JPH11179213A - Raw material for purification of environment and purifying material for environment using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To firmly fix a photoreactive semiconductor and to prevent it from falling apart by fixing a photoreactive semiconductor by CVD or PVD method on a fiber, solid or sheet carrier to form a material for cleaning an environment which decomposes contaminants such as harmful gases, bacteria and org. substances and purifies the environment. SOLUTION: A photoreactive semiconductor is firmly fixed to one kind of a carrier in a fiber, solid or sheet state by CVD or PVD method to produce a material for purification of environment. As the fiber carrier, a nonwoven fabric, paper or woven fabric is used, and as the solid carrier, a coating material or coating liquid on a base body is used. As the sheet carrier, a coated metal sheet, glass sheet or film can be used. The photoreactive semiconductor has a photocatalytic function which causes photochemical reaction by irradiation of light at specified wavelength. Titanium oxide is preferably used, and its particles having 10 to 500 m<2> /g specific surface area are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to toxic gas, various bacteria,
Regarding environmental purification materials that can decompose and purify contaminants such as organic substances and environmental purification materials using the same, more specifically, photoreactive semiconductors are firmly applied to fibrous, solid, and sheet carriers. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an environment-purifying material that is fixed and does not fall off a photoreactive semiconductor and an environment-purifying material using the same.

[0002]

2. Description of the Related Art With the deterioration of the global environment in recent years, it has been highlighted as a social problem, and its interest is increasing more and more. Various activities have been carried out to create a comfortable living environment, such as greening of cities and parks, and setting up houseplants in offices and homes. However, environmental problems such as exhaust gas from flooding automobiles, domestic wastewater and sewage from households, and cigarette smoke caused by smoking are great, and the demand for purification is increasing day by day.

[0003] In particular, odor is regarded as a familiar problem, and various methods have been adopted. For example, a masking method that eliminates unpleasant odors due to the strong aroma of rose, lily of the valley, jasmine, etc., a biomimetic method that decomposes malodorous molecules using artificial enzymes, neutralizes amines with acids, and neutralizes hydrogen sulfide with alkali Chemical methods to convert malodorous molecules to other substances using very fast chemical reactions, such as biological methods to kill spoilage bacteria by microorganisms and enzymes, and to suppress or decompose malodorous substances, and porous materials There are physical methods for adsorbing malodorous molecules and the like, and among these various methods, the physical method is widely used.

[0004] As the above physical method, products of various shapes using powder or granular activated carbon having micropores therein are widely used. Furthermore, fibrous activated carbon made from carbon fiber as a raw material has been developed from powdered or granular activated carbon, and it can be processed into sheets, molded products, electrostatic flocking, etc. due to its fibrous characteristics, for water purifiers and for deodorizing deodorizing equipment It is used for seats, honeycomb filters for deodorizing air conditioning equipment, and the like.

[0005] Conventional techniques using fibrous activated carbon include:
For example, JP-A-56-24151 can be mentioned.
The publication discloses an adsorbent in which activated carbon fiber and hot-melt synthetic resin fiber are blended or mixed and then heated to fuse or bond the two together, deodorizing and purifying air, It describes uses such as solvent recovery and solvent concentration.

However, even if an adsorbent composed of activated carbon fibers having a high adsorbent capacity is used, the adsorbent capacity is limited. To re-activate the adsorbent which has reached the limit, a regeneration treatment or a new process is required. It is necessary to prepare an adsorbent, and a simple and inexpensive one has been demanded. In addition, it is only ideal that the odor is absorbed, and it is most ideal that the odor can be decomposed and removed.

In recent years, application studies of photocatalytic reactions using semiconductor powders represented by titanium oxide, which are called photocatalysts (photoreactive semiconductors in the present invention), have been actively conducted. Titanium oxide has a property of decomposing water by causing a photochemical reaction when irradiated with ultraviolet rays.
Further, it has a function of decomposing various organic substances in addition to water, and has been applied in many fields. Numerous prior arts can also be found on the patent side.

For example, as a method for removing low-concentration nitrogen oxides from air, Japanese Patent Publication No. 2-62297 discloses a method for removing low-concentration nitrogen oxides from air using artificial light or sunlight of 300 nm or more. A method for removal by an activated carbon mixture is disclosed.

As a method for removing harmful substances, Japanese Patent Laid-Open No.
JP-256755-A discloses that by irradiating a photoreactive harmful substance removing material composed of granular pulp carrying a photoreactive semiconductor with ultraviolet light, harmful substances such as malodorous substances, pungent odorous substances, and horticultural crop growth promoting components are removed. A method of removing is disclosed.

[0010] Further, as a photodecomposition method, JP-A-6-2
No. 33929 discloses that sunlight is divided into a long wavelength band and a short wavelength band, a solution in which a photocatalyst is dispersed is irradiated with light in a short wavelength band, and a product by a photochemical reaction, for example, hydrogen and oxygen from water, A method is disclosed for decomposing an aqueous CO ₂ solution into CH ₃ OH and CH ₄ .

As exemplified above, a photocatalyst such as titanium dioxide is irradiated with specific light such as artificial light, sunlight, ultraviolet light, or light in a short wavelength band as a light source to remove harmful substances. I have.

Incidentally, the photoreactive semiconductor has a thickness of 400 nm.
When irradiated with light of the following wavelengths, it is an advantage that almost all organic substances in the vicinity are decomposed, and it is also a disadvantage, so immobilization to the substrate is one problem. I have.

For example, Japanese Patent Application Laid-Open No. 6-315614 discloses a purifying material using a fluorine-based resin which is relatively hard to decompose in a photoreactive semiconductor. In the same publication, purification is performed by molding titanium dioxide or a photocatalyst powder containing titanium dioxide and activated carbon as main components into a sheet or panel using a synthetic resin, or attaching the powder to a sheet or panel surface using an adhesive. The material is disclosed. Here, a fluororesin is used as a base material to be formed into a sheet or panel shape, and as an adhesive for a surface-adhering material. However, although there is an advantage that it can be used regardless of the form and type of titanium dioxide, there are great restrictions on the strength problem and the type of substrate to be fixed.

JP-A-6-296874 discloses a sheet-like ethylene decomposition catalyst in which a photocatalyst is supported on a sheet-like carrier using a binder. This publication discloses a sheet-like ethylene decomposition catalyst in which titanium oxide fine particles having a specific particle diameter are supported on a sheet-like carrier having a high reflectance surface using a binder having good light transmittance. Here, as the binder, a silica binder having a good light transmittance is mentioned. However, there is a problem that the adhesiveness to the sheet-like carrier is not sufficient and that the photocatalytic activity is reduced by the binder.

As a titanium oxide coating film forming composition for photocatalyst capable of firmly coating and adhering a photocatalyst to the surface of a substrate, Japanese Patent Application Laid-Open No. 8-
There is 164334 gazette. This publication discloses a titanium oxide coating composition for a photocatalyst comprising titanium oxide, a hydrolyzate of a specific hydrolyzable silicon compound, and a solvent, wherein titanium and silicon are mixed at a specific weight ratio. It is stated that a composite coating film of titanium oxide and silicon oxide can be formed by using the composition and applying and drying it on the surface of a substrate such as glass, metal, cement, wallpaper, and plastic. However, the hydrolyzate covers the titanium oxide surface and also has a role as a binder for the substrate, so that the photocatalytic activity tends to decrease and the adhesive strength tends to be insufficient.

Further, as a photocatalyst fixed film in which semiconductor powder is fixed to a porous polymer film, there is JP-A-1-135842. This publication discloses a method in which a polymer film material such as polysulfone, cellulose acetate, polyvinyl alcohol, or the like is dissolved in an appropriate solvent, and a semiconductor powder is mixed to form a film. However, when semiconductor powder is fixed as a polymer film, there is a problem that the semiconductor powder is buried in the polymer film and the photocatalytic activity is not sufficiently exhibited.

On the other hand, as a nonwoven fabric using fibers containing an oxide-based fine powder deodorant (the photoreactive semiconductor in the present invention), there is JP-A-1-156576. The gazette contains an oxide-based fine powder deodorant, is exposed to an atmosphere in which active species are present, the surface is finely etched, and the film on the fine powder deodorant is destroyed. Discloses a nonwoven fabric composed of fibers having a part exposed. Here, the fibers constituting the nonwoven fabric are made of fibers spun in advance by adding a fine powder deodorant to the fiber material, and the fibers are subjected to an etching treatment to expose the fine powder deodorant to the fiber surface. It is. Fiber by such a method,
Although the fine powder deodorant is easily exposed to the fiber surface and the degree of immobilization is high, there is a problem that the fiber is inferior in strength.

As described above, various methods have been studied as a method for immobilizing a photoreactive semiconductor on various substrates, and these methods have been used in accordance with the respective methods. However, there is no satisfactory method. At present, technology development is desired.

[0019]

SUMMARY OF THE INVENTION The present invention relates to a toxic gas,
An environmental purification material that can decompose and purify contaminants such as germs and organic substances, and an environmental purification material using the same. An object of the present invention is to provide an environment-purifying material that is fixed and does not fall off a photoreactive semiconductor, and an environment-purifying material using the same.

[0020]

Means for Solving the Problems As a result of earnest research, the present inventor has found that the above object can be achieved by an environmental purification material in which a photoreactive semiconductor is supported on a carrier and an environmental purification material using the same. I found it.

In the environmental purification material of the present invention, the environmental purification material is obtained by fixing a photoreactive semiconductor by a CVD method or a PVD method to a carrier made of any one of fibrous, solid, and sheet. It is.

In the present invention, the PVD method is preferably
It is characterized by the RF plasma method.

The fibrous carrier is preferably either an organic fiber or an inorganic fiber.

It is preferable that the solid carrier is any one of an organic granular material, an inorganic granular material, and a metallic granular material.

As the sheet-like carrier, an organic sheet,
Preferably, the sheet is either an inorganic sheet or a metal sheet.

The environment-purifying material of the present invention is characterized in that the environment-purifying material is a nonwoven fabric mainly composed of an environment-purifying fiber material obtained by fixing a photoreactive semiconductor to a fibrous carrier by a CVD method or a PVD method. Environmental purification material.

In the environment-purifying material of the present invention, the fibrous carrier is an environment-purifying fiber material made of activated carbon fiber, and a nonwoven fabric made of the fiber material and organic fibers.
An environmental purification material characterized by being a nonwoven fabric in which the organic fibers are mutually entangled or the organic fiber and the fiber material are three-dimensionally entangled.

[0028] An environmental purification material characterized in that it is a wallpaper in which an adhesive layer is applied on one side of the above-mentioned environmental purification material of the present invention.

The environment-purifying material of the present invention is characterized in that the material is an environment-purifying solid material in which a photoreactive semiconductor is fixed to a solid carrier by a CVD method or a PVD method, and a paint mainly composed of an adhesive. It is a purification material.

In the environmental purification material of the present invention, the sheet-like carrier is a glass sheet, and the photoreactive semiconductor is fixed on the surface of the glass sheet by a CVD method or a PVD method. is there.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The environmental purification material of the present invention and the environmental purification material using the same will be described in detail below.

The environmental purification material according to the present invention is a material in which a photoreactive semiconductor is firmly fixed to a carrier, such as a fibrous, solid or sheet type, by a CVD method or a PVD method. Depending on the method of using the carrier to which is immobilized, various forms of environmental purification materials having a wide range of applications can be obtained. The features of the environmental purification material and the environmental purification material of the present invention are that the photoreactive semiconductor is
By performing the immobilization treatment by the VD method or the PVD method,
In order to be able to produce an environment-purifying material in which the photoreactive semiconductor does not fall off from the surface of the carrier, it can be processed without requiring specific conditions to an environment-purifying material as various applied products.

For example, a fibrous carrier may be a non-woven fabric, a base paper, a woven fabric, etc., a solid carrier may be a coating, a coating liquid for coating a substrate, a sheet-shaped carrier may be a coated metal plate, Examples include a glass plate and a film.

In the present invention, the means for firmly fixing the photoreactive semiconductor to the carrier is carried out by using the CVD method or the PVD method. That is, the CVD method or P
RF plasma method (Radio
The carrier to be coated is continuously or semi-continuously supplied into a flow containing the ultra-fine particles of the photoreactive semiconductor generated in the gas phase by the frequency plasma, and the ultra-fine particles of the photoreactive semiconductor are supplied. The carrier to be coated is contacted with the ultrafine particles in an active state to adhere them,
Thus, an environmental purification material can be obtained in which ultrafine particles are firmly bonded and fixed to the surface of the carrier to be coated.

The environment-purifying material of the present invention can sufficiently exhibit the function of the present invention in a state where the surface of the carrier is not completely covered with the ultrafine particles of the photoreactive semiconductor but is covered in a projecting manner on the surface of the carrier. Have

In producing the environmental purification material of the present invention, ultra-fine particles of photoreactive semiconductor are produced by plasma jet generation by arc discharge, by arc electrolysis, by high-frequency plasma generation, by gas evaporation method. It can be produced by physical means such as, or by chemical means involving reduction or oxidation. The carrier to be coated is introduced into an airflow containing the generated ultra-fine particles of the photoreactive semiconductor, the ultra-fine particles and the carrier are brought into contact with each other in an active state, and the two are strongly chemically bonded, Manufacture environmental purification materials.

In the present invention, the main photoreactive semiconductor is a semiconductor having a function as a photocatalyst that causes a photochemical reaction when irradiated with light of a specific wavelength, and includes a valence band filled with electrons and an empty conduction band. , And a forbidden band separating them. When light having energy equal to or higher than the forbidden band is absorbed, electrons in the valence band are excited to the conduction band. With this photoexcitation, holes, that is, vacancies of electrons remain in the valence band. On the semiconductor surface, excited electrons and holes reduce and oxidize components in the gas phase and the liquid phase, respectively, and harmful substances can be removed by using this chemical reaction.

The form of the photoreactive semiconductor is preferably in the form of particles, and these particles have a specific surface area of 10 to 500.
m ² / g is appropriately selected and used.

Examples of such a photoreactive semiconductor include those disclosed in JP-A-2-273514, such as zinc oxide, tungsten trioxide, titanium oxide, cerium oxide, and ferric oxide. Of these are preferred, and among these, titanium oxide is preferred because of its excellent deodorizing properties.

Examples of titanium oxide include titanium dioxide, hydrous titanium oxide, hydrated titanium oxide, metatitanic acid,
Ortho titanic acid, titanium hydroxide and the like can be mentioned. The crystal type is not particularly limited.

The titanium oxide has a specific surface area of 50 to 4
Those having a range of 00 m ² / g are preferred.

The carrier used in the present invention has a role of supporting a photoreactive semiconductor. Photoreactive semiconductors can remove harmful substances such as malodors by photocatalysis, but also have the disadvantage of deteriorating and discoloring organic components such as resin-based binders that come into contact with the photoreactive semiconductor. When a photoreactive semiconductor is supported on a carrier, direct contact with a resin-based binder or a base material can be reduced, and deterioration of an environmental purification material, which is a molded product,
It is very effective in preventing discoloration.

The carrier used in the present invention includes various types of carriers such as fibrous, solid, and sheet.

Examples of the fibrous carrier include organic fibers and inorganic fibers. For example, polyester fibers, polyolefin fibers, polyacrylonitrile fibers, polyvinyl alcohol fibers, nylon fibers, urethane fibers, etc., especially aramid fibers and polyphenylene fibers In addition to organic engineering plastic fibers, such as sulfide fibers, polyetherimide fibers, and polyparaphenylene benzoxazole fibers, which have high flame retardancy, polyester fibers and polyolefin fibers kneaded with flame retardants in general-purpose organic polymers , Acrylic fiber, vinylon fiber, organic fiber such as vegetable fiber, metal fiber such as Cu, Al, Fe, glass fiber, alumina fiber, Tyranno fiber, activated carbon fiber,
Examples include inorganic fibers such as SiC whiskers and alumina whiskers.

In particular, among the fibrous carriers, activated carbon fibers are preferably used. Activated carbon fibers usually have a fiber diameter of 2 to 30 μm, a fiber length of 0.5 to 10 mm, and a pore diameter of 8
It has fine pores of ~ 20 angstroms and a specific surface area of 50
0-2500 m ² / g, rayon type, polyacrylonitrile type, phenolic resin type, coal pitch type,
A petroleum pitch type or the like can be mentioned, and there is no limitation.

The solid carrier includes organic particles, inorganic particles, and metal particles. For example, organic carriers such as polyester resin, polyamide resin, polyimide resin, polyphenylene sulfide resin, epoxy resin, and phenol resin. Inorganic particles such as glass, shirasu balloon, silica, and alumina, Ag, Al, Au,
Co, Cu, Fe, Mg, Mn, Ni, Sn, W, P
Metal-based particles such as b, Zn, Zr, and Cr are exemplified.

As the sheet-shaped carrier, organic sheets,
There are inorganic sheets, metal sheets, etc., for example, organic sheets such as polyester films, polyamide films, polyimide films, polyolefin films, inorganic sheets such as glass plates, Fe, Al, N
Metallic sheets such as i, Zn, and the like. Among these sheet-shaped carriers, a glass sheet is preferable in terms of durability.

In the above-mentioned carrier, it is more effective if the carrier itself has the ability to adsorb odorous substances. When a carrier having such an adsorption ability is used, a malodorous substance can be adsorbed by the carrier and then decomposed and removed by the photocatalytic action of the photoreactive semiconductor. This stepwise removal method of harmful substances called adsorption and decomposition is very efficient. Further, a carrier having a catalytic action can also be preferably used.

Specifically, as those having an adsorption ability,
Activated carbon powder, activated carbon fiber, zeolite and the like, which have a catalytic action, include iron-based metal compounds such as iron sesquioxide. In addition, zinc oxide, magnesium oxide,
Examples include aluminum oxide, silica, silica-alumina-zinc oxide composite, composite phyllosilicate, silica-zinc oxide composite, or a mixture thereof.

As described above, each carrier constituting the environmental purification material of the present invention has been individually described. The environmental purification material may be appropriately changed depending on the form and properties of each carrier. For example, it is difficult to use an environment-purifying solid material in which a photoreactive semiconductor is immobilized on a solid carrier as it is as an environment-purifying material. Solid environmental purification material (environmental purification solid material) can be made easy to use itself by agglomerating it into a size that is easy to handle and forming it into granules, pellets, tablets, etc. it can.

Next, an environmental purification material using the environmental purification material of the present invention will be described below.

The first invention of the environmental purification material is an environmental purification material using an environmental purification fiber material in which a photoreactive semiconductor is immobilized on a fibrous carrier.

Conventionally, there are a number of environmental purification materials which use a powdery photoreactive semiconductor and are supported on a nonwoven fabric by various methods. However, a method for immobilizing the photoreactive semiconductor on the nonwoven fabric has been devised. However, immobilization is insufficient and the photoreactive semiconductor falls off the nonwoven fabric. On the other hand, the environmental purification material of the present invention comprises a photoreactive semiconductor on
It is an environment-purifying fiber material immobilized by the D method or the PVD method, and is used as a nonwoven fabric. Already, since the photoreactive semiconductor is firmly fixed to the fibrous carrier, a nonwoven fabric can be manufactured regardless of a dry or wet manufacturing method. Does not fall off.

As the fibers constituting the nonwoven fabric, the above-mentioned various organic fibers and inorganic fibers can be used, and the nonwoven fabric is produced in combination with the fibers supporting the photoreactive semiconductor. -Organic fibers or inorganic fibers may be used depending on the application.

The method for producing the nonwoven fabric is not particularly limited, and a web obtained by a dry method, a wet papermaking method, a melt blown method, a spun bond method, etc. may be used in accordance with the purpose and application. , A physical method such as a stitch bond method, a heat bonding method such as a thermal bond method, a method of developing strength by a method using an adhesive such as a resin bond method, and the like, as appropriate.

The second invention of the environment-purifying material is an environment-purifying material comprising a nonwoven fabric in which a photoreactive semiconductor is immobilized on activated carbon fibers and three-dimensionally entangled with the photoreactive semiconductor.

The environmental purification material of the present invention is an environmental purification fiber material using activated carbon fiber as a fibrous carrier.
By using the fiber material and the organic fiber to form a nonwoven fabric in which organic fibers are three-dimensionally entangled with each other or between the organic fiber and the fiber material, the activated carbon fiber itself exhibits the ability to adsorb odorous substances. At the same time, it is possible to provide an environmental purification material having more durability.

The activated carbon fibers used usually have a fiber diameter of 2
３０30 μm, fiber length 0.5-10 mm, pore diameter 8〜
20 angstrom fine pores, specific surface area 500
2,500 m ² / g, and examples thereof include rayon-based, polyacrylonitrile-based, phenolic resin-based, coal pitch-based, and petroleum pitch-based systems, without any limitation.

As such activated carbon fibers, cotton,
Hemp, regenerated cellulose fiber, polyvinyl alcohol fiber,
Raw materials such as acrylic fiber, aromatic polyamide fiber, cross-linked formaldehyde fiber, lignin fiber, phenol fiber, petroleum pitch fiber, coal pitch fiber, etc., are obtained by performing carbonization treatment and surface activation treatment at high temperature according to a conventional method. Things.

The shape, fiber diameter, and fiber length of the activated carbon fiber are not particularly limited, but it is possible to prevent the activated carbon fiber from falling off when a high-pressure columnar water stream is applied to the fiber web, and to provide a good formation. In order to obtain a nonwoven fabric, the average fiber diameter is preferably 5 to 30 μm, and more preferably. Further, the average fiber length is preferably 3 mm to 15 mm.

The types of the organic fibers used in the present invention include:
There is no particular limitation, and polyester fibers, polyolefin fibers, polyacrylonitrile fibers, polyvinyl alcohol fibers, nylon fibers, and urethane fibers can be used alone or in any combination thereof. In addition, exfoliated splittable conjugate fibers, which are fibers in which two or more types of components having low compatibility with each other are joined and are easily split by a mechanical action or an action of a swelling agent to generate ultrafine fibers, can also be used. .

The organic fibers used in the present invention preferably have an aspect ratio in the range of 1000 to 2500 and a fiber diameter of the organic fibers of 9 μm or less. When the fiber diameter is not more than this, the number of fibers in the sheet increases, so that the amount of the fiber for obtaining a sufficient reinforcing effect can be reduced. In addition, the organic fiber having a fiber diameter or less is easy to bend, and the high-pressure columnar water interposes the activated carbon fiber,
The fibers can easily be entangled with each other.

Here, the state in which the organic fibers are entangled with each other with the activated carbon fibers interposed therebetween is such that the organic fibers bend when hitting the high-pressure columnar water, surround and capture the activated carbon fibers, and Refers to a state in which the organic fibers around are intertwined with each other.

The cross-sectional shape of the organic fiber used in the present invention may be not only a circle but also an ellipse, and more preferably, a so-called irregular cross-section such as a triangular, Y-shaped, T-shaped, U-shaped, star-shaped or dog-bone shaped. Those having a shape are preferred. When the cross-sectional area of the organic fiber is the same between the perfect circle and the irregular cross section, the behavior with respect to bending is different, and the organic fiber having the irregular cross section causes anisotropy in bending stiffness and rigidity in the short axis direction. Is extremely small, so that it is easy to bend in the short axis direction, and at the time of hydroentanglement, the active carbon fibers are surrounded and the fibers are easily entangled via the active carbon fibers. In addition, the irregular cross section has more corners and is better hooked on activated carbon fibers,
As compared with a perfect circle, there is an effect that the falling off of the activated carbon fiber is small.

The fiber length of the organic fiber used in the present invention is 5 to 5.
25 mm is preferred. If the fiber length is longer than 25 mm, the dispersing process in water is difficult, so it is necessary to select a dispersant and use an appropriate amount. In addition, after dispersing once, coagulation occurs again, causing entanglement, entanglement, and lumps. The problem that it becomes easy to come up arises. In addition, the dispersion concentration must be reduced, resulting in poor productivity.

On the other hand, if the fiber length is shorter than 5 mm, the dispersing step is easy, but the fiber is easily moved by the high-pressure columnar water flow.
Not only is it difficult to obtain a sheet (nonwoven fabric) having a high strength because it is difficult to bend and entangle the fibers, but also it is not possible to sufficiently capture the activated carbon fibers, which causes the activated carbon fibers to fall off. In addition, since the whole fibers move, a displacement between the fibers occurs, a distortion occurs inside the sheet, and a problem arises that many wrinkles are generated in the nonwoven fabric after the high-pressure columnar water jet is jetted.

Next, a method for producing an environmental purification material composed of a nonwoven fabric using activated carbon fibers will be described. First, there are a dry method and a wet method for producing a web of activated carbon fibers.The sheet obtained by the dry method has good air permeability, but the sheet formation is poor, and the activated carbon fiber is also used. The fiber breaks during the opening process, and the yield of activated carbon fibers is reduced, which is uneconomical. The sheet made by the wet method has a uniform sheet and good formation. Also, the yield of activated carbon fibers is good.

In the production method, the activated carbon fiber and the organic fiber are disintegrated with a pulper or a mixer, and dispersed in water under gentle stirring with an agitator or the like to form a uniform slurry. The slurry is made into a paper using a paper machine having at least one of a wire of a circular net, a long net or an inclined type to produce a well-formed web.

After the formed wet paper web is pressed, it is loaded on a porous support having an opening ratio of 40% or less and one opening size of 0.07 mm ² or less. Is sprayed to relatively move the high-pressure columnar water stream and the web, surround the activated carbon fibers with organic fibers, and entangle the organic fibers three-dimensionally with the activated carbon fibers interposed. As a method of relatively moving the high-pressure columnar water flow and the web, a method of rotating a conveyor-type support or a drum-type support is convenient. At this time, the carrier can be transported at a speed of 3 to 100 m / min.

Here, if the porosity of the support is greater than 40%, porosity is formed in the obtained sheet. Conversely, the smaller the aperture ratio, the better the surface quality of the obtained sheet. However, even if the aperture ratio is 40% or less, the size of one aperture is 0.005.
^On a porous support of ² mm or less, the water required for entanglement does not fall down from the support, after hitting the support, rebounds on the web again, the rebound water pushes up the web, and the web breaks A phenomenon occurs, which is not preferable.

Examples of such a porous support include wires made of metal such as stainless steel and bronze, or plastics such as reinforced polyester and polyamide in a weave method such as plain weave and twill weave.

Next, the sheet thus obtained is dried using a cylinder drier, an air drier or the like. Then, it is also possible to perform hot-press processing such as hot calender roll processing to adjust the thickness to an appropriate value.

In the above environment-purifying material, there is a method of using it as a general base paper instead of a nonwoven fabric. For example, a base paper can be made by mixing and adjusting a vegetable fiber and the above-mentioned environment-purifying fiber material on which a photoreactive semiconductor is immobilized.

Vegetable fibers are broadly classified into two types: woody cellulose fibers and herbaceous cellulose fibers.
Woody cellulosic fibers include kraft pulp, sulfite pulp, thermomechanical pulp, mechanical pulp, vascular bundle fibers such as bamboo, and bast fibers such as mulberry, goose, etc. Pulp may be used. Examples of the plant-based cellulose fibers include cotton fibers, hemp fibers, espart, and kenaf. It also includes pulp obtained from straw, waste paper and the like. Those obtained by chemically treating these vegetable fibers can also be used. At least one of these fibers can be selected and used.

In the environment-purifying material, if the fibrous carrier for immobilizing the photoreactive semiconductor is a continuous thread, it can be formed into a sheet-shaped woven fabric, which is cut and processed. Various uses are possible depending on the use such as clothing and curtains.

The third aspect of the environmental purification material comprises wallpaper obtained by applying an adhesive layer to one surface of the environmental purification material comprising the nonwoven fabric of the first or second invention.

The environmental purification material according to the first or second invention is excellent in immobilizing a photoreactive semiconductor as described above,
Although it does not fall off from the fiber and sufficiently exerts its function as a photoreactive semiconductor, it can exhibit even more effects when applied to wallpaper having a large area.

As the pressure-sensitive adhesive layer in the present invention, any of a type exhibiting tackiness upon heating and a type exhibiting tackiness at room temperature can be used. The former is preferable because it can be handled at room temperature after the application of the adhesive layer. Also,
The latter needs to be handled as a set with release paper because it has tackiness at room temperature.

The types having tackiness when heated include:
There is an adhesive layer consisting of a heat seal layer, a delayed tack layer, and a hot melt layer.

Regarding the heat seal layer, the heat seal coating agent constituting the heat seal layer is “all of converting” (published by Processing Technology Research Institute, 1993, p. 35).
This is a so-called heat seal coating agent in a narrow sense as described in 1) and is different from a solventless hot melt coating resin. For example, the constituent resin may be in the form of an organic solvent solution such as polyolefin resin, polyester, ethylene / vinyl acetate copolymer resin, polyacrylate, vinyl chloride acetate, ethylene / acrylic acid copolymer resin, or an aqueous dispersion solution. Used. A heat seal layer obtained by preparing and applying a coating liquid using this resin and drying at a temperature higher than the minimum film forming temperature is dried to a state where there is no stickiness even with a finger in a normal state. . Once heated above the melting point, the heat seal layer is plasticized and becomes tacky and can be applied to the wall with light pressure.

The heat seal layer can be applied by coating and drying as a solvent solution or emulsion.

The delayed tack layer may be formed of a resin such as an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a styrene / acrylic copolymer resin, a styrene / butadiene copolymer resin, a polystyrene resin, or the like. A polyamide resin is exemplified. The resin contains one or several crystalline (solid) plasticizers such as dicyclohexyl phthalate, diphenyl phthalate, N-cyclohexyl-p-toluenesulfonamide, o / p-toluenesulfonamide and the like. The delayed tack layer obtained by preparing a coating liquid using this resin, applying the coating liquid, and drying it at or below the melting point of the plasticizer is dried in a normal state so that there is no stickiness even when touched with a finger. Once heated above the melting point of the plasticizer, the delayed tack layer is plasticized and becomes tacky and can be applied to wall surfaces with light pressure.

For the hot melt layer, the resin constituting the same is generally a thermoplastic material (100% solid) that melts at a temperature in the range of 60 ° C. to 180 ° C. Used. Alkyd (modified polyester), asphalt and coal tar bluish blue, cumarone-indene resin,
Rosin and its derivatives, terpene resins, waxes (mineral, vegetable and petroleum), ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, polyethylene, polyvinyl acetate and its copolymers, polycarbonate, polystyrene and The copolymer, polystyrene and the copolymer, polypropylene, polyvinyl ether, polyamide, polyester (thermoplastic), phenoxy resin (plasticized), polyisoprene, polyurethane,
A resin such as a thermoplastic elastomer (SBS, SIS, SEBS, etc.) is used.

The hot melt layer can be applied as a solvent solution or as an emulsion and dried, or can be applied by hot melt extrusion.

The types having tackiness at room temperature include:
General acrylic resin, natural and synthetic rubber, styrene /
Butadiene copolymer, polyvinyl acetate, vinyl acetate / ethylene copolymer, starch, silicone compound, glue, casein, polyvinyl alcohol, polyurethane,
Polyurethane or the like can be used alone or in the form of a solution, an aqueous solution, or an emulsion.

[0086] A fourth aspect of the present invention relates to an environment-purifying material comprising a coating material mainly composed of an environment-purifying solid material obtained by fixing a photoreactive semiconductor to a solid carrier by a CVD method or a PVD method, and an adhesive. .

In the coating of the present invention, the conventional photoreactive semiconductor is treated in the form of fine particles, whereas the photoreactive semiconductor of the present invention is used as an environment-purifying solid material immobilized on a solid carrier. Can be handled by appropriately changing the particle size, and therefore, it is easy to handle even when it is applied to various substrates.

The coating material may be an aqueous type or a solvent type, and the adhesive may be changed according to the type.

Examples of the aqueous adhesive include polyvinyl alcohol, silanol-modified polyvinyl alcohol, vinyl acetate, oxidized starch, phosphated starch, etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, casein,
Gelatin, soy protein, silyl-modified polyvinyl alcohol, etc .; conjugated diene copolymer latex such as maleic anhydride resin, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer; polymers of acrylate and methacrylate Or an acrylic polymer latex such as a copolymer, a polymer or copolymer of acrylic acid and methacrylic acid; or a functional group-modified polymer latex of a functional group-containing monomer such as a carboxyl group of these various polymers; Can be used alone or in appropriate combination. In addition, the use of a known natural or synthetic resin adhesive is not particularly limited.

Examples of the solvent-based adhesive include, for example,
Ketone resin, polyamide resin, maleic acid resin, phenol resin, epoxy resin, alkyd resin, melamine resin, urea resin, nitrocellulose, ethyl cellulose,
Butyral resin and the like.

As the solvent, linseed oil, tung oil, soybean oil,
Plant solvents such as cottonseed oil, methanol, ethanol, N-
Examples thereof include alcohol solvents such as propyl alcohol, isopropyl alcohol and butanol, ester solvents such as ethyl acetate and propyl acetate, and hydrocarbon solvents such as hexane and light oil.

The characteristics of the substrate are that it has air permeability for passing harmful substances and light transmittance for activating the photoreactive semiconductor. Examples of the shape of such a base material include a cloth shape, a nonwoven fabric shape, and a porous film shape, and the nonwoven fabric shape is easy to control the basis weight and air permeability and is excellent in workability. Is particularly preferred.

As the porous film, JP-A-50-7
As described in No. 4667, an acid, an alkali or a water-elutable inorganic filler and a nonionic surfactant are mixed into a polyolefin resin, and after being formed into a film,
Stretched and then produced by dissolving the inorganic filler with an acid or the like, as described in JP-A-57-47334, comprising blending a filler and a liquid rubber with a high-density polyolefin resin. A film obtained by stretching a film obtained by melt-molding the composition can be used as appropriate.

In the coating composition of the present invention, the amount of the adhesive used is based on 100 parts by weight of the total weight of the environmental purification solid material.
The amount of the adhesive is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight. When an aqueous or non-aqueous solvent is used, it is used by appropriately changing it according to the type of the base material, and is not limited at all.

The fifth aspect of the present invention in the environmental purification material uses a glass sheet as a sheet-like carrier, and a photoreactive semiconductor is coated on the surface of the glass sheet by CVD or PV.
It was immobilized by Method D.

Conventionally, a glass sheet surface coated with titanium oxide, which is a photoreactive semiconductor, is known. However, there is room for various improvements such as selection of a suitable binder and fixing by heat treatment after coating. was there.

The environmental purification material of the present invention can solve the above problems at once, and the immobilized photoreactive semiconductor does not fall off the surface of the glass sheet at all. It can be a certain environmental purification material. Examples of this include residential windowpanes, mirrors,
Interiors include, but are not limited to.

[0098]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, of course, are not intended to limit the scope of the present invention. In addition, all percentages described in the text are percentages by weight.

Example 1 As an apparatus for producing a high-frequency plasma method for immobilizing a fibrous carrier using a photoreactive semiconductor, for example, an apparatus described in JP-A-7-242904 is used. used. The equipment includes an ultrafine material supply unit, a gas supply unit, a plasma torch, a coating material supply device, a chamber,
It consists of a coating material recovery section in which ultrafine particles are immobilized.

First, an argon gas and oxygen are supplied from a gas supply section above the plasma torch. The mixed gas of argon gas and oxygen was turned into plasma by high-frequency heating to form a plasma flame in the plasma torch. At the lower part of the plasma torch, an ultrafine particle feeder is provided,
From here, titanium oxide (manufactured by Ishihara Techno; ST-21) having an average particle diameter of 20 nm was introduced into the plasma flame together with an argon gas as a carrier gas. On the other hand, polyester fibers (Asahi Kasei; Visilon, fineness 0.15 denier, fiber length 7.5 mm) are introduced from the coating raw material supply unit. Here, the polyester fiber comes into contact with the activated titanium oxide fine particles generated in the plasma flame, and the titanium oxide is fixed on the polyester fiber surface. The polyester fiber having titanium oxide immobilized thereon was recovered from a recovery section provided at a lower portion through a chamber, and an environmental purification fiber material of Example 1 was obtained. The obtained environment-purifying fiber material was dispersed in water using a high-speed stirrer, and the immobilized state was observed. The immobilized titanium oxide was immobilized at almost half the coverage of the polyester fiber surface, and was firmly immobilized without falling off the polyester fiber surface.

Example 2 40 parts of the environment-purifying fiber material obtained in Example 1 and 60 parts of aramid fiber (manufactured by DuPont; Nomex, fineness: 2 denier, fiber length: 15 mm) were mixed with 3% of a nonionic surfactant in water. And stirred vigorously until the fiber bundle disappeared with the pulper. Then, after adding water and diluting, a 0.1% solution of high molecular weight polyacrylamide is added while gently stirring with an agitator to increase the viscosity, and stirring is continued to form an aqueous slurry. A non-woven fabric having a dry weight of 50 g / m ² was produced using a machine, and an environmental purification material of Example 2 was obtained. In the obtained environmental purification material of Example 2, no titanium oxide was dropped off from the fibrous carrier (coating material) during the manufacturing process. In addition, the material was excellent in removing pollutants as an environmental purification material.

Comparative Example 1 Hydrous titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.) as a photoreactive semiconductor
ST-31) 15 parts, polyester fiber (manufactured by Asahi Kasei; Visilon, fineness 0.15 denier, fiber length 7.5 mm)
35 parts, aramid fiber (Dupont; Nomex,
50 parts of a fineness of 2 denier and a fiber length of 15 mm) were put into water together with 3% of a nonionic surfactant, and the mixture was vigorously stirred with a pulper until the fiber bundle disappeared. Then, after adding water and diluting, a 0.1% solution of high molecular weight polyacrylamide is added while gently stirring with an agitator to increase the viscosity, and stirring is continued to form an aqueous slurry. A non-woven fabric having a dry weight of 50 g / m ² was produced using a machine to obtain an environmental purification material of Comparative Example 1. In the obtained environmental purification material of Comparative Example 1, almost no titanium oxide was discharged during the manufacturing process and was not filled between the fibers. Further, titanium oxide was easily removed from the surface of the obtained environmental purification material.

Example 3 As a fibrous carrier, the polyester fiber of Example 1 was replaced with activated carbon fiber (average fiber diameter: 15 μm, fiber length: 8 mm, specific surface area: 1,000 m ² / g), and titanium oxide was coated on the surface of the activated carbon fiber. It was immobilized to obtain an environment-purifying fiber material of Example 3. The obtained environment-purifying fiber material was dispersed in water using a high-speed stirrer, and the immobilized state was observed. The titanium oxide immobilized in the same manner as in Example 1 was firmly immobilized without falling off the activated carbon fiber surface.

Example 4 The environment-purifying fiber material obtained in Example 3 and a fiber diameter of 3.9 μm
m, polyester fiber of 7.5 mm in fiber length, compounding ratio 4
The mixture was put into water together with 3% of a nonionic surfactant, and vigorously stirred with a pulper until there was no fiber bundle. Then, after adding water and diluting, a 0.1% solution of high molecular weight polyacrylamide is added while gently stirring with an agitator to increase the viscosity, and stirring is continued to form an aqueous slurry. A nonwoven fabric using activated carbon fibers having a dry weight of 55 g / m ² as a fibrous carrier was produced using a machine.

Subsequently, the nonwoven fabric was placed on a porous support made of a 100-mesh stainless steel wire, and a water stream was jetted from the web to entangle the fibers. For confounding, two convolutions were performed on each of the front and back sides using two nozzle heads equipped with nozzles. The nozzle head has a diameter of 120 μm as a nozzle of the first head, a water pressure of 100 kg / cm ^{2 in} two rows with an interval of 1.2 mm, and a diameter of 10 as a nozzle of the second head.
0μm, water pressure 125kg / cm ^{2 in} one row with 0.6mm spacing
Were used. After the confounding, the resultant was dried with an air dryer at 100 ° C. to obtain an environmental purification material of Example 4. In the obtained environmental purification material of Example 4, no titanium oxide was dropped off from the fibrous carrier (coating material) during the manufacturing process. In addition, the material was excellent in removing pollutants as an environmental purification material.

Example 5 An adhesive (Alontack HV manufactured by Toagosei Chemical Industry Co., Ltd.) was applied to one side of the environmental purification material produced in Example 2 above.
C-3300) was applied using a roll coater so as to have a dry application amount of 25 g / m ² , dried, and then bonded to a release paper to produce wallpaper of Example 5. As a result of observing the effect of removing contaminants by attaching the obtained wallpaper to a wall surface, the effect was sufficiently exhibited.

Example 6 An adhesive (Alontack HV manufactured by Toagosei Chemical Industry Co., Ltd.) was applied to one side of the environmental purification material produced in Example 4 above.
C-3300) was applied using a roll coater so as to have a dry application amount of 25 g / m ² , dried, and then bonded to a release paper to produce wallpaper of Example 5. As a result of observing the effect of removing contaminants by sticking to the wall surface using the obtained wallpaper, it was found that the effect was more excellent than the wallpaper obtained in Example 5 by using the activated carbon fiber. .

Example 7 As the solid carrier, the polyester fiber of Example 1 was mixed with silica having an average particle diameter of 1.0 μm (trade name: Nipsil E2).
20A, manufactured by Nippon Silica Industry Co., Ltd.), and titanium oxide was immobilized on the silica surface to obtain an environmental purification solid material of Example 7. The obtained environment-purifying solid material was dispersed in water using a high-speed stirrer, and the immobilized state was observed. Example 1
The titanium oxide immobilized in the same manner as in Example 1 was firmly immobilized without falling off the silica surface.

Example 8 A paint was produced using the environmentally purified solid material produced in Example 7, and an example of its use will be described. Using polyvinyl alcohol as a dispersing agent, 25 parts of an environmental purification solid material was added to 75 parts of a 1% aqueous solution of polyvinyl alcohol to obtain an aqueous dispersion. Subsequently, 20 parts of a 25% aqueous solution containing an ethyl acrylate-methyl methacrylate copolymer as a binder was mixed with the aqueous dispersion to obtain a coating material of Example 8. The obtained paint was applied to base paper having a basis weight of 75 g / m ² using an air knife coater to obtain an environmental purification material. The obtained environmental purification material was excellent in the effect of removing pollutants.

Example 9 As a sheet-shaped carrier, the polyester fiber of Example 1 was replaced with a glass plate having a thickness of 3 mm, and titanium oxide was immobilized on the glass surface to obtain an environmental purification sheet material of Example 9. This was used as it was as the environmental purification material of Example 9. The immobilized titanium oxide does not fall off the glass surface,
It was firmly immobilized. Using the obtained environmental purification material as a window glass, the effect of removing contaminants was observed, but the effect was sufficiently exhibited.

[0111]

As described above, the environment-purifying material in which the photoreactive semiconductor of the present invention is immobilized on carriers of various shapes by the CVD method or the PVD method can be firmly immobilized on the carriers of various shapes. In addition, an environment-purifying material using the same can be an environment-purifying material that does not fall off the photoreactive semiconductor, is excellent in removing pollutants, and has excellent long-term durability.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification code FI B32B 33/00 B32B 33/00 C01G 23/04 C01G 23/04 Z C03C 17/22 C03C 17/22 Z D06M 11/46 D06M 11 / 12

Claims (10)

[Claims] 1. One of a fibrous, solid, and sheet form
An environmental purification material comprising a photoreactive semiconductor immobilized on a seed carrier by a CVD method or a PVD method. 2. The environmental purification material according to claim 1, wherein the PVD method is an RF plasma method. 3. The fibrous carrier is one of an organic fiber and an inorganic fiber.
Environmental purification material as described. 4. The environmental purification material according to claim 1, wherein the solid carrier is any one of an organic granular material, an inorganic granular material, and a metallic granular material. 5. The environmental purification material according to claim 1, wherein the sheet-shaped carrier is any one of an organic sheet, an inorganic sheet, and a metal sheet. 6. A photo-reactive semiconductor on a fibrous carrier by CVD.
An environmental purification material characterized by being a nonwoven fabric mainly composed of an environmental purification fiber material fixed by a PVD method or a PVD method. 7. The fibrous carrier according to claim 7, wherein the fibrous carrier is an environment-purifying fiber material made of activated carbon fiber, and a non-woven fabric made of the fiber material and organic fiber. An environmental purification material, wherein the fiber material is a three-dimensionally entangled nonwoven fabric. 8. An environment-purifying material according to claim 7 or 8, which is a wallpaper in which an adhesive layer is applied to one side of the environment-purifying material. 9. A photo-reactive semiconductor on a solid carrier by CVD.
An environment-purifying material comprising an environment-purifying solid material fixed by a PVD method or a PVD method and a paint mainly composed of an adhesive. 10. An environment-purifying material, wherein the sheet-like carrier is a glass sheet, and a photoreactive semiconductor is fixed on the surface of the glass sheet by a CVD method or a PVD method.