WO2007023558A1

WO2007023558A1 - Tungsten oxide photocatalyst, process for producing the same, and fiber cloth having deodorizing/antifouling function

Info

Publication number: WO2007023558A1
Application number: PCT/JP2005/015510
Authority: WO
Inventors: Yasutaro Seto; Tatsuo Nakamura; Shuichi Yonezawa; Kazuya Nishihara
Original assignee: Suminoe Textile Co., Ltd.
Priority date: 2005-08-26
Filing date: 2005-08-26
Publication date: 2007-03-01
Also published as: JP5102034B2; JPWO2007023558A1

Abstract

A tungsten oxide photocatalyst that exhibits excellent photocatalytic activity as a visible light responsive photocatalyst, exerting satisfactory deodorizing/antifouling effects, etc. and that is available at low cost. There is provided a tungsten oxide photocatalyst characterized in that tungsten oxide is supported within the pores of an inorganic porous substance of 0.4 to 40 nm average pore diameter.

Description

Specification

Tungsten oxide photocatalyst, method for producing the same, and fiber cloth having deodorizing and antifouling function

Technical field

The present invention relates to a tungsten oxide photocatalyst that responds to visible light to exhibit a sufficient deodorizing effect and the like, and a method for producing the same.

Background art

[0002] In recent years, as represented by sick house syndrome, for example, the problem of pollution of living environment by harmful substances such as formaldehyde which is generated from housing construction materials etc. has rapidly become serious. Under these circumstances, not only formaldehyde but also persistent VOCs having an aromatic ring such as toluene or xylene are being regulated by the indoor air environment guidelines.

[0003] By the way, it is known that photocatalysts such as titanium oxide have the ability to decompose organic substances such as formaldehyde into carbon dioxide gas and water (see Patent Document 1), and such photocatalysts can be used as fiber fabrics. Various deodorant fabrics having a fixed structure have been proposed (see, for example, Patent Document 2). That is, in Patent Document 2, it is described that isovaleric acid can be deodorized by a deodorizing fabric in which a titanium oxide photocatalyst is fixed to a fiber fabric with a silicone crosslinkable resin. Patent Document 1: Japanese Patent Application Laid-Open No. 2002-282704

Patent Document 2: Japanese Patent Application Laid-Open No. 10-1879

Disclosure of the invention

Problem that invention tries to solve

[0004] While the titanium oxide photocatalyst is responsive to ultraviolet light, its photocatalytic activity under visible light is extremely low, so that it is used, for example, when it is used indoors with a small amount of ultraviolet light. Sufficient deodorizing effect can not be obtained. New photocatalysts such as nitrogen-doped titanium oxide and oxygen-deficient titanium oxide have been developed that allow this titanium oxide photocatalyst to respond on the visible light side, but advanced manufacturing technology is required to manufacture these photocatalysts. As a result, the cost is very high. In addition, oxidation as a visible light responsive photocatalyst Tungsten is known for its deodorizing performance is insufficient.

The present invention has been made in view of the strong technical background, and has excellent photocatalytic activity as a visible light responsive photocatalyst and exhibits a sufficient deodorizing'antifouling effect etc. It is an object of the present invention to provide a low cost tungsten oxide photocatalyst, a method for producing the same, and a fiber fabric that exhibits sufficient deodorizing and antifouling functions in response to visible light.

Means to solve the problem

In order to achieve the above object, the present invention provides the following means.

[1] A tungsten oxide based photocatalyst characterized in that tandastane oxide is supported in the pores of an inorganic porous material having an average pore diameter of 0.4 to 40 nm.

[2] A tungsten oxide based photocatalyst characterized in that tungsten oxide is supported on the surface and pores of an inorganic porous material having an average pore diameter of 0.4 to 40 nm.

[0009] [3] The tungsten oxide in the pores becomes a tungsten oxide by heating and calcining in a state in which a solution of a tungsten compound is contained in the pores of the inorganic porous material. The tungsten oxide based photocatalyst as described in 1 or 2 above, which is supported in the pores.

[4] The tungsten oxide based photocatalyst according to any one of the above items 1 to 3, wherein the supported amount of the tungsten oxide is 20 to 150 parts by mass with respect to 100 parts by mass of the inorganic porous material. .

[5] The tungsten oxide based photocatalyst according to the above item 3 or 4, wherein the tungsten compound is ammonium metatungstate.

[6] The tungsten oxide photocatalyst according to any one of the above items 1 to 5, wherein the inorganic porous material is a hydrophobic inorganic porous material.

[7] The tungsten oxide photocatalyst according to any one of [1] to [5], wherein the inorganic porous material is hydrophobic zeolite.

[8] [8] including a solution of a tungsten compound in pores of an inorganic porous material having an average pore size of 0.4 to 40 nm;

The tungsten compound is converted into oxidized tandasten by heating and firing in the inclusion state to support tungsten oxide in the pores of the inorganic porous material. A method of producing a tungsten oxide based photocatalyst comprising:

[9] The method for producing a tungsten oxide based photocatalyst according to the above [9], wherein an aqueous solution of ammonium metatungstate is used as the solution of the tungsten compound.

[10] The method for producing a tungsten oxide based photocatalyst according to the above 8 or 9, wherein a hydrophobic inorganic porous material is used as the inorganic porous material.

[11] The method for producing a tungsten oxide based photocatalyst according to the above 8 or 9, wherein hydrophobic zeolite is used as the inorganic porous material.

[12] The method for producing a tungsten oxide based photocatalyst according to any one of [8] to [11] above, wherein the heating temperature during the heating and firing is 250 to 1500 ° C.

[13] An oxidized tandasten-based photocatalyst produced according to the production method described in any one of [4] to [12].

[14] A deodorant characterized in that the tungsten oxide photocatalyst according to any one of the above items 1 to 7 or 13 is fixed to at least a part of a fiber fabric by a binder resin. Fiber cloth having antifouling function.

[15] Force of adhesion of the tungsten oxide photocatalyst to the fiber fabric Fiber fabric 100 parts by mass: 0.:! To 50 parts by mass, adhesion amount of the binder resin to the fiber fabric Force fiber The textile fabric which has the deodorizing and antifouling function of the preceding clause 14 which is 0.05-5 mass parts to 100 mass parts of textiles.

[16] The fiber fabric according to the above 14 or 15, wherein the binder resin is fixed to the fiber fabric in a substantially reticulated manner.

Effect of the invention

[0023] The tungsten oxide photocatalyst according to the invention of [1] and [2] has tungsten oxide supported in the pores of the inorganic porous material having an average pore diameter of 0.4 to 40 nm. The photocatalytic activity of the tungsten oxide is extremely high, so that the tungsten oxide photocatalyst exhibits a very excellent deodorizing effect, antifouling effect and the like. In addition, since oxidized tandastane is a visible light responsive photocatalyst, it exhibits sufficient deodorizing effect, antifouling effect, etc. even when used indoors with a small amount of ultraviolet light.

In the invention of [3], the tungsten oxide in the pores is a solution of a tungsten compound as an inorganic substance. Since the tungsten compound is converted into tungsten oxide and supported in the pores by heating and calcining in the state of being contained in the pores of the porous substance, it is possible to be contained in the pores of the inorganic porous substance. The supported tungsten oxide is sufficiently micronized.

In the invention of [4], since the loading capacity of tungsten oxide is 20 to 150 parts by mass with respect to 100 parts by mass of the inorganic porous material, the photocatalytic activity per unit mass of tungsten oxide is further improved. Can.

In the invention of [5], since metatungstate ammonium is used as a tungsten compound, it can be converted to tungsten oxide with sufficient conversion efficiency to prevent generation and mixing of unnecessary other compounds. It becomes a high quality tungsten oxide photocatalyst.

[0027] In the invention of [6], a hydrophobic inorganic porous material is used as the inorganic porous material, and the hydrophobic inorganic porous material is a hydrophobic strong ring, an aromatic ring such as toluene or xylene. Since it is easy to attract V 〇 C, it is possible to decompose and remove VOCs with aromatic rings such as toluene and xylene at high efficiency by oxidizing tan- dastene supported in the pores of the inorganic porous material.

In the invention of [7], hydrophobic zeolite is used as the inorganic porous material, and this hydrophobic zeolite is very easy to attract VOCs having strong aromatic rings such as toluene and xylene. Thus, the tungsten oxide carried in the pores of the inorganic porous material can decompose and remove VOCs having an aromatic ring such as toluene and xylene with higher efficiency.

[0029] In the invention of [8], the one in which tungsten oxide is supported in the pores of the inorganic porous material having an average pore diameter of 0.4 to 40 nm (tungsten oxide based photocatalyst) is efficiently produced. be able to. Since tan dustene is supported in the pores of the inorganic porous material having an average pore size of 0.4 to 40 nm, the photocatalytic activity of the tungsten oxide is extremely high, and thus the tungsten oxide photocatalyst is Demonstrates very good deodorizing effect, antifouling effect, etc. In addition, since tungsten oxide is a visible light responsive photocatalyst, it exhibits sufficient deodorizing effect, antifouling effect and the like even when it is used indoors with a small amount of ultraviolet light.

[0030] In the production method of [8], not only in the pores of the inorganic porous material but also on the surface thereof It goes without saying that those supporting tungsten oxide are also included.

In the invention of [9], since an aqueous solution of ammonium metatungstate is used as a solution of a tungsten compound, the tungsten compound can be converted to tungsten oxide with sufficient conversion efficiency, and generation of other unnecessary compounds is caused. As a result, high quality tungsten oxide photocatalyst can be manufactured.

In the invention of [10], a hydrophobic inorganic porous material is used as the inorganic porous material. Since this hydrophobic inorganic porous material easily attracts V o C having a strong hydrophobic aromatic ring such as toluene, xylene, etc., in the obtained photocatalyst, the oxidation carried by the pores of the inorganic porous material is caused. Tungsten can decompose and remove VOCs with aromatic rings such as toluene and xylene with high efficiency.

In the invention of [11], hydrophobic zeolite is used as the inorganic porous material. Since this hydrophobic zeolite is very easy to attract VOC having aromatic ring such as strong hydrophobic toluene, xylene, etc., in the obtained photocatalyst, the oxidation supported in the pores of the inorganic porous material is caused. Tungsten can decompose and remove VOCs having aromatic rings such as toluene and xylene with high efficiency.

In the invention of [12], since the heating temperature at the time of heating and firing is set to 250 to 1500 ° C., the tungsten compound can be converted to tungsten oxide with sufficient conversion efficiency.

[0035] In the invention of [13], a tungsten oxide based photocatalyst having excellent photocatalytic activity as a visible light responsive photocatalyst to exhibit sufficient deodorizing and antifouling effects and the like and at low cost is provided. Ru.

In the invention of [14], at least a part of the fiber cloth is fixed by the tungsten oxide photocatalytic activity S binder resin described in any one of the preceding items [1] to [7] or the preceding item [13]. Thus, a fiber fabric is provided that exhibits sufficient deodorizing and antifouling functions in response to visible light.

In the invention of [15], it is possible to secure a sufficient deodorizing and antifouling function while securing a good texture as a fiber fabric.

[0038] In the invention of [16], the Noinder resin is adhered to the fiber fabric in a substantially reticulated manner, whereby the fibers constituting the fiber fabric can move relatively freely. cloth Sufficient flexibility can be secured as a navel. Furthermore, it is possible to leave a space (room) as a part for imparting other functions other than deodorizing and antifouling to the fiber fabric, for example, to impart other functions such as flame retardancy, water repellency, oil repellency, etc. It is possible, and there is an advantage that further multifunctionalization can be achieved in this way.

Brief description of the drawings

FIG. 1 is a graph showing an absorption spectrum of the tungsten oxide based photocatalyst obtained in each example.

FIG. 2 is a graph showing the results of the endurance performance test of the tungsten oxide photocatalyst of the present invention.

FIG. 3 is a schematic cross-sectional view showing an embodiment of the fiber cloth according to the present invention.

Explanation of sign

[0040] 1 ... Deodorant · fiber fabric with antifouling function

2 ... Textile fabric

3 ... Tungsten oxide photocatalyst

4 Binder resin BEST MODE FOR CARRYING OUT THE INVENTION

The tungsten oxide based photocatalyst according to the present invention is obtained by supporting tungsten oxide in pores of an inorganic porous material having an average pore diameter of 0.4 to 40 nm.

Since the tungsten oxide is supported in the pores of the inorganic porous material having an average pore diameter of 0.4 to 40 nm, the photocatalytic activity of the supported tungsten oxide is extremely high, and hence the oxidation Tungsten-based photocatalysts exhibit very excellent deodorizing effects, antifouling effects, and the like. In addition, since tungsten oxide is a visible light responsive photocatalyst, the present tungsten oxide photocatalyst has a sufficient amount of deodorizing effect, antifouling effect, etc. even when it is used indoors with a small amount of ultraviolet light. Demonstrate. If the average pore size is less than 0.4 nm, or if the average pore size exceeds 40 nm, the photocatalytic activity of the supported tungsten oxide is significantly reduced. Among them, it is preferable to use a tungsten oxide based photocatalyst in which tungsten oxide is supported in the pores of the inorganic porous material having an average pore diameter of 0.5 to 30 nm. Particularly preferred are the pores of the inorganic porous material having an average pore size of 0.5 to 15 nm. It is a tungsten oxide based photocatalyst in which tungsten oxide is supported.

Tungsten oxide may be supported at a location (for example, the surface) other than the inside of the pores in the inorganic porous material. However, in the case of adopting a configuration in which the tungsten oxide based photocatalyst is fixed by a binder resin to at least a part of the fiber fabric as described later, from the viewpoint of preventing the decomposition of the binder resin by the photocatalytic action of tungsten oxide. Preferably, the amount of the tungsten oxide photocatalyst supported on the surface of the inorganic porous material other than in the pores is small or zero.

The above-mentioned tungsten oxide is not particularly limited, but may be heated and fired in a state in which a solution of a tungsten compound is contained in the pores of the inorganic porous material. It is preferable to use one in which the compound is tungsten oxide and is supported in the pores. When this configuration is adopted, tungsten oxide supported in the pores of the inorganic porous material is sufficiently micronized, which can contribute to further improvement of the photocatalytic activity.

As the tungsten oxide, one having a structure in which platinum metal such as platinum, palladium, rhodium or the like is supported to enhance its photocatalytic activity may be used, or silver or copper may be used.

It is also possible to use a configuration in which a bactericidal metal such as zinc is carried.

The inorganic porous material is not particularly limited, but it is preferable to use a hydrophobic inorganic porous material. Since this hydrophobic inorganic porous material has a good affinity for VOCs (volatile organic compounds) having aromatic rings such as toluene and xylene, and it is easy to attract VOCs having these aromatic rings, tungsten oxide There is an advantage that VOCs having aromatic rings such as toluene and xylene can be decomposed and removed with high efficiency by photocatalysis.

The hydrophobic inorganic porous material is not particularly limited. For example, hydrophobic zeolite, activated carbon, alumina porous particles whose surface is coated with a fluorine resin, porous surfaces whose surface is coated with a water repellent agent Quality silicon oxide etc. are mentioned. Among these, it is preferable to use hydrophobic zeolite. In this case, the intermediate product generated by the decomposition action of tungsten oxide (photocatalyst) can be adsorbed and captured more efficiently by this hydrophobic zeolite. In addition, since hydrophobic zeolite is white, it is advantageous in applications such as interior textiles where color and design are important. In addition, the aforementioned "hydrophobic The “organic porous material” does not include the water-absorbing inorganic porous material.

As the above-mentioned hydrophobic zeolite, it is particularly preferable to use one having a Si〇 / Al molar ratio of 30 or more. It is a hydrophobic zeolite having a Si〇 / Al 2 O molar ratio of 60 or more.

[0049] In order to obtain the hydrophobic zeolite, for example, a method of directly synthesizing a high SiZAl ratio zeolite such as silicalite, a method of removing A1 in the framework of zeolite by post-treatment, and modification of surface silanol group of zeolite Methods etc. As a method of removing A1 in the framework of zeolite by post treatment, a method of hydrothermally treating NH ⁺ -type or H ⁺ -type zeolite at a high temperature and then acid treatment, a method of directly removing A1 by acid treatment, in an aqueous EDTA solution Methods of treatment with Further, as a method of modifying the surface silanol group of zeolite, there is a method of introducing an alkyl group (hydrophobic group) by reaction with an alkylsilane or alcohol.

[0050] The average particle size of the inorganic porous material is preferably 0.05 to 30 x m. Those with a particle diameter of 0.5 μm or more are easy to manufacture and low cost, and by being 30 μm or less, for example, when applied to a fiber fabric, the texture of the fiber fabric is soft and good. It is possible to make it into a state S.

The supported amount of the tungsten oxide is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the inorganic porous material. When the amount is less than 20 parts by mass, the UV spectrum of tungsten oxide supported in the pores of the inorganic porous material is shifted to the short wavelength side (ultraviolet light region), and it has almost no absorption in the visible light region. It is not preferable because the expression of photocatalytic activity by visible light becomes insufficient. If the amount is more than 150 parts by mass, a large amount of the inorganic porous material is necessarily supported not only in the pores of the inorganic porous material but also on the outer surface, or the proportion of tungsten oxide crystallized alone increases. Since the fiber base material and the binder resin will be decomposed a lot, it is preferable. Among them, the loading amount of the tungsten oxide is more preferably 25 to 80 parts by mass with respect to 100 parts by mass of the inorganic porous material.

Next, preferred examples of the method for producing a tungsten oxide based photocatalyst according to the present invention will be described below. First, a solution of a tantalum compound is included in the pores of the inorganic porous material having an average pore size of 0.4 to 40 nm. For example, the inorganic porous material is a tungsten compound The solution of tungsten compound is included in the pores of the inorganic porous material by immersing in the solution of Examples of the solution of the tungsten compound include an aqueous solution of a tungsten compound and an alcohol solution of the tungsten compound.

At this time, although the concentration of the tungsten compound in the solution of the tungsten compound is not particularly limited, it is preferable to set in the range of 10 to 50% by mass.

The tungsten compound is not particularly limited as long as it becomes tungsten oxide by heating and firing, and examples thereof include ammonium metatungstate, tungsten ethoxide, tungstic acid, ammonium tungstate parapentahydrate, and tandust silicic acid. Hydrate, tandust silicic acid ammonium hydrate, sand dust sodium silicate hydrate, sand dust phosphoric acid hydrate, sand dust phosphoric acid ammonium hydrate, sand dust sodium phosphate hydrate, etc. It becomes tungsten oxide by heating and firing over ° C. In addition to those exemplified above, potassium tungstate, calcium tungstate, cobalt tungstate, zirconia tungstate, cerium tungstate, copper tandastate, sodium tungstate hydrate, sodium tungstate, sodium tungstate Lithium, manganese tungstate, lithium tungstate and the like, which become tungsten oxide by high-temperature firing at 1000 ° C. or higher.

Next, the inorganic porous material including the solution of the tungsten compound in the pores is heated and calcined to convert the tungsten compound into tungsten oxide, thereby supporting the tungsten oxide in the pores of the inorganic porous material. Do. In this way, a tungsten oxide based photocatalyst in which tungsten oxide is supported in the pores of the inorganic porous material is obtained.

The heating temperature at the time of the heating and firing is preferably set to 250 to 1500 ° C. By setting the temperature to 250 ° C. or higher, the tungsten compound can be converted to tungsten oxide at a sufficient conversion rate, and by setting the temperature to 1,500 ° C. or lower, the energy cost of firing can be reduced. Among them, it is particularly preferable to set the heating temperature at the time of heating and firing to 350 to: 1300 ° C.

The tungsten oxide photocatalyst of the present invention is not particularly limited to one produced by the above-described production method.

The fiber cloth (1) having a deodorizing and antifouling function according to the present invention has at least one of the fiber cloth (2) Also in part, the tungsten oxide photocatalyst (3) having the above-described structure is fixed by the binder resin (4) (see FIG. 3).

The binder resin is not particularly limited, and examples thereof include acrylic resins, urethane resins, and acrylic silicone resins.

The adhesion amount of the tungsten oxide photocatalyst to the fiber fabric is preferably from 0.:! To 50 parts by mass with respect to 100 parts by mass of the fiber fabric. When the content is 50 parts by mass or less, the texture of the fabric can be softened, and when the content is 0.1 parts by mass or more, the photocatalytic action can be sufficiently exhibited. Among them, the adhesion amount of the tungsten oxide photocatalyst to the fiber fabric is more preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the fiber fabric.

In addition, the adhesion amount of the binder resin to the fiber cloth is preferably 0.05 to 50 parts by mass with respect to 100 parts by mass of the fiber cloth. While the texture of the fabric can be made soft by being 50 parts by mass or less and sufficient fixing power can be secured by making it 0.50 parts by mass or more, the falling off of the tungsten oxide photocatalyst can be effectively prevented. can do. Among them, the adhesion amount of the binder resin to the fiber fabric is more preferably 0.15 to 20 parts by mass with respect to 100 parts by mass of the fiber fabric.

The fiber cloth (1) having a deodorizing and antifouling function of the present invention is produced, for example, as follows. That is, after a treatment liquid containing the above-mentioned tungsten oxide photocatalyst (having porous titanium oxide supported in pores of the inorganic porous material) and a binder resin is attached to at least a part of the fiber fabric, It can be manufactured by drying. The application of the treatment liquid is performed by, for example, a dipping method, a coating method, or the like.

As the immersion method, for example, after immersing the fiber cloth in a treatment liquid containing the tungsten oxide photocatalyst and the binder resin, a method of squeezing the cloth with a mundal and drying can be exemplified. If manufactured by this immersion method, there is an advantage that the tungsten oxide photocatalyst and the binder resin can be fixed to the fiber cloth in a uniform state.

An example of the coating method is a method in which a treatment liquid containing the tungsten oxide photocatalyst and binder resin is applied to at least a part of a fiber fabric and coated, and then dried. If manufactured by this coating method, productivity will be There is an advantage that it can be significantly improved and the amount of adhesion can be controlled with high accuracy. In addition, in this coating method, it is possible to bond the binder resin in a substantially mesh shape. Specific examples of the coating method include, but not particularly limited to, gravure roll method, transfer printing method, screen printing method and the like.

The proportion of each component in the treatment liquid is not particularly limited, but if the amount of the binder resin is too large with respect to the amount of the photocatalyst, the ratio of covering the surface of the photocatalyst with the binder resin increases. It is not preferable because the deodorizing and antifouling effects are reduced. The preferred content is 50 to 500 parts by mass of the tungsten oxide photocatalyst relative to 100 parts by mass of the binder resin.

[0066] In the present invention, the fiber fabric (2) is not particularly limited, and examples thereof include woven fabric, knitted fabric, non-woven fabric, napped fabric (tuffed force mesh, moquette etc.) and the like. Be Moreover, the kind, form, etc. of the fiber which comprises the said fiber fabric are not specifically limited. Examples of the fibers constituting the fiber fabric include synthetic fibers such as polyester, polyamide and acrylic, semi-synthetic fibers such as acetate and rayon, and natural fibers such as wool, silk, cotton and hemp. You may employ | adopt the structure which used 1 type or 2 types or more together. Example

Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

Example 1>

In 1 L of an aqueous solution of ammonium metatungsate at a concentration of 10% by mass, the average pore size is

An aqueous solution of ammonium metatungstate is included in the pores of the hydrophobic zeolite by immersing 200 g of hydrophobic zeolite (Si〇 / Al 2 O 3 monolith ratio: 1500) with an average particle diameter of 0.6 nm for 2 hours for 2 hours. I did. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain a tungsten oxide photocatalyst having tungsten oxide (WW) supported in the pores of hydrophobic zeolite. In the obtained tungsten oxide based photocatalyst, the loading amount of tungsten oxide with respect to 100 parts by mass of hydrophobic zeolite was 30 parts by mass. In addition, it was confirmed by ultraviolet absorption spectrum and XRD analysis (X-ray diffraction analysis) that the product (supporting material) obtained by calcination is WO. Example 2

By immersing 200 g of mesoporous silica gel having an average pore diameter of 5 nm and an average particle diameter of 10 μm for 2 hours in 1 L of an aqueous solution of ammonium tungstate having a concentration of 10% by mass, An aqueous solution of ammonium tungstate was included. Subsequently, the resultant was calcined in air at 700 ° C. for 3 hours to obtain a tungsten oxide based photocatalyst in which tungsten oxide (WO) is supported in the pores of the mesoporous silica gel. In the obtained tungsten oxide based photocatalyst, mesoporous silica gel 1

The supported amount of tungsten oxide was 00 parts by mass with respect to 00 parts by mass.

Example 3>

By immersing 200 g of mesoporous silica gel having an average pore diameter of 10 nm and an average particle diameter of 10 μm for 2 hours in 1 L of an aqueous solution of ammonium metatungstate having a concentration of 10% by mass, An aqueous solution of ammonium tungstate was included. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain a tungsten oxide based photocatalyst in which tungsten oxide (WO 3) is supported in the pores of the mesoporous silica gel. In the obtained tungsten oxide based photocatalyst, the loading amount of tungsten oxide with respect to 100 parts by mass of mesoporous silica gel was 30 parts by mass.

Example 4

By immersing 200 g of mesoporous silica gel having an average pore diameter of 30 nm and an average particle diameter of 10 μm for 2 hours in 1 L of an aqueous solution of ammonium metatungstate having a concentration of 10% by mass, An aqueous solution of ammonium tungstate was included. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain a tungsten oxide photocatalyst having tungsten oxide supported in the pores of the mesoporous silica gel. In the obtained tungsten oxide photocatalyst, the amount of tungsten oxide supported per 100 parts by mass of the mesoporous silica gel was 30 parts by mass.

Comparative Example 1>

Immerse 200 g of hydrophobic zeolite (Si Al / Al 2 O 3 ratio: 1300) with an average pore diameter of 0.3 nm for 2 hours in 1 L of an aqueous solution of ammonium tungstate with a concentration of 10% by mass. Through the pores of hydrophobic zeolites. An aqueous solution of monium was included. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain an oxidized tandasten-based photocatalyst in which tungsten oxide is supported in the pores of the hydrophobic zeolite. In the obtained tungsten oxide based photocatalyst, the amount of tungsten oxide supported was 100 parts by mass with respect to 100 parts by mass of hydrophobic zeolite.

Comparative Example 2>

By immersing 200 g of mesoporous silica gel having an average pore diameter of 50 nm and an average particle diameter of 10 μm for 2 hours in 1 L of an aqueous solution of ammonium metatungstate having a concentration of 10% by mass, An aqueous solution of ammonium tungstate was included. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain a tungsten oxide photocatalyst having tungsten oxide supported in the pores of the mesoporous silica gel. In the obtained tungsten oxide photocatalyst, the amount of tungsten oxide supported per 100 parts by mass of the mesoporous silica gel was 30 parts by mass.

Example 5

Hydrophobic zeolite (Si Al / Al 2 O 3 ratio: 1500) having an average pore diameter of 0.6 nm and an average particle diameter of 5 / im in 1 L of an aqueous solution of ammonium tungstate having a concentration of 30% by mass 246

2 2 3

An aqueous solution of ammonium metatungstate was incorporated into the pores of the hydrophobic zeolite by soaking the g for 2 hours. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain an oxidized tandasten-based photocatalyst in which tungsten oxide is supported in the pores of the hydrophobic zeolite. In the obtained tungsten oxide based photocatalyst, the amount of tungsten oxide supported was 100 parts by mass with respect to 100 parts by mass of hydrophobic zeolite.

Example 6

Hydrophobic zeolite (Si Si / Al 2 O 3 ratio: 1500) with an average pore size of 0.6 nm and an average particle size of 1 in 1 L of an aqueous solution of ammonium tungstate with a concentration of 70% by mass 210

2 2 3

An aqueous solution of ammonium metatungstate was incorporated into the pores of the hydrophobic zeolite by soaking the g for 2 hours. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain an oxidized tandasten-based photocatalyst in which tungsten oxide is supported in the pores of the hydrophobic zeolite. In the obtained tungsten oxide based photocatalyst, the supported amount of tungsten oxide was 70 parts by mass with respect to 100 parts by mass of hydrophobic zeolite. Example 7

Immerse 270 g of hydrophobic zeolite (SiO 2 / Al 2 O 3 monolith ratio is 1500) with an average pore diameter of 0.6 nm and an average particle diameter of 5 / im for 2 hours in 1 L of an aqueous solution of ammonium tungstate with a concentration of 3% by mass Thus, an aqueous solution of ammonium metatungstate was incorporated into the pores of the hydrophobic zeolite. Next, the resultant was calcined in air at 700 ° C. for 3 hours to obtain an oxidized tandasten-based photocatalyst in which tungsten oxide is supported in the pores of the hydrophobic zeolite. In the obtained tungsten oxide based photocatalyst, the amount of tungsten oxide supported was 100 parts by mass with respect to 100 parts by mass of hydrophobic silica.

The UV absorption spectrum of the tungsten oxide based photocatalyst obtained in Examples 1, 5 and 7 is shown in FIG. It can be seen from FIG. 1 that as the amount of tungsten oxide supported in the pores increases, the absorption in the visible light region increases and the resorption increases.

The decomposition performance of each tungsten oxide based photocatalyst obtained as described above was evaluated according to the following test method. The results are shown in Table 1.

[0079] [Table 1]

(Acetaldehyde decomposition)

Tungsten oxide photocatalyst was placed in a bag with a content of 5 L so that the amount of tungsten oxide was 0.2 g, and then acetaldehyde gas was injected into the bag so that the concentration was 200 ppm. . After leaving in a place for 3 hours after injection, place this bag 30 cm immediately below the fluorescent lamp (using a UV cut filter to cut wavelengths shorter than 390 nm, illuminance lux: lux), and after 4 hours The amount of carbon dioxide gas generated by the decomposition of aldehyde was measured, and based on this, the amount of carbon dioxide gas generated per hour was measured.

(Tonoreen's minute horn)

After putting the tungsten oxide photocatalyst into the bag with a content of 5 L so that the amount of tungsten oxide is 0.2 g, toluene gas is injected into the bag so that the concentration becomes 200 ppm. After leaving in a place for 3 hours after injection, place this bag 30 cm directly under a fluorescent lamp (using UV cut filter with a wavelength shorter than 390 nm, illuminance 6,000 norethex), and after 4 hours, use toluene The amount of carbon dioxide gas generated by the decomposition of the carbon dioxide was measured, and the amount of carbon dioxide gas generated per hour was measured based on this.

As apparent from Table 1, the tungsten oxide photocatalysts of Examples 1 to 7 according to the present invention were able to exhibit excellent decomposition performance with respect to acetaldehyde and toluene under visible light irradiation.

On the other hand, in the photocatalyst of Comparative Example 1 in which oxidized tandasten is supported in the pores of the inorganic porous material having an average pore diameter of 0.3 nm, the decomposition performance is insufficient under visible light irradiation. Met. In addition, the photocatalyst of Comparative Example 2 in which oxidized tungsten is supported in the pores of the inorganic porous material having an average pore diameter of 50 nm also has insufficient decomposition performance under visible light irradiation.

Next, with respect to the tungsten oxide photocatalyst of Example 5, a durability test (repeated test) was performed. The results are shown in Figure 2. This endurance performance test was conducted as follows. That is, after putting the tungsten oxide type photocatalyst obtained in Example 5 into a bag with an inner volume of 5 L so that the amount of tungsten oxide is 0.2 g, the concentration in the bag will be 200 ppm. Cetaldehyde gas was injected. After leaving in a place for 3 hours after injection, this bag was placed directly on a fluorescent lamp (using a UV cut filter to cut wavelengths shorter than 390 nm, illuminance of 6000 lux). Lower position Positioned at 30 cm, under this light irradiation state, while measuring acetaldehyde gas concentration and carbon dioxide concentration every unit time, the concentration in the bag was newly set at 200 ppm after 54 hours and 94 hours. Acetoaldehyde gas was injected to achieve

As apparent from the graph of FIG. 2, even when the repeated test is conducted, the degradation performance of the oxidized tandasten-based photocatalyst of the present invention is excellent in the durability of the degradation performance without any deterioration. I understand.

Example 8>

After 10 parts by mass of the tungsten oxide based photocatalyst of Example 1 was mixed with 84 parts by mass of water, the mixture was sufficiently stirred by a stirrer to obtain a dispersion. 6 parts by mass of an acrylic resin (solid content: 50% by mass) was added to the dispersion, and the mixture was sufficiently stirred to obtain a uniform dispersion treatment liquid. A polyester spunbond non-woven fabric (40 g / m ² basis weight) is dipped in this dispersion treatment solution, taken out, squeezed with a mandarin, and dried to obtain a fiber fabric having a deodorizing and antifouling function (Fig. 3 Reference) got. The adhesion amount of the tungsten oxide photocatalyst to the fiber fabric was 3 parts by mass with respect to 100 parts by mass of the fiber fabric. In addition, the adhesion amount of the binder resin to the fiber cloth was 1 part by mass with respect to 100 parts by mass of the fiber cloth.

Example 9

In the same manner as in Example 8 except that the tungsten oxide photocatalyst of Example 2 was used as the tungsten oxide photocatalyst, a fiber cloth having a deodorizing and antifouling function was obtained.

Example 10

In the same manner as in Example 8 except that the tungsten oxide photocatalyst of Example 3 was used as the tungsten oxide photocatalyst, a fiber cloth having a deodorizing and antifouling function was obtained.

Example 11

A fiber cloth having a deodorizing and antifouling function was obtained in the same manner as in Example 8 except that the tungsten oxide photocatalyst of Example 4 was used as the tungsten oxide photocatalyst.

Comparative Example 3>

A fiber cloth having a deodorizing and antifouling function was obtained in the same manner as in Example 8 except that the tungsten oxide photocatalyst of Comparative Example 1 was used as the tungsten oxide photocatalyst.

Comparative Example 4> In the same manner as in Example 8 except that the tungsten oxide photocatalyst of Comparative Example 2 was used as the tungsten oxide photocatalyst, a fiber cloth having a deodorizing and antifouling function was obtained.

The respective fiber fabrics obtained as described above were evaluated for degradation performance according to the following test method. The results are shown in Table 2.

[Table 2]

The test pieces (10 × 10 cm square) cut out from each fiber cloth were placed in a bag having an inner volume of 5 L, and then acetaldehyde gas was injected so that the concentration was 200 ppm in the bag. After leaving in the same place for 3 hours after injection, place this bag 30 cm directly under a fluorescent lamp (using a UV cut filter to cut wavelengths shorter than 390 nm, illuminance lux: lux), and after 4 hours pass acetate aldehyde The amount of carbonic acid gas generated by the decomposition of the binder resin (including the decomposition of the binder resin) was measured, and based on this, the amount of carbon dioxide gas generated per hour (X) was measured.

Similarly, in the case of a system in which the atmosphere in the bag is only air (containing no acetate aldehyde gas), the amount of carbon dioxide gas generated per hour (the amount of carbonic acid gas generated by the decomposition of the binder resin) Y) was measured. Therefore, the amount of carbon dioxide gas generation derived from the decomposition of acetaldehyde was calculated by (X-Y).

As is clear from Table 2, the deodorant / antifouling fiber fabric of Examples 8 to 11 of the present invention exhibits excellent decomposition performance to acetaldehyde under visible light irradiation. did it.

On the other hand, in the fiber fabrics of Comparative Examples 3 and 4, the degradation performance was insufficient under visible light irradiation.

From Table 2, in the fiber fabric of Examples 8 to 11 using the tungsten oxide photocatalyst produced according to the production method of the present invention, the binder resin is hardly decomposed by the photocatalyst substantially. The On the other hand, it was found that the binder resin was decomposed by the photocatalyst in the fiber fabric of Comparative Example 3 using the tungsten oxide photocatalyst produced by using an inorganic porous material with an average pore diameter of 0.3 nm.

The terms and explanations used herein are used to explain the embodiments of the present invention, and the present invention is not limited thereto. This invention tolerates any design change within the scope of the claims unless it deviates from the spirit of the invention.

Industrial applicability

The tungsten oxide photocatalyst according to the present invention is not particularly limited, but examples are For example, it is used as a deodorant, an antibacterial agent, a sterilizer, an antifouling agent, a waste water treatment agent, a water purification treatment agent and the like.

The fiber cloth having deodorizing and antifouling functions according to the present invention is not particularly limited. For example, carpets, curtains, wallpaper, interior cloths such as upholstery, ceiling materials, etc. Automobiles, vehicles, ships And textile fabrics for interiors such as aircraft, or as clothes.

Claims

The scope of the claims

[I] A tungsten oxide based photocatalyst characterized in that tungsten oxide is supported in pores of an inorganic porous material having an average pore diameter of 0.4 to 40 nm.

[2] A tungsten oxide based photocatalyst characterized in that tungsten oxide is supported on the surface and pores of an inorganic porous material having an average pore size of 0.4 to 40 nm.

[3] Tungsten oxide in the pores is converted into tungsten oxide by heating and baking in a state in which a solution of a tungsten compound is included in the pores of the inorganic porous material, and the tungsten oxide is converted into the pores. The tungsten oxide photocatalyst according to claim 1 or 2, which is supported.

[4] The supported amount power of the tungsten oxide The present invention is 20 to 150 parts by mass with respect to 100 parts by mass of the inorganic porous material, The tungsten oxide based optical catalyst according to any one of claims 1 to 3.

[5] The tungsten oxide based photocatalyst according to claim 4 or 5, wherein the tungsten compound is ammonium metatungstate.

[6] The tungsten oxide photocatalyst according to any one of claims 1 to 5, wherein the inorganic porous material is a hydrophobic inorganic porous material.

[7] The tungsten oxide photocatalyst according to any one of claims 1 to 5, wherein the inorganic porous material is hydrophobic zeolite.

[8] including a solution of a tungsten compound in pores of the inorganic porous material having an average pore size of 0.4 to 40 nm,

A step of converting the tungsten compound into oxidized tandasten by heating and calcining in the inclusion state, and supporting tungsten oxide in the pores of the inorganic porous material. Manufacturing method.

[9] The method for producing a tungsten oxide based photocatalyst according to claim 8, wherein an aqueous solution of ammonium metatungstate is used as the solution of the tungsten compound.

[10] The method for producing a tungsten oxide based photocatalyst according to claim 8 or 9, wherein a hydrophobic inorganic porous material is used as the inorganic porous material.

[II] The acid according to claim 8 or 9, wherein hydrophobic zeolite is used as the inorganic porous material. Method of producing tungsten carbide based photocatalyst.

[12] The method for producing a tungsten oxide based photocatalyst according to any one of claims 8 to 11, wherein a heating temperature at the time of the heating and firing is 250 to 1500 ° C.

[13] An oxidized tandastane-based photocatalyst produced by the production method according to any one of [4] to [12].

[14] A deodorant and anti-deodorant characterized in that the tungsten oxide photocatalyst according to any one of claims 1 to 7 is fixed to at least a part of a fiber fabric by a binder resin. Fiber cloth having a stain function.

[15] The adhesion amount of the tungsten oxide photocatalyst to the fiber fabric is 0.:! To 50 parts by mass with respect to 100 parts by mass of the fiber fabric, and the adhesion amount of the binder resin to the fiber fabric. The fiber cloth having a deodorizing and antifouling function according to claim 14, which is 0.05 to 50 parts by mass with respect to the mass part.

[16] The fiber fabric having a deodorizing and antifouling function according to claim 14 or 15, wherein the binder resin is fixed to the fiber fabric in a substantially reticulated manner.