bundled with a binding band, for example, opens in a fan shape over the other end portion. The shape may be different.
光源装置６としては、可視光光源を有する光源装置であれば特に限定されず、例えば、青色ＬＥＤ素子、白色ＬＥＤ素子、レーザーダイオード、半導体レーザーを用いた照射装置などが挙げられる。可視光の波長としては、４００ｎｍを超える波長を使用することができ、４２０ｎｍを超える波長をも使用することもでき、さらには、例えば、波長４５５ｎｍの可視光を出射する青色ＬＥＤをも使用することができる。 The light source device 6 is not particularly limited as long as it is a light source device having a visible light source, and examples thereof include a blue LED element, a white LED element, a laser diode, and an irradiation device using a semiconductor laser. As the wavelength of visible light, a wavelength exceeding 400 nm can be used, and a wavelength exceeding 420 nm can also be used. Furthermore, for example, a blue LED that emits visible light having a wavelength of 455 nm should also be used. Can do.
本発明の可視光応答型光触媒装置は、抗菌防かび、脱臭、大気浄化、水質浄化、防汚等様々な用途に使用することができる。 The visible light responsive photocatalyst device of the present invention can be used for various applications such as antibacterial and antifungal, deodorization, air purification, water purification, and antifouling.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
調製例１（鉄化合物担持酸化チタン粒子の調製）
室温（２５℃）にて、四塩化チタン水溶液（和光純薬工業（株）製試薬化学用、約１６．５重量％Ｔｉ含有希塩酸溶液）をＴｉ濃度が５．４重量％になるように水で希釈した。希釈後の四塩化チタン水溶液２８４ｇをテフロン（登録商標）カップが装着された容量５００ｍＬのオートクレーブに入れ密閉した。
上記オートクレーブをオイルバスに投入し、１時間かけてオートクレーブ内温度を１４０℃まで昇温した。その後、１４０℃、その温度における蒸気圧の条件下で１０時間保持した後、オートクレーブを氷水につけて冷却した。オートクレーブ内温度が４０℃以下になったことを確認した後、オートクレーブを開封して粗酸化チタン水分散液を取出した。
粗酸化チタン水分散液について、遠心分離後の上澄み液がｐＨ４になるまで水分散−水洗−遠心分離を繰り返し、精製酸化チタン水分散液（１）を得た。
精製酸化チタン水分散液（１）に塩化鉄水溶液（３５重量％）０．２ｇを添加し、室温（２５℃）にて１時間撹拌した。その後、メタノール ６ｍＬを添加し、１００Ｗの高圧水銀ランプを使用して紫外線を３時間照射して、粗鉄化合物担持酸化チタン水分散液を得た。
得られた粗鉄化合物担持酸化チタン水分散液について、遠心分離後の上澄み液が５０μＳ／ｃｍになるまで遠心分離−水分散−水洗を繰り返して、精製鉄化合物担持酸化チタン水分散液を得た。その後、精製鉄化合物担持酸化チタン水分散液を減圧下、６０℃で１５時間乾燥して２５．０ｇの鉄化合物担持酸化チタン（１）を得た。
得られた鉄化合物担持酸化チタン（１）の鉄の含有量は１０００ｐｐｍであった。なお、得られた鉄化合物担持酸化チタン（１）を走査型電子顕微鏡（ＳＥＭ）、エネルギー分散型蛍光Ｘ線分析装置（ＥＤＸ）、及び透過型電子顕微鏡（ＴＥＭ）で確認したところ、（１１０）（１１１）面を有する棒状ルチル型酸化チタン粒子の（１１１）面に鉄化合物（III）が選択的に担持されていた。
Preparation Example 1 (Preparation of iron compound-supported titanium oxide particles)
At room temperature (25 ° C.), an aqueous solution of titanium tetrachloride (for reagent chemistry manufactured by Wako Pure Chemical Industries, Ltd., dilute hydrochloric acid solution containing about 16.5 wt% Ti) is diluted with water so that the Ti concentration becomes 5.4 wt%. Diluted with 284 g of diluted titanium tetrachloride aqueous solution was placed in a 500 mL autoclave equipped with a Teflon (registered trademark) cup and sealed.
The autoclave was put into an oil bath, and the temperature inside the autoclave was raised to 140 ° C. over 1 hour. Then, after maintaining at 140 ° C. under the condition of vapor pressure at that temperature for 10 hours, the autoclave was cooled by putting it in ice water. After confirming that the internal temperature of the autoclave was 40 ° C. or lower, the autoclave was opened and the crude titanium oxide aqueous dispersion was taken out.
About a crude titanium oxide aqueous dispersion, water dispersion-water washing-centrifugation was repeated until the supernatant liquid after centrifugation became pH 4, and the refined titanium oxide aqueous dispersion (1) was obtained.
To the purified titanium oxide aqueous dispersion (1), 0.2 g of an aqueous iron chloride solution (35% by weight) was added and stirred at room temperature (25 ° C.) for 1 hour. Thereafter, 6 mL of methanol was added and irradiated with ultraviolet rays for 3 hours using a 100 W high pressure mercury lamp to obtain a crude iron compound-supported titanium oxide aqueous dispersion.
The obtained crude iron compound-supported titanium oxide aqueous dispersion was repeatedly centrifuged, dispersed in water and washed until the supernatant liquid after centrifugation was 50 μS / cm to obtain a purified iron compound-supported titanium oxide aqueous dispersion. . Thereafter, the purified iron compound-supported titanium oxide aqueous dispersion was dried at 60 ° C. under reduced pressure for 15 hours to obtain 25.0 g of an iron compound-supported titanium oxide (1).
The iron content of the obtained iron compound-supported titanium oxide (1) was 1000 ppm. In addition, when the obtained iron compound carrying | support titanium oxide (1) was confirmed with the scanning electron microscope (SEM), the energy dispersive X-ray fluorescence spectrometer (EDX), and the transmission electron microscope (TEM), (110) The iron compound (III) was selectively supported on the (111) face of rod-shaped rutile-type titanium oxide particles having a (111) face.
調製例２（塗布液の調製）
調製例１で得られた鉄化合物担持酸化チタン粒子（１）の１０重量％水分散液１００ｇと、バインダーとしての過酸化チタンの水溶液（商品名「ティオスカイコートＣ」、（株）ティオテクノ製、過酸化チタン濃度：１重量％）１８５ｇを混合して、塗布用の液（光触媒塗布液）とした。
Preparation Example 2 (Preparation of coating solution)
100 g of a 10% by weight aqueous dispersion of iron compound-supported titanium oxide particles (1) obtained in Preparation Example 1 and an aqueous solution of titanium peroxide as a binder (trade name “Tio Sky Coat C”, manufactured by Tio Techno Co., Ltd.) 185 g of titanium peroxide concentration: 1% by weight) was mixed to prepare a coating solution (photocatalyst coating solution).
実施例１（可視光応答型光触媒部材）
三菱レイヨン社の光ファイバー素線（商品名「エスカＣＫ２０」、コア材料：ポリメチルメタクリレート樹脂、クラッド材料：フッ素樹脂、コア屈折率１．４９、ファイバー径０．５ｍｍ、コア径４８５μｍ）を長さ３０ｃｍに切りそろえ、一方の端から１ｃｍ以降を♯４０〜♯６００の研磨剤で表面を粗した。この粗面化した光ファイバーに、調製例２で調製した光触媒塗布液をスプレー塗布して光触媒層を形成し、室温にて２４時間乾燥し、可視光応答型光触媒部材を作製した。この光触媒塗布後の光ファイバー（可視光応答型光触媒部材）を１００本用意し、粗面化していない末端のみを揃えてエポキシ系接着剤にて固定し、他の部分はシート状にして並べて結束バンドで結束し、ファイバーの束とした。なお、光触媒層の乾燥後の厚みは、４μｍである。
Example 1 (Visible light responsive photocatalyst member)
Mitsubishi Rayon optical fiber (trade name “ESCA CK20”, core material: polymethyl methacrylate resin, cladding material: fluororesin, core refractive index 1.49, fiber diameter 0.5 mm, core diameter 485 μm) 30 cm long The surface was roughened with an abrasive of # 40 to # 600 after 1 cm from one end. The photocatalyst coating liquid prepared in Preparation Example 2 was spray-coated on the roughened optical fiber to form a photocatalyst layer, which was dried at room temperature for 24 hours to produce a visible light responsive photocatalyst member. Prepare 100 optical fibers (visible light responsive photocatalyst members) after applying this photocatalyst, align only the unroughened ends and fix them with an epoxy adhesive, and arrange the other parts in sheet form and tie them together And bundled into a fiber bundle. In addition, the thickness after drying of a photocatalyst layer is 4 micrometers.
実施例２（可視光応答型光触媒装置）
実施例１で用意したファイバー束の固定端を光源（青色ＬＥＤ：発光波長４５５ｎｍ Ｌｕｍｉｌｅｄｓ Ｌｉｇｈｔｉｎｇ社製、商品名「ＬＸＨＬ−ＭＲＲＣ」）に接触させることで可視光応答型光触媒装置を作製した（図２参照）。
Example 2 (Visible light responsive photocatalytic device)
A visible light responsive photocatalytic device was produced by bringing the fixed end of the fiber bundle prepared in Example 1 into contact with a light source (blue LED: emission wavelength 455 nm, manufactured by Lumileds Lighting, trade name “LXHL-MRRC”) (FIG. 2). reference).
実施例３（揮発性有機物の分解特性１）
実施例２で作製した可視光応答型光触媒装置を１リットルのテドラーバックにセットし、容器内のメチルメルカプタンガスを濃度１０ｐｐｍに調整した。その後、光源に通電して出力強度０．７ｍＷで発光させ、ファイバー表面をファイバー内部から２４時間光照射した後、容器内のメチルメルカプタンの濃度を求めたところ、２ｐｐｍであった。
Example 3 (Decomposition characteristics 1 of volatile organic substances)
The visible light responsive photocatalyst device produced in Example 2 was set in a 1 liter Tedlar bag, and the methyl mercaptan gas in the container was adjusted to a concentration of 10 ppm. Thereafter, the light source was energized to emit light with an output intensity of 0.7 mW, and the fiber surface was irradiated with light from the inside of the fiber for 24 hours. The concentration of methyl mercaptan in the container was determined to be 2 ppm.
比較例１（揮発性有機物の分解特性２）
実施例３と同様に、実施例２で作製した可視光応答型光触媒装置を１リットルのテドラーバックにセットし、容器内のメチルメルカプタンガスを濃度１０ｐｐｍに調整した。光源をｏｆｆにし、暗所にて２４時間放置した後、容器内のメチルメルカプタンの濃度を求めたところ、９ｐｐｍであった。
Comparative Example 1 (Decomposition characteristics 2 of volatile organic substances)
As in Example 3, the visible light responsive photocatalyst device produced in Example 2 was set in a 1 liter Tedlar bag, and the methyl mercaptan gas in the container was adjusted to a concentration of 10 ppm. After the light source was turned off and left in the dark for 24 hours, the concentration of methyl mercaptan in the container was determined to be 9 ppm.
１ 可視光応答型光触媒部材
２ コア
３ クラッド
４ 可視光応答型光触媒層
５ 結束バンド
６ 光源装置
７ 台
DESCRIPTION OF SYMBOLS 1 Visible light response type photocatalyst member 2 Core 3 Cladding 4 Visible light response type photocatalyst layer 5 Binding band 6
Claims (4)
前記可視光応答型光触媒が、鉄化合物が酸化面に選択的に担持されたルチル型酸化チタンであり、
前記導光体が光ファイバーであり、且つ複数の可視光応答型光触媒部材が束ねられた構造を有しており、
前記光ファイバーが、光の透過するコアが該コアの屈折率よりも低い屈折率を有するクラッドで被覆された構造を有し、且つ可視光応答型光触媒を担持する部位のクラッド表面を粗すことによりコア内部を通る光がクラッド表面から漏れ出す構造をしており、
前記光ファイバーのコア材料が有機高分子であり、且つクラッド材料がフッ素系ポリマーであり、
前記光ファイバーの径が０．１〜５ｍｍであり、
厚みが１ｎｍ〜１００μｍの可視光応答型光触媒層を有する可視光応答型光触媒部材。 It has a structure in which visible light responsive photocatalyst particles are supported on the surface of the light guide, and the light guided to the light guide is irradiated onto the visible light responsive photocatalyst particles from the surface of the light guide. A visible light responsive photocatalytic member that exhibits a photocatalytic function,
The visible light responsive photocatalyst is a rutile type titanium oxide in which an iron compound is selectively supported on an oxidized surface,
The light guide is an optical fiber, and has a structure in which a plurality of visible light responsive photocatalytic members are bundled;
The optical fiber has a structure in which a core through which light passes is coated with a clad having a refractive index lower than the refractive index of the core, and roughens the clad surface of a portion carrying a visible light responsive photocatalyst The light passing through the core leaks from the cladding surface,
The core material of the optical fiber is an organic polymer, and the cladding material is a fluorine-based polymer,
The optical fiber has a diameter of 0.1 to 5 mm,
A visible light responsive photocatalyst member having a visible light responsive photocatalyst layer having a thickness of 1 nm to 100 μm.
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