JPH10286456A - Adsorbing functional body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fix an adsorbing functional material onto a substrate without deteriorating the adsorbing function, by coating the substrate with a mixture of fine particles of the adsorbing functional material with an amorphous titanium peroxide sol as a binder and carrying out drying and firing at a specified temp. SOLUTION: A substrate is coated with a mixture of fine particles of an adsorbing functional material with an amorphous titanium peroxide sol as a binder and drying and firing is carried out at ordinary temp. to a temp. of <250 deg.C. The adsorbing functional material is an inorg. material such as zeolite, silica or alumina or an org. material such as cellulose, chaff, activated carbon, porous phenolic resin or melamine resin. The amorphous titanium peroxide sol is prepd. by adding an alkali hydroxide to an aq. soln. of a titanium slat such as titanium tetrachloride, bringing them into reaction at pH 6-7, separating and washing the resultant bluish white amorphous titanium hydroxide (orthotitanic acid) and treating it with a hydrogen peroxide soln.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for fixing an adsorbent material for adsorbing contaminants or the like in air or water and a photocatalytic material for decomposing contaminants adsorbed on the adsorbent material to a substrate. In particular, the present invention relates to a method for fixing an adsorption function material or a photocatalytic function material using a viscous amorphous titanium peroxide having excellent adhesiveness as a binder even to a substrate having a water-repellent surface on the substrate.

[0002]

2. Description of the Related Art Conventionally, a fine powder of an adsorbing functional material such as activated carbon, carbon, alumino, silica, phenolic resin, polyamide cellulose or the like having an adsorbing function is fixed on the surface of a substrate, or an adsorbing functional material and a photocatalyst are fixed on the surface of a substrate. It has been proposed to fix a functional material, to deodorize pollutants in air and water, and to adsorb and decompose pollutants (Japanese Patent Laid-Open No. 1-18).
No. 9321, JP-A-1-218635).

Further, a deodorizing method comprising forming an inorganic coating film composed of a photocatalyst, an adsorbent and a colloidal silica-based binder, which absorbs ultraviolet light and has excellent far-infrared radiation characteristics, on the surface of a radiation glass of a light emitting ultraviolet light. Element (Japanese Unexamined Patent Publication No.
No. 173512) or a deodorizing photocatalyst containing titanium oxide-supported activated carbon as a main component, which is obtained by uniformly mixing an activated carbon precursor organic material and a titanium-containing solution, then carbonizing by firing, and activating. Activated carbon is known (JP-A-8-332378).

[0004] In addition, as a method of supporting a photocatalyst on a substrate, a method of sintering and supporting photocatalyst particles at a high temperature on a substrate, or a method of supporting a photocatalyst on a substrate using a certain fluorine-based polymer as a binder. Methods have also been proposed. For example, a method of laminating and pressing a mixture of photocatalyst particles and a fluorine-based polymer (Japanese Patent Laid-Open No. 4-284851), a method of heat-fusing photocatalyst particles to a fluorine-based polymer (Japanese Patent Laid-Open No. 4-334552), For bonding photocatalyst particles to a substrate via a hard-to-decompose binder composed of an inorganic material such as water glass and an organic material such as a silicon-based polymer; And a method for producing a photocatalyst in which a second layer comprising a hardly decomposable binder and photocatalyst particles is provided on the first layer (Japanese Patent Application Laid-Open No.
No. 171408), a method for fixing a photocatalyst using a glaze, an inorganic glass, a thermoplastic resin, solder, or the like as a binder (Japanese Patent Application Laid-Open No. Hei 7-232080), or SnO _2.
For fixing a photocatalyst to a substrate to be used as a coagulant (Japanese Patent Application Laid-Open No. 155598/1995), or as a metal oxide alkoxide, acetylacetonate, carboxylate used in a sol-gel method as a fixing material for supporting a photocatalyst powder. Using a metal oxide produced from a metal oxide compound obtained by hydrolyzing an alcohol solution of a metal organic compound such as titanium tetrachloride or an alcohol solution of a chloride such as titanium tetrachloride in the presence of an acid or an alkali catalyst (JP-A-5-309267) ) And a photocatalyst composition comprising a component composed of a semiconductor photocatalytic compound and a component composed of a compound having a high light-absorbing ability in the wavelength region of 320 to 410 nm (JP-A-8-309203).

However, in the sputtering method and the vapor deposition method used in the above-mentioned conventional methods, a coating apparatus for fixing the fine particles of the adsorption function material and the fine particles of the photocatalytic function material becomes very expensive, and the transfer printing method is used. In this case, the thermal stress applied to the substrate or the like must be taken into consideration depending on the thermal processing conditions for fixing the fine particles of the adsorptive functional material and the fine particles of the photocatalytic functional material.
In the method of fixing the fine particles of the adsorptive functional material or the fine particles of the photocatalytic functional material using a binder, when the surface of the substrate has a water repellent property, it is necessary to pretreat the substrate surface with a surfactant or a solution of caustic soda. was there. Furthermore, it has been difficult for these fine particles of the adsorptive functional material and the fine particles of the photocatalytic functional material to be buried in various binders to sufficiently function in the adsorption action and the redox action by the photocatalyst.

On the other hand, titanium peroxide is disclosed in
Japanese Patent No. 286114 describes a coating liquid for forming a film comprising peroxopolytitanic acid, which is a polymer of peroxotitanic acid. This peroxopolytitanic acid is obtained by adding hydrogen peroxide to a gel or sol of titanium oxide hydrate or a mixed dispersion thereof and heating the mixture at room temperature or at 90 ° C. or lower (in Example 1, heating at 80 ° C. for 1 hour). It is stated that it can be obtained. Further, a viscous liquid or a jelly-like liquid obtained by condensing an aqueous solution of titanium hydrogen peroxide is also known (JP-A-62-252319). This product is obtained as a yellow film by adding aqueous hydrogen peroxide to fine titanium hydride powder to obtain a yellow aqueous titanium peroxide solution, leaving it at room temperature and gradually evaporating water and condensing solutes. Is described.

However, Japanese Patent Application Laid-Open No. 7-28611 discloses
No. 4 peroxopolytitanic acid is obtained by adding hydrogen peroxide to a gel, a sol of titanium oxide hydrate or a mixed dispersion thereof, and heating the mixture at room temperature or 90 ° C. or lower. The hydrogenated titanium oxide hydrate is added with hydrogen peroxide and reacted at 15 ° C. or lower. The “viscous amorphous titanium peroxide” of the present invention is obtained not only by a different production method, but also by physical properties, In particular, there is a problem that the viscosity is greatly different, the function as a binder is inferior, and it is difficult to form a thin layer of an adsorption function material or a photocatalytic function material.

In the case of a viscous liquid or a jelly-like product obtained by condensing an aqueous solution of titanium peroxide described in JP-A-62-252319, an aqueous solution of hydrogen peroxide is added to fine powder of titanium hydride. Is obtained as a yellow film by evaporation of water from an aqueous solution of titanium peroxide. On the other hand, hydrogen peroxide is added to titanium oxide hydrate and reacted at 15 ° C. or lower to form a viscous jelly-like substance. The "viscous amorphous titanium peroxide" of the present invention differs not only in the production method but also in physical properties, and is also described in JP-A-7-286114 (column 2). As described above, it is stable only at an extremely low concentration and cannot exist in a stable state for a long period of time. The coating formed on the base material is liable to crack and peel, and when fired at a high temperature, it is fired. The coating has a problem that to become porous.

[0009]

The adsorbing function body having the adsorbing function material fixed to the surface of the base is combined with a laminated molded product or a porous material to be used as a wall material for a toilet, a decorative material for a vehicle, a unit bath, and the like. Adsorption / decomposition functional bodies that combine this adsorption function with a photocatalytic function have a semi-permanent adsorption capacity because they can decompose adsorbed contaminants, etc., and their commercialization is urgent. Is the current situation. An object of the present invention is to apply to any substrate such as resin (plastic), fiber, and non-woven fabric of an organic polymer material under a mild temperature condition without impairing the adsorption function and the photocatalytic function, In addition, it is another object of the present invention to provide a practical method for fixing an adsorption function material or the like in which the substrate is not decomposed and deteriorated by a redox reaction of a photocatalyst.

[0010] The object of the present invention is, more specifically,
Even if the surface is a substrate having water repellency or a substrate having thermoplasticity, it is not necessary to perform a hydrophilic treatment with a surfactant or the like, and the fine particles or photocatalyst of the adsorption functional material do not limit the thermoplasticity of the substrate. It provides a method for fixing the fine particles of the functional material, and it is easy to form a thin layer of the adsorption functional material and the photocatalytic functional material and control its thickness, and the fine particles of the adsorptive functional material and the fine particles of the photocatalytic functional material are not buried by the binder An object of the present invention is to provide a film forming and fixing method.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a viscous amorphous mold was used as a binder for fixing the fine particles of the adsorption function material and the fine particles of the photocatalytic function material to the substrate. Using titanium oxide, etc.,
By adhering the fine particles of the adsorption function material and the fine particles of the photocatalytic function material to the amorphous titanium peroxide layer in a uniform scattering state in a gas, the viscous amorphous titanium peroxide as a binder of the adsorption function material, etc. Was heated and calcined to obtain an adsorption / decomposition functional body having an adsorption function and a photocatalytic function, and completed the present invention.

That is, the present invention relates to a method of fixing fine particles of an adsorptive material to a substrate, wherein a mixture of the fine particles of the adsorptive function material and an amorphous titanium peroxide sol as a binder is coated on a substrate, and then the mixture is cooled to room temperature to 250 ° C. ° C
A method of fixing fine particles of an adsorptive functional material to a substrate, characterized in that the particles are dried and calcined at a temperature of less than 1. The method of fixing fine particles of an adsorptive functional material to a substrate, comprising the steps of: Without performing a hydrophilic treatment, a mixture of fine particles of an adsorption functional material and a viscous amorphous titanium peroxide as a binder is coated on a substrate, and then dried and fired at room temperature to less than 250 ° C. A method of fixing fine particles of an adsorption function material to a substrate (Claim 2), a method of fixing a thin layer of the adsorption function material to a substrate, wherein the substrate is coated with an amorphous titanium peroxide sol; Is formed, and while the amorphous type titanium peroxide layer has an adhesive property, the fine particles of the adsorptive functional material are uniformly dispersed in gas on the amorphous type titanium peroxide layer. A method of fixing a thin layer of the adsorption function material, wherein the method comprises fixing the thin layer of the adsorption function material to the substrate, the method comprising: Without performing the coating, a viscous amorphous titanium peroxide is coated to form an amorphous titanium peroxide layer, and the fine particles of the adsorption functional material are removed while the amorphous titanium peroxide layer has an adhesive property. A method of fixing a thin layer of an adsorption functional material, wherein the thin layer is adhered to the amorphous titanium peroxide layer in a state of being uniformly scattered in a gas (claim 4). A method for fixing fine particles of an adsorption functional material to a substrate, wherein a mixture of the fine particles of the adsorption functional material and an amorphous titanium peroxide sol as a binder is coated on the substrate. Grayed, then 25
A method of fixing fine particles of an adsorption functional material to a substrate, characterized by firing at 0 ° C. or higher (Claim 6). A method of fixing fine particles of an adsorption functional material to a substrate, the method comprising: Without performing the hydrophilic treatment, a mixture of the fine particles of the adsorptive functional material and the viscous amorphous titanium peroxide as a binder is coated on a substrate, and then the mixture is coated with 250 μm.
A method of fixing fine particles of an adsorption functional material to a substrate, characterized by firing at a temperature of at least ℃, a method of fixing fine particles of an adsorption functional material and fine particles of a photocatalytic functional material to a substrate, The substrate is coated with a mixture of the fine particles of the material, the fine particles of the photocatalytic functional material, and the amorphous titanium peroxide sol as a binder, and then at a normal temperature to 250 ° C.
A method of fixing fine particles of an adsorption functional material and fine particles of a photocatalytic functional material to a substrate, wherein the fine particles of the adsorptive functional material and the fine particles of the photocatalytic functional material are fixed to the substrate. A method of coating a substrate with a mixture of fine particles of an adsorption functional material, fine particles of a photocatalytic functional material, and a viscous amorphous titanium peroxide as a binder without performing hydrophilic treatment on the surface of the substrate having water repellency. A method of fixing the fine particles of the adsorption function material and the fine particles of the photocatalytic function material to the substrate, wherein the drying and baking are performed at room temperature to less than 250 ° C. (claim 9); Fixing a thin layer of the amorphous peroxy acid, coating the substrate with an amorphous titanium peroxide sol to form an amorphous titanium peroxide layer, While the titanium layer has adhesion, particulates and particulate photocatalytic material of the adsorbing functional materials,
A method for fixing a thin layer of an adsorption function material and a photocatalytic function material, wherein the thin layer is attached to the amorphous titanium peroxide layer in a state of being uniformly scattered in a gas (claim 10). A method of fixing a thin layer of, without performing a hydrophilic treatment of the substrate surface having water repellency, coating a viscous amorphous type titanium peroxide, forming an amorphous type titanium peroxide layer, the amorphous type The method is characterized in that fine particles of an adsorption function material and fine particles of a photocatalytic function material are adhered to the amorphous titanium peroxide layer in a state of being uniformly scattered in a gas while the titanium oxide layer has an adhesive property. A method for fixing a thin layer of an adsorption functional material and a photocatalytic functional material (claim 11), and claims 6 to 1.
The present invention relates to an adsorption / decomposition functional body (claim 12) produced by the method according to any one of the first to third aspects.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the substrate in the present invention include inorganic materials such as ceramics and glass, organic materials such as plastic, rubber, wood and paper, and metal materials such as aluminum and steel. . Among these, acrylonitrile resin, vinyl chloride resin,
Application to organic polymer resin materials such as polycarbonate resin, methyl methacrylate resin (acrylic resin), polyester resin, and polyurethane resin exhibits excellent effects.
The size and shape are not limited, and may be a film shape, a honeycomb shape, a fiber shape, a filter sheet shape, a bead shape, a foam shape, or a shape obtained by accumulating them. Furthermore, a photocatalytic functional material can be applied to the inner surface of a substrate that transmits ultraviolet light, and can also be applied to painted articles.

As the adsorptive functional material in the present invention, any material can be used as long as it can adsorb contaminants and the like in the air and water. Are preferred. The adsorption function material is selected from inorganic and organic materials,
Examples of the inorganic material include zeolite, silica (silicon dioxide), alumina, zinc oxide, magnesium oxide, titanium oxide, zirconium phosphate, and the like. Examples of the organic material include cellulose, fir, coconut and charcoal. Activated carbon, a porous phenol resin or a melamine resin.

[0015] One or more of these adsorbing functional materials are combined to form an adsorbing functional body having the respective adsorbing function characteristics, for example, excellent in the adsorbing characteristics of a wide range of acidic to alkaline pollutant gases. Can be. The particle size of the fine particles of the adsorption functional material is preferably about 1 nm to 1 μm. And, as in the case of the adsorption / decomposition function body,
When the adsorbing function material is adjacent to the photocatalytic function material, it is desirable to use activated carbon or black carbon, which has more fibrous material than the organic resin, as the adsorbing function material if possible. As these fine-particle adsorption functional materials, commercially available ones can be used. In some cases, it may be advantageous to use a substance whose adsorption function is not deteriorated by heating at 250 ° C. or higher, or an activated carbon precursor organic substance capable of exhibiting the adsorption function by heating at 250 ° C. or higher.

In the present invention, the “photocatalytic functional material” includes TiO ₂ , ZnO, SrTiO ₃ , CdS, CdO,
CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ ,
K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , SaO ₂ , B
i ₂ O ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , Mo
S _2, MoS _3, InPb, there may be mentioned a substance having photocatalyst activity, such as RuO _2, CeO _2, these are preferably titanium oxide TiO _2, among photocatalytic function material,
It is used in the form of fine particles or fine powder having a diameter of about 0.001 μm to 20 μm. Examples of these photocatalytic functional materials include commercially available “ST-01” (manufactured by Ishihara Techno) and “ST-31” (manufactured by Ishihara Techno).

Along with the photocatalytic functional material, particles composed of a spontaneous ultraviolet radiation material or a phosphorescent ultraviolet radiation material, or particles mixed with these radiation materials can be mixed. Spontaneous UV radiation material (Spontaneous luminescent ceramic)
Is composed of a substance that consumes internal energy and emits light by itself, utilizes the radiative decay of radium and promethium, and has an ultraviolet region in light emission. At present, crushed particles obtained by re-crushing solidified refined powder of rock containing such components are used. The phosphorescent ultraviolet radiating material (phosphorescent luminescent ceramic) is made of a substance that emits light while taking in external energy and releasing it, and has an ultraviolet region in light emission. “Luminova” (trade name, Nemoto Special Chemicals Co., Ltd.) and “Kiplus” (trade name, Next Eye Co., Ltd.) are commercially available. These are mainly composed of strontium aluminate (SrAl ₂ O ₄ ) containing components such as high-purity alumina, strontium carbonate, europium and dysprosium. The maximum of the absorption spectrum is at 360 nm and the particle size is 20
μm to 50 μm. However, the crushed particles before crushing can be directly obtained as crushed particles.

When such spontaneous luminescent ceramic or phosphorescent luminescent ceramic particles or fine particles of these ceramics are used together with the photocatalytic functional material, the spontaneous luminescent ceramic particles emit light even when the irradiation of the photocatalytic functional material with ultraviolet light is interrupted. The photocatalytic material is excited by the ultraviolet light emitted or the ultraviolet light emitted by the phosphorescent luminescent ceramic particles consuming the energy accumulated so far, the photocatalytic function is maintained, and even when there is no ultraviolet irradiation, the adsorption function material The decomposition of the contaminants adsorbed by the gas proceeds.

The photocatalytic function material is adjusted in its composition (addition of inorganic pigments and metals) or by heat treatment in the manufacturing process to adjust the wavelength of the ultraviolet light (absorption band) required for exhibiting the catalytic function. ), Ie the excitation wavelength can be changed. For example, when a small amount of CrO ₃ is added to TiO ₂ , the absorption band shifts to the longer wavelength side. Thus, the photocatalytic function material side can be adjusted to the emission spectrum characteristics of the spontaneous ultraviolet light emitting material or the luminous ultraviolet light emitting material, and the photocatalytic function material can be selected according to the wavelength of the supplied ultraviolet light.

On the other hand, on the other hand, the emission spectrum characteristics of the spontaneous ultraviolet light emitting material or the phosphorescent ultraviolet light emitting material can be adjusted to the excitation wavelength of the photocatalytic functional material. For example,
The excitation wavelength of titanium oxide is from 180 nm to 400 nm, but there is no luminous ultraviolet radiating material that is currently commercially available. Commercially available phosphorescent ceramics that emit light for a long time include “N Yakko” by Nemoto Special Chemical Co., Ltd.
Some afterglow times exceed 1000 minutes. This is based on strontium carbonate and calcium carbonate, with alumina as the main raw material, with eurobium and dysprosium as activators, and lanthanum, cerium, praseodymium, samarium, cadmium, terbium, holmium, erbium, thulium, ytterbium, lutetium, manganese, Either tin or bismuth element and boric acid as a flash are added and heated at 1300 ° C. to produce a long-lasting phosphorescent ceramic. In this mixed production method, it is a blue light-emitting material having a peak at 440 nm even at the shortest wavelength. This is referred to as the excitation wavelength of titanium oxide, 4
To achieve an emission wavelength of 00 nm or less, use the "N night light" described above.
Has an absorption wavelength having a peak at 360 nm;
An additive metal element is added to make the emission wavelength close to the peak at 0 nm, or the original phosphorescence wavelength characteristic of minerals such as strontium, potassium, and borax is added.
If the emission wavelength of 440 nm or less does not occur due to the blue emission of about 50 nm, phosphorescent light will not be emitted, but a mineral element having an emission wavelength of 400 nm or less, which has a shorter wavelength than strontium and does not emit color, will be purified. Then, the phosphorescent ultraviolet radiating material can be developed by blending.

For complementing the photocatalytic function, Pt, Ag, Rh,
RuO ₂ , Nb, Cu, Sn, NiO and the like can also be used as additives. In addition, SiO ₂ , Ta ₂ O ₅ , T
_{iO 2, SrTiO 3, BaTiO 3} , Pb -based or a dielectric ceramic material of perovskite compounds such as, copper, nickel, chromium, titanium, a conductive ceramic material base metal alloys such as aluminum. Further, antibacterial metals, fine particles for capturing electrons, ions or aqueous solutions may be added and fixed. These ceramic materials and the like are used in the form of fine particles or fine powder having a diameter of about 0.001 μm to 20 μm. Fine powder having such a particle size can be suspended in a uniform and dispersed state in a gas.

The amorphous titanium peroxide sol of the present invention can be produced, for example, as follows. Aqueous ammonia or an alkali hydroxide such as sodium hydroxide is added to a titanium salt aqueous solution such as titanium tetrachloride TiCl ₄ and reacted at pH 6 to 7. The resulting pale blue-white, amorphous titanium hydroxide Ti (OH) ₄ (also called orthotitanate H ₄ TiO ₄ ) is washed and separated.
When treated with aqueous hydrogen peroxide, an amorphous titanium oxide sol is obtained.

The thus obtained amorphous titanium peroxide sol according to the present invention has a pH of 6 to 7 and a particle size of 8 to 20 nm, is a yellow transparent liquid, and is stable even when stored at room temperature for a long period of time. It is. In addition, the sol concentration is usually adjusted to 1.4 to 1.6% by weight, but the concentration can be adjusted as needed. When using at a low concentration, dilute with distilled water or the like. use.

This amorphous titanium peroxide sol is in an amorphous state at room temperature and has not yet crystallized into anatase titanium oxide, and has excellent adhesion, high film-forming properties, and a uniform and flat thin film. And the dried film has the property of being insoluble in water. The amorphous titanium peroxide sol was 100
When heated for several hours at a temperature of not less than 250 ° C., an anatase-type titanium oxide sol is obtained.
To form anatase-type titanium oxide.

The viscous amorphous titanium peroxide of the present invention can be produced, for example, as follows. Aqueous ammonia or an alkali hydroxide such as sodium hydroxide is added to an aqueous solution of a titanium salt such as titanium tetrachloride TiCl ₄ to adjust the pH to an acidic range, preferably pH 2
-6, particularly preferably at pH2. After washing and separating the sedimented pale blue-white, amorphous titanium hydroxide Ti (OH) ₄ (also called orthotitanate H ₄ TiO ₄ ),
It is obtained by treating with aqueous hydrogen peroxide, reacting at low temperature, preferably at 15 ° C. or less, particularly preferably at 5 to 8 ° C. with stirring, and then curing at room temperature for 7 to 10 days.

The thus obtained viscous amorphous titanium peroxide of the present invention has a pH of 2 to 4 and a particle diameter of about 8 to 20 nm, and has a yellow transparent, slightly viscous sol to semi-jelly-like appearance. That is, it has various viscosities, has a very strong adhesive force, and is stable even when stored at room temperature for a long period of time. The solid content concentration is
Usually, the concentration is adjusted to 0.2 to 0.6% by weight, preferably 0.3% by weight, but the concentration can be adjusted as needed.

In the production process, the viscous amorphous titanium peroxide of the present invention is prepared by reacting a titanium salt aqueous solution such as titanium tetrachloride TiCl ₄ with an aqueous ammonia or an alkali hydroxide such as sodium hydroxide. The pH at the time is changed in an acidic region, desirably in a range of pH 2 to 6, so that the solid content concentration is 0.2 to 0.6.
By changing the amount within the range of weight%, various viscosities can be obtained, and various uses can be considered according to the viscosities. It is desirable to have a jelly-like viscosity.

When the pH of the above reaction exceeds 6,
Amorphous titanium peroxide sol with low viscosity,
When coating the surface of a substrate such as a metal or plastic having a strong water repellency, a hydrophilic treatment with a surfactant or the like is required. When the pH is less than 2, there is a disadvantage that the precipitation of orthotitanic acid is extremely reduced. On the other hand, if the solid content exceeds 0.6% by weight, a problem arises in that it becomes inhomogeneous semi-jelly-like, and it becomes difficult to form a thin film having a uniform thickness. On the other hand, when coating the surface of the substrate, there is a disadvantage that a hydrophilic treatment such as surface activity is required.

As described above, the viscous amorphous titanium peroxide of the present invention is a novel substance having a transparent and viscous yellow color, and has not yet crystallized in an anatase type titanium oxide in an amorphous state at room temperature. The adhesion / adhesiveness is extremely excellent in substrates of all kinds including a substrate having water repellency. In addition, it has a high film-forming property, a uniform and flat thin film can be easily formed, and the dried film does not dissolve in water.

Then, this viscous amorphous titanium peroxide is coated on a substrate,
When dried and fired at a temperature lower than 0 ° C., an amorphous titanium peroxide layer having a very strong adhesive force is formed. Also, 25
When heated and dried and baked at 0 ° C. to 940 ° C., an anatase type titanium oxide layer is formed, and when heated at 940 ° C. or more, a rutile type titanium oxide layer is formed, and the function of the photocatalyst is extremely reduced.

In the present invention, as a method for fixing the fine particles of the adsorption functional material or the fine particles of the photocatalytic functional material to the substrate, the fine particles of the adsorptive functional material or the fine particles of the photocatalytic functional material are used as a binder with an amorphous titanium peroxide sol or a viscous titanium oxide sol. Mixed with a non-crystalline amorphous titanium peroxide, coated on a substrate by a known coating method such as dipping and spraying, and then dried and calcined at room temperature to less than 250 ° C., as well as an adsorption function material and a photocatalytic function. As a method of fixing a thin film of a material to a substrate, an amorphous titanium peroxide sol or a viscous amorphous titanium peroxide is coated on the substrate to form an amorphous titanium peroxide layer, and the amorphous titanium peroxide layer is While adhering, the fine particles of the adsorption function material and the fine particles of the photocatalytic function material are uniformly dispersed in gas. As a method of adhering the amorphous titanium peroxide layer to the amorphous titanium peroxide layer in a turbulent state, and a method of fixing the fine particles of the adsorptive functional material to the substrate, amorphous titanium peroxide sol or viscous Mixed with crystalline amorphous titanium peroxide,
There is a method of applying and coating on a substrate, and then firing at 250 ° C. or higher. In this way, by fixing the fine particles of the adsorption functional material and the fine particles of the photocatalytic functional material to the substrate, and by fixing the thin film of the adsorptive functional material and the photocatalytic functional material to the substrate, An adsorption / decomposition functional body can be obtained.

When the fine particles of the adsorption functional material are mixed with the amorphous titanium peroxide sol or the viscous amorphous titanium peroxide as a binder, the mixing ratio (weight ratio) is 0.1 to 4: 1 (titanium). Conversion) is preferable,
For example, 1: 1 (in terms of titanium) is usually used.
Further, when mixing the fine particles of the adsorption functional material and the fine particles of the photocatalytic functional material and amorphous titanium peroxide sol or viscous amorphous titanium peroxide as a binder,
The mixing ratio (weight ratio) is 0.1-2: 0.1-2:
1 (in terms of titanium) is preferable, and for example, 1: 1: 1 (in terms of titanium) is usually used. In addition, the fine particles of the adsorption function material and the fine particles of the photocatalytic function material mixed with the amorphous titanium peroxide sol or the viscous amorphous titanium peroxide as the binder are not limited to the powder form, but may be in the form of a suspension, sol, or the like. May be mixed.

When the thin film of the adsorption function material and the photocatalytic function material is fixed to the substrate, the fine particles of the adsorption function material and the fine particles of the photocatalytic function material are mixed in advance, and the mixture is uniformly scattered in a gas to improve the adhesion. It can be attached to the amorphous titanium peroxide layer that it has. Alternatively, either one can be attached first and then the other, but from the viewpoint of exposing a large amount of the adsorption function material to the surface, first, the fine particles of the photocatalytic function material are first attached, and then the fine particles of the adsorption function material are attached. Is more preferable. When the fine particles of the adsorption functional material and the fine particles of the photocatalytic functional material are mixed in advance and used, the mixing ratio (weight ratio) is 0.1%.
1-4: 0.1 to 4 is preferable, and for example, 1: 1 is usually used.

The method for fixing the thin layers of the adsorption function material and the photocatalytic function material in the present invention will be described with reference to FIG. 1. An amorphous titanium peroxide sol is applied to a substrate 4 which has been subjected to a hydrophilic treatment with a surfactant or the like. Coating or
Alternatively, a viscous amorphous titanium peroxide is directly coated on a substrate without performing a hydrophilic treatment to form an amorphous titanium peroxide layer 3 while the amorphous titanium peroxide layer has an adhesive property. (Usually within 1 to 10 minutes at room temperature after coating), the fine particles 2 of the adsorption function material and the fine particles 1 of the photocatalytic function material are uniformly scattered in a gas using a closed / normal pressure vessel, and are naturally attached or There is a method in which the fine particles are adhered to the amorphous titanium peroxide layer by air pressure adhesion to remove excess fine particles. Further, by fixing a thin layer of the adsorption function material or the photocatalytic function material to the amorphous titanium peroxide layer and then applying pressure, the adhesion between the layers is significantly improved.

As described above, by forming a thin layer of the adsorption function material or the photocatalytic function material on the surface of the amorphous titanium peroxide layer, the adsorption function body of the present invention having excellent adsorption function and adsorption / decomposition function can be obtained. An adsorption / decomposition functional body can be obtained.

In the present invention, as described above, the fine particles of the adsorptive functional material are mixed with an amorphous titanium peroxide sol or viscous amorphous titanium peroxide as a binder, applied to a substrate, and coated at 250 ° C. ~ 4
By sintering at around 00 ° C. to produce anatase-type titanium oxide, an adsorption / decomposition functional body can be produced. Such an adsorption / decomposition function body has a photocatalytic function even if the fine particles of the photocatalytic function material are not mixed beforehand. In this case, the adsorption function material used in combination is sintered at about 250 ° C to 400 ° C. Does not deteriorate even if
Alternatively, it is necessary to use a precursor that can exhibit an adsorption function when sintered at around 250 ° C. to 400 ° C. When an organic polymer resin which is easily decomposed by a photocatalyst, polytetrafluoroethylene (PTFE) which is a high-performance engineering plastic, polyamideimide (PAI) or polyimide (PI) which is a super heat-resistant engineering plastic is used as a substrate. ,
Prior to coating, it is preferable to reduce the photocatalytic function of titanium oxide by allowing a sodium source to be present by, for example, cleaning the resin surface with a substance containing sodium ions such as a sodium hydroxide solution.

The binder comprising the amorphous titanium peroxide sol or the viscous amorphous titanium peroxide is as follows:
It has the characteristic that a thin film of a predetermined thickness can be obtained by one coating. The thickness of the titanium oxide layer formed by coating or the thin film of the titanium oxide layer obtained by heating and baking at 250 ° C. or higher is determined by the concentration of titanium peroxide in viscous amorphous titanium peroxide or the like. (% By weight), viscosity and coating thickness before drying.
Many fine particles of the adsorption function material are exposed on the surface layer of these thin films,
An excellent adsorption function can be exhibited.

The amorphous titanium peroxide sol or the amorphous titanium peroxide layer formed from the viscous amorphous titanium peroxide as the binder has excellent weather resistance. In addition to protecting the substrate from the like, when a photocatalytic function material layer is provided on the surface of the amorphous titanium peroxide layer, a substrate such as an organic polymer material which is easily decomposed by the photocatalytic function can be protected.

[0039]

EXAMPLES The present invention will be described more specifically below with reference to examples, but the technical scope of the present invention is not limited to these examples.

REFERENCE EXAMPLE 1 (Production of amorphous titanium peroxide sol) A 50% solution of titanium tetrachloride TiCl ₄ (Sumitomo Sytics Co., Ltd.) was diluted 70 times with distilled water, and ammonium hydroxide NH ₄ OH was used. A 25% solution (Takasugi Pharmaceutical Co., Ltd.) diluted 10 times with distilled water was added to p
H is adjusted to 6.5 to 6.8 to carry out the reaction. After the reaction, the mixture is left for a while and the supernatant is discarded. Distilled water about 4 times the amount of the remaining Ti (OH) ₄ gel is added, sufficiently stirred, and allowed to stand.
Washing with water is repeated with a conductivity meter until the conductivity becomes 2 to 10 μS. Finally, the supernatant is discarded to leave only the precipitate. In some cases, the concentration treatment can be performed by a concentrator. To 3600 ml of this pale blue-white Ti (OH) ₄ , 35%
210 ml of aqueous hydrogen peroxide is added in two portions every 30 minutes and stirred at about 5 ° C. overnight to obtain about 3800 ml of a yellow transparent amorphous titanium peroxide sol. In addition, in the above steps, if the heat generation is not suppressed, a substance insoluble in water such as metatitanic acid may be precipitated. Therefore, it is preferable that all the steps are performed with the heat generation suppressed.

Reference Example 2 (Production of Viscous Amorphous Titanium Peroxide) A solution obtained by diluting 100 ml of a 50% solution of titanium tetrachloride TiCl ₄ (Sumitomo Sytics Co., Ltd.) 70 times with distilled water and ammonium hydroxide NH ₄ OH 25% solution (Takasugi Pharmaceutical Co., Ltd.) diluted 10 times with distilled water
Adjust to H2.0 and perform the reaction. After the reaction, the mixture is left for a while and the supernatant is discarded. The remaining orthotitanate Ti (O
H) ₄ of about 4 times the distilled water of the gel volume was added well stirred standing. Washing with water is repeated with a conductivity meter until the conductivity becomes 2 to 10 μS. Finally, the supernatant is discarded to leave only the precipitate. In some cases, the concentration treatment can be performed by a concentrator. This pale blue white orthotitanate Ti (OH)
₄ aqueous 2550ml, 35% aqueous hydrogen peroxide 200m
l was added twice every 30 minutes, stirred at about 5 ° C. overnight, and then cured at a daily temperature of 7 to 10 to obtain about 2800 ml of a yellow transparent jelly-like amorphous titanium peroxide sol.

REFERENCE EXAMPLE 3 (Preparation of Viscous Viscous Amorphous Titanium Peroxide) The procedure of Reference Example 2 was repeated except that the pH during the reaction was changed to 3, 4 and 5. As compared with the viscous amorphous titanium peroxide obtained in Reference Example 2, as the pH increased, a hard jelly-like one was obtained, and the solid concentration gradually increased.

Example 1 Glass beads (manufactured by Toshiba Palotini KK; GB60)
2) Place 180 g in a 120 mm x 80 mm mold,
The resultant was baked at a temperature of 30 ° C. for 30 minutes. Next, 0.85% by weight of an amorphous titanium peroxide sol as a binder prepared in Reference Example 1 (in terms of titanium)
In 200 ml of liquid, 1.7 g of coconut shell activated carbon (manufactured by Character Industry Co., Ltd .; BFG dry) as an adsorption function material and 1.7 g of anatase TiO ₂ (manufactured by Ishihara Techno Co., Ltd .; ST-01) as a photocatalytic function material ( Titanium equivalent)
Was coated on the glass bead substrate by dipping, and the amount of the mixture attached was 15 g / 180 g in a water-containing state. This one
After drying at 00 ° C. for 30 minutes, an adsorption / decomposition functional body was obtained. Also,
This adsorption / decomposition functional body was further baked at 300 ° C. for 30 minutes to obtain another adsorption / decomposition functional body. These two adsorbing / decomposing functional bodies were both excellent in contaminant adsorbing ability and resolution by photocatalysis after adsorption.

Example 2 An acrylic resin plate, a methacrylic resin plate, and a methyl methacrylate resin plate were used as substrates. The surfaces of these resin plates were washed with water and dried, and the resin plates were coated once with viscous titanium peroxide having a concentration of 1.85% by weight (in terms of titanium) prepared in Reference Example 2 by dipping. When the coating surface is in a wet state, coconut shell activated carbon (manufactured by Character Industry Co., Ltd .; BFG dry) as an adsorption function material is adhered in a gaseous uniform suspension state in the container.
After drying at 0 ° C., the film was heated at 200 ° C. under pressure and then washed to prepare an adsorption function body on which a thin film of the adsorption function material was fixed. There was no danger of peeling of the thin film of the adsorptive material layer or the amorphous titanium peroxide layer in the adsorptive function body, and the adsorbability was remarkably excellent because the fine particles of the adsorptive material covered the surface layer.

Example 3 As a substrate, a semi-porcelain glazed tile (manufactured by INAX Corporation:
100 × 100 × 5 mm), a ceramic coated steel plate (210 × 296 × 0.8 mm), and a keramit plate (glazed type: 157 × 223 × 4 mm) were used. These surfaces were washed and dried at room temperature, and then 0.3% by weight of the viscous titanium peroxide prepared in Reference Example 2 was squeezed on a porcelain glazed tile at 0.1 to 0.2 g / g. Sheets, 2.0 to 2.3 g /
And a keramit plate were coated at 1.5 to 1.8 g / sheet, respectively. When the coating surface is in a wet state, an equal amount mixture of coconut shell activated carbon (manufactured by Character Industry Co., Ltd .; BFG dry) and anatase type titanium oxide powder ST-01 (manufactured by Ishihara Techno Co., Ltd.) is uniformly suspended in a gas in a container. When it was adhered for 1 minute in the state, it was 0.01 to 0.02 g / sheet for the glazed porcelain tile and 0.1 to 0.2 g / sheet for the ceramic coated steel plate.
Sheet, 0.1 g / sheet for keramit board, Yashigara activated carbon (Character Industry Co., Ltd .; BFG dry)
And an anatase-type titanium oxide powder adhering thereto, which was dried at 50 ° C. to prepare an adsorption / decomposition functional body.

Example 4 As a substrate, a polyester / rayon nonwoven fabric (30
0 × 300 mm). The nonwoven fabric is washed with water, dried and adhered by viscous titanium peroxide having a concentration of 1.85% by weight (in terms of titanium) prepared in Reference Example 2 by dipping, and then coconut shell activated carbon (manufactured by Character Industry Co., Ltd .; BFG) Dry) and anatase type titanium oxide powder ST
-01 (manufactured by Ishihara Techno Co., Ltd.) was adhered in a gaseous uniform suspension state, and dried and fixed at 50 ° C. Thereafter, the dried product was pressed with an iron at 120 to 150 ° C. to further improve the adhesion between the layers. This adsorption / decomposition functional body was excellent not only in adsorption / decomposition performance but also in cosmetic properties.

Example 5 An organic substance decomposition test was performed as follows. Paragrass (methacrylic resin manufactured by Kuraray Co., Ltd.) measuring 210 × 296 mm in length and width was used for the substrate. 0.3% by weight of the viscous titanium peroxide prepared in Reference Example 2 was adhered to this substrate by dipping, and then coconut shell activated carbon (manufactured by Character Industries Co., Ltd .; BFG dry) and anatase type titanium oxide powder ST-01 ( (Ishihara Sangyo Co., Ltd.) was adhered in a gaseous uniform suspension state, and dried and fixed at 50 ° C. Thereafter, the dried product is pressed with an iron at 120 to 150 ° C. to further improve the adhesion between the layers, thereby obtaining an adsorption / decomposition function body carrying a thin film composed of an adsorption function material and a photocatalytic function material. Was. For these tests,
The decomposed functional body was placed in a 5-liter transparent test container, and then ammonia gas, which was an organic substance to be decomposed, was injected and sealed into the container so that the concentration became 40 ppm. One excitation lamp BL20W was irradiated from a distance of about 70 cm from the adsorption / decomposition functional body, and the ammonia gas concentration in the container was measured by a detection tube method. As a result, the ammonia gas concentration dropped sharply to 2 ppm 30 minutes after the start of the test. On the other hand, the ammonia gas concentration after 30 minutes in the control without the adsorption / decomposition functional body was 38 ppm.

[0048]

According to the present invention, when viscous amorphous titanium peroxide is used as a binder for fixing the fine particles of the adsorption functional material and the fine particles of the photocatalytic functional material to the substrate, hydrophilicity by a surfactant or the like can be applied to any substrate. Amorphous titanium peroxide layer can be formed without the need for thermal treatment, and its excellent adhesion makes it possible to fix thin layers of adsorbent and photocatalytic materials, making practical adsorption function possible. The body and the adsorption / decomposition functional body are obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a method of fixing a thin layer of an adsorption function material or a photocatalytic function material.

[Explanation of symbols]

 1 Fine Particles of Photocatalytic Functional Material 2 Fine Particles of Adsorbent Functional Material 3 Amorphous Titanium Peroxide Layer 4 Base

Claims (12)

[Claims] 1. A method of fixing fine particles of an adsorptive material to a substrate, comprising coating a mixture of the fine particles of the adsorptive material and an amorphous titanium peroxide sol as a binder on a substrate, and then at room temperature to less than 250 ° C. A method of fixing fine particles of an adsorption functional material to a substrate, characterized by drying and firing. 2. A method for fixing fine particles of an adsorptive functional material to a substrate, wherein the fine particles of the adsorptive functional material and a viscous amorphous mold as a binder are not subjected to hydrophilic treatment on the surface of the substrate having water repellency. A method of coating fine particles of an adsorption functional material on a substrate, comprising coating a mixture with titanium oxide on a substrate, followed by drying and firing at room temperature to less than 250 ° C. 3. A method of fixing a thin layer of an adsorption function material to a substrate, comprising coating a substrate with an amorphous titanium peroxide sol to form an amorphous titanium peroxide layer, wherein the amorphous titanium peroxide layer is A method of fixing a thin layer of an adsorption function material, wherein the fine particles of the adsorption function material are adhered to the amorphous titanium peroxide layer in a state of being uniformly scattered in a gas while having an adhesive property. 4. A method of fixing a thin layer of an adsorptive material to a substrate, comprising coating a viscous amorphous titanium peroxide without performing a hydrophilic treatment on the surface of the substrate having water repellency. Forming a titanium peroxide layer, and adhering fine particles of the adsorption function material to the amorphous titanium peroxide layer in a uniform scattering state in a gas while the amorphous titanium peroxide layer has an adhesive property. A method of fixing a thin layer of an adsorption functional material, characterized by the following. 5. An adsorption function body produced by the method according to claim 1. 6. A method for fixing fine particles of an adsorption function material to a substrate, wherein a mixture of the fine particles of the adsorption function material and an amorphous titanium peroxide sol as a binder is coated on the substrate, and then fired at 250 ° C. or higher. A method for fixing fine particles of an adsorption functional material to a substrate, characterized by comprising: 7. A method for fixing fine particles of an adsorption function material to a substrate, wherein the fine particles of the adsorption function material and a viscous amorphous mold as a binder are treated without performing a hydrophilic treatment on the surface of the substrate having water repellency. A method of fixing fine particles of an adsorption functional material to a substrate, comprising coating a mixture with titanium oxide on a substrate and then firing the mixture at 250 ° C. or higher. 8. A method for fixing fine particles of an adsorption functional material and fine particles of a photocatalytic functional material to a substrate, comprising a mixture of the fine particles of the adsorptive functional material, the fine particles of the photocatalytic functional material, and the amorphous titanium peroxide sol as a binder. A method of fixing fine particles of an adsorption functional material and fine particles of a photocatalytic functional material to a substrate, wherein the fine particles are coated on a substrate and then dried and calcined at room temperature to less than 250 ° C. 9. A method for fixing fine particles of an adsorption function material and fine particles of a photocatalytic function material to a substrate, wherein the fine particles of the adsorption function material and the photocatalytic function material are not subjected to hydrophilic treatment of the surface of the substrate having water repellency. A mixture of fine particles of the above and a viscous amorphous titanium peroxide as a binder coated on a substrate, and then dried and calcined at room temperature to less than 250 ° C. Method to fix the fine particles. 10. A method for fixing a thin layer of an adsorption function material and a photocatalytic function material to a substrate, comprising coating an amorphous titanium peroxide sol on the substrate, forming an amorphous titanium peroxide layer, An adsorption function wherein the fine particles of the adsorption function material and the fine particles of the photocatalytic function material are adhered to the amorphous titanium peroxide layer in a uniform scattering state in a gas while the titanium oxide layer has an adhesive property. A method for fixing a thin layer of a material and a photocatalytic functional material. 11. A method for fixing a thin layer of an adsorption function material and a photocatalytic function material to a substrate, comprising coating a viscous amorphous titanium peroxide without performing a hydrophilic treatment on the surface of the substrate having water repellency. Then, an amorphous titanium peroxide layer is formed, and while the amorphous titanium peroxide layer has adhesiveness, the fine particles of the adsorption function material and the fine particles of the photocatalytic function material are uniformly dispersed in a gas. A method for fixing a thin layer of an adsorption function material and a photocatalytic function material, wherein the thin layer is attached to an amorphous titanium peroxide layer. 12. An adsorption / decomposition body produced by the method according to claim 6. Description: