JPH11164877A - Harmful material removing agent and photocatalyst carrier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a harmful material removing agent which has characters to prompt decomposition caused by reaction of light and to prolong its effect, and which well coats the substrate and is well formed into a grain material, and to provide a photocatalyst carrier made from the harmful material removing agent which has a carrier layer with higher coating ability, adhesion, and durability to substrate such as honeycomb, etc., and prompts decomposition caused by reaction of light and prolongs its effect. SOLUTION: This harmful material removing agent contains a water swellable trioctahedral type smectite, a light reactive semiconductor, or, additionally, aluminum-containing phyllosilicate zinc, and silicate compound of the same. This photocatalyst carrier is composed of a substrate, a binder of water- swellable trioctahedral type smectite supported on the substrate, and inorganic compound layers containing a light reactive semiconductor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a harmful substance remover which is excellent in coating properties and moldability on a substrate, and has excellent decomposition promoting properties by photoreaction and excellent persistence. The present invention also relates to a photocatalyst carrier provided with a carrier layer having excellent adhesion and durability.

[0002]

2. Description of the Related Art It has long been known that a photoreactive semiconductor such as titanium dioxide is excited by light (ultraviolet light) and exhibits an excellent chemical action such as oxidizing power. It is well known to use it for decomposition removal.

[0003] For example, JP-A-1-234729 discloses an example in which a photocatalyst layer is formed on the surface of an adsorbent installed in an air conditioner, in which an anatase-type titanium dioxide photocatalyst layer is formed on an activated carbon honeycomb. Are listed.

Japanese Unexamined Patent Publication (Kokai) No. 3-157125 discloses a three-dimensional porous body (porous alumina ceramic fiber) impregnated with titania sol by dipping and drying.
It describes a deodorant which is heat-treated at 00 to 700 ° C. and carries titanium oxide.

Japanese Patent Application Laid-Open No. 7-155598 discloses that when a titanium oxide particle film is sintered on a substrate having a smooth surface such as a tile, a substance having a higher vapor pressure than titanium oxide is agglomerated between the particles. It is described that a photocatalytic film having high film strength without cracks can be obtained.

Japanese Unexamined Patent Publication (Kokai) No. 9-10582 discloses a harmful substance removing agent comprising a granulated or molded article containing titanium dioxide and bentonite (montmorillonite). An oxidizable harmful substance remover using a clay molded body to which a semiconductor having a band gap of ５5 eV is added is described.

[0007]

A photoreactive semiconductor such as titanium dioxide is generally a particle, and it is difficult to directly support it on a substrate such as a honeycomb. Therefore, it is necessary to use some kind of binder. Conventionally, as this binder, an inorganic binder such as silica sol and alumina sol, and an organic polymer binder are generally used,
These binders still have problems in coatability and adhesion to the surface of the honeycomb substrate, and have not been sufficiently satisfactory in the reactivity of the formed photocatalyst layer.

First, it is important from the viewpoint of photoreactivity that a photoreactive semiconductor is contained in a coating layer on the surface of a substrate such as a honeycomb at a high concentration. When the ratio of the reactive semiconductors becomes large, there is a problem that it is difficult to adjust the viscosity of the coating solution to an appropriate range, and that the coating solution is easily aggregated when dried.

That is, when the viscosity of the coating solution is low, solid components such as photoreactive semiconductors settle in a solution for dip coating on a substrate such as a honeycomb, or solid components flow down from the honeycomb surface during drying. On the other hand, if the viscosity is too high, dip coating itself tends to be difficult, and adjustment of the thickness of the photoreactive layer tends to be difficult.

Further, the tendency of aggregation when drying the coating liquid is also an important problem, and if aggregation occurs between the binders or between the binder and the photoreactive semiconductor, a uniform coating on the surface of the substrate such as a honeycomb is required. It becomes difficult and the adhesion of the coating is significantly reduced. These tendencies are remarkable when an inorganic binder such as silica sol is used.

Another problem is the decrease in the activity of the photoreactive semiconductor. When the surface of the photoreactive semiconductor is covered with a binder, the photoreactivity tends to decrease. This tendency is remarkable when an organic binder is used, and in the case of an organic binder, the binder itself is deteriorated by a photo-oxidation action, so that the life of the photoreactive layer is shortened.

Accordingly, an object of the present invention is to provide a harmful substance remover which is excellent in promoting decomposition by a photoreaction and its persistence, and is also excellent in coatability to a substrate and moldability to a molded article such as a granular material. To be. Another object of the present invention is to provide a photocatalyst carrier having a carrier layer excellent in coatability, adhesion, and durability to a substrate such as a honeycomb, and excellent in photoreactivity and durability.

[0013]

According to the present invention, (A)
A water-swellable trioctahedral smectite;
A harmful substance remover comprising an inorganic composition containing (B) a photoreactive semiconductor or (C) a zinc-containing aluminum phyllosilicate or a siliceous complex thereof is further provided.
According to the present invention, there is also provided a photocatalyst carrier comprising a substrate and a layer of the inorganic composition. In the present invention, 1) the (A) water-swellable trioctahedral smectite and the (B) photoreactive semiconductor are (A) :( B)
2) (C) the aluminum-containing zinc phyllosilicate or the siliceous composite thereof (C) contains 10% by weight of the components (A) and (B);
3) The (B) photoreactive semiconductor is titanium dioxide, 4) The (A) trioctahedral smectite is present in an amount of 1 to 40 parts by weight per 0 parts by weight.
Formula (1) Tx = η ₁ / η ₂ ‥‥ (1) In the formula, η ₁ is a viscosity (centipoise) of an aqueous dispersion having a sample concentration of 2% measured at a rotation speed of 6 rpm using a B-type viscometer. And η ₂ is a viscosity (centipoise) measured at 60 rpm using a B-type viscometer with respect to an aqueous dispersion having a sample concentration of 2%, and has a thixotropy index (Tx) of 3 to 3. 5) the trioctahedral smectite (A) is 5
Having a BET specific surface area of 0 to 700 m ² / g; 6) the (A) trioctahedral type smectite having an ultraviolet absorbance of 60% or less as measured at a wavelength of 400 to 250 nm. 7) that the (A) trioctahedral smectite is stevensite, hectorite, and saponite;
Is preferred. Further, in the photocatalyst carrier of the present invention, 8) a layer of an inorganic composition containing (A), (B) and / or (C) is provided in a loading amount of ^{2 to} 50 g / m ² per substrate surface area. 9) The substrate is a honeycomb; 10) Further, it is a dispersion obtained by dispersing the harmful substance removing agent comprising the above 1) to 7) in a solvent.

[0014]

[Action] The harmful substance removing agent of the present invention is characterized in that a water-swellable trioctahedral-type smectite is selected as a binder, and this is combined with a photoreactive semiconductor.

Trioctahedral (3-octahedral) type smectite is characterized in that it has water swelling properties and its dispersion exhibits thixotropic properties. Therefore, when trioctahedral type smectite is used as a binder for a photoreactive semiconductor, a high photoreactive semiconductor /
The binder ratio is also maintained at an appropriate viscosity to prevent sedimentation of the photoreactive semiconductor particles in the coating solution and run-off from the substrate.Moreover, due to the thixotropy of the dispersion, the viscosity is compared by stirring at the time of application to the substrate. It has a remarkable effect that the coating layer is kept at a very low viscosity to achieve excellent coating workability, and that the coating layer is allowed to stand still during drying, thereby increasing the viscosity and preventing the coating layer from flowing out.

As will be apparent from Examples and Comparative Examples which will be described later, among the smectite clays, trioctahedral smectite has excellent coatability and adhesion, and a dioctahedral smectite such as bentonite has a sufficient effect. Absent.

In addition, trioctahedral smectite has a high specific surface area, is excellent in adsorption properties, and has the additional advantages of increasing the efficiency of photoreaction. In other words, the reactant (hazardous substance) can be adsorbed on the trioctahedral smectite to create an environment in which the reactant is concentrated around the photoreactive semiconductor, so that the photoreaction can be performed efficiently and at a high reaction rate. It is possible to do.

Furthermore, trioctahedral smectite has an advantage that the absorbance to ultraviolet rays is smaller than that of other inorganic binders, and it is difficult to inhibit the activation of the photoreactive semiconductor by light.

The above-mentioned effects have been found as phenomena as a result of a number of experiments. The reason is not necessarily limited to the present invention in some sense, but is considered as follows. Trioctahedral smectite is a sandwiched three-layer structure MgO ₆ octahedra layer with two of SiO ₄ silica tetrahedral layer and the base layer, the base layer has a laminated structure, MgO ₆ eight A part of the face layer is isomorphically substituted with alkali metal ions or becomes vacant, or the silica SiO ₄ tetrahedral layer is isomorphously substituted with aluminum. Cations exist between the base layer layers in such a manner as to compensate for the lack of charge due to the isomorphous substitution or vacancy.

For this reason, when trioctahedral type smectite is dispersed in water, water enters between the layers of the basic layer and swells to cause a thickening action. The viscosity becomes low, and in a stationary state, a so-called card house structure is formed, and thixotropy is developed.

In trioctahedral smectite, especially synthetic trioctahedral smectite, the degree of stacking of the basic three-layer structure is small, and the dimension of the basic three-layer structure in the plane direction may be small. Therefore, it is recognized that a large specific surface area is exhibited. Furthermore, in the drying of the dispersion in which the photoreactive semiconductor coexists, the interaction of the electric charge with the photoreactive semiconductor tends to disturb the stacking of the basic three-layer structure, which also contributes to an increase in the specific surface area. Presumed.

The harmful substance removing agent of the present invention preferably contains aluminum-containing zinc phyllosilicate or a siliceous complex thereof. Aluminum-containing zinc phyllosilicate is
Has the basic structure and the octahedral layer is bonded to two layers of tetrahedral layer and the MO ₆ of SiO ₄ and AlO ₄ (M represents Zn and Al), are those the basic structure are laminated optionally The feature of these layers is that they exhibit strong adsorptivity to both basic substances and acidic substances. The aluminum-containing zinc phyllosilicate or its siliceous composite has excellent adsorption performance for various substances due to its fine basic structure and physical adsorption between layers of the multilayer structure and chemical adsorption based on each layer. It exhibits excellent action for adsorbing harmful substances and promoting its decomposition.

In summary, according to the present invention, there is provided a harmful substance which is excellent in promoting decomposition by a photoreaction and its persistence, and is excellent in moldability to a molded article such as a granular material and coating property to a substrate. A remover is provided, and the composition is excellent in applicability, adhesion, and durability to a substrate such as a honeycomb, and those having this support layer are excellent in photoreactivity and durability. Give you the advantage.

[Trioctahedral smectite] The trioctahedral smectite used in the present invention has the following formula (1) Tx = η ₁ / η ₂ (1) in terms of thixotropy. ₁ is a viscosity (centipoise) measured at a rotation speed of 6 rpm using a B-type viscometer for an aqueous dispersion having a sample concentration of 2%, and η ₂ is a B-type viscometer for an aqueous dispersion having a sample concentration of 2%. The thixotropy index (Tx), defined as the viscosity (centipoise) measured at a rotation speed of 60 rpm using the above formula, is preferably in the range of 3 to 10, particularly 6 to 8. When the thixotropy index is smaller than the above range, the adsorptivity of harmful substances is inferior, and the coating solution is easily washed out during drying. Become.

Further, the trioctahedral smectite used in the present invention has a photoreactivity of 50 to 700,
In particular, it is preferable to have a BET specific surface area of 200 to 700 m ² / g. When the specific surface area is smaller than the above-mentioned range, the harmful substance adsorbing property is inferior, and the photodegradation promoting effect cannot be obtained.

It is important from the viewpoint of photodegradability that the trioctahedral smectite has an ultraviolet absorbance of 60% or less as measured at a wavelength of 400 to 250 nm.

The trioctahedral smectite used in the present invention is not particularly limited as long as it has the above-mentioned physical properties, but is preferably stevensite, hectorite or saponite from the viewpoint of easy availability.

I) Stevensite As the Stevensite, any naturally occurring Stevensite or synthetic Stevensite can be used as long as it satisfies the above conditions. Preferred stevensites for the purposes of the present invention are synthetic stevensites whose metal component consists essentially of only magnesium, sodium and silicon, which have an X-ray diffraction peak at an interplanar spacing of 16 to 26 Angstroms with ethylene glycol treatment. Have.

A preferred synthetic stevensite is substantially the following formula (2) MgxNaySi ₄ O ₁₀ (OH) ₂ .Naz (2) where x and y are x + y <3 and x is 2 or more. Is a number, y is a number from 0 to 0.1, and z is a number from 0 to 1.0.

In the above-mentioned synthetic stevensite, the fact that the total number of atoms of Mg and Na in the layer is smaller than 3 is based on the fact that some of the Mg atoms in the MgO ₆ octahedral layer
And that the rest is vacant. Further, another part of the Mg atom may be replaced with a hydrogen atom. Some of the Mg atoms are N
a to compensate for the lack of valence charge due to the substitution with a and the remaining part of the Mg atom being vacant.
g (Na) O ₆ octahedron layer -SiO ₄ tetrahedra layer -Mg (N
a) Between the laminated layers of the basic layer structure composed of O ₆ octahedral layers,
Na ions are present.

In the above synthetic stevensite, x +
y is smaller than 3, particularly preferably 2 or more. x
Is a value of 2 or more within a range satisfying this condition,
A range from 2.6 to 2.8 is preferred. y is also a value of 0 to 0.1 within a range satisfying the above condition, and particularly preferably a range of 0 to 0.05. The value of z generally ranges from 0 to 1.0. Theoretically, the cation exchange capacity (z-
The value of α) is represented by the following formula: z−α = y + 2 (3-xy) (3) where α simply represents the number of attached Na atoms.
Is represented by

FIG. 1 shows an X-ray diffraction image of the synthesized stevensite. From FIG. 1, it can be seen that this synthetic stevensite shows an X-ray diffraction image specific to the smectite clay mineral. In addition, smectite and smectite-containing mixed layer minerals treated with ethylene glycol show X-ray bottom reflection at 16 to 26 angstroms.

Further, this synthetic stevensite has a maximum exothermic peak at 750 to 820 ° C. in differential thermal analysis. Further, this synthetic stevensite is obtained in a form containing no impurity metal component, and generally has a Hunter whiteness of 80%.
Above, especially 90% or more of white powder. Furthermore, the cation exchange capacity of this synthetic stevensite is generally 0.2
It is in the range of 0 to 1.58 milliequivalents (meq / g), especially 0.20 to 1.0 meq / g.

The synthetic stevensite has a particularly large specific surface area among trioctahedral smectites as a characteristic of a fine layered compound.
The T specific surface area is generally 300 to 600 m ² / g, especially 3
It is in the range of 50 to 550 m ² / g. FIG. 2 shows a scanning electron micrograph of the surface of the particle aggregate of the synthetic stevensite. From FIG. 2, it can be seen that the synthetic stevensite has a fine and large specific surface area.
For this reason, when synthetic stevensite is used, the effect of increasing the adsorptivity of harmful substances and promoting photodegradability is particularly large. Further, the UV absorbance of the synthetic stevensite is generally 20% or less, and among the trioctahedral smectites, the UV absorbance is particularly low, and the degree of inhibiting the photoreaction is particularly low.

Further, the synthetic stevensite swells with water to give a transparent thickening liquid, and is particularly excellent in the action as a binder and in the thixotropy imparting performance.

The above-mentioned synthetic stibsite is obtained by subjecting an aqueous mixture containing basic magnesium carbonate and sodium silicate or a combination of amorphous silica and sodium hydroxide to hydrothermal treatment.

Prior to the hydrothermal reaction, it is desirable to mix the raw materials used as uniformly as possible to form a homogenized aqueous slurry from the viewpoint of improving yield and purity. This homogenous mixing is preferably performed under strong shear stirring, and for this purpose, a high-speed shear mixer, a ball mill, a sand mill, a colloid mill, ultrasonic irradiation or the like can be used. The solids concentration in the aqueous mixture is generally in the range from 1 to 30% by weight, especially in the range from 5 to 15% by weight.

This mixture is charged into an autoclave and subjected to hydrothermal treatment. Hydrothermal treatment conditions may be relatively mild compared to conventional methods, for example, generally 100 to 3 times.
0 to 10 at a temperature of 00 ° C, especially 150 to 200 ° C.
It is preferable to carry out under a pressure of 0 kg / cm ² G (gauge), especially 6 to 40 kg / cm ² G. The reaction time is generally 0.5 to 20
An order of time is sufficient. The synthetic stevensite obtained by the reaction is solid-liquid separated from the mother liquor, washed with water and dried to obtain a product.

Ii) Hectorite As hectorite, any of hectorite produced naturally or synthetic hectorite can be used as long as it satisfies the above conditions.

The hectorite is expressed by the following equation is basically _{(4) Na 2/3 (Mg 16/3} Li 2/3) Si 8 O 20 (OH) 4-x F x ...... (4) It has a basic skeleton. Hectorite, which is usually easily obtained, contains fluorine ions.

A preferred hectorite is one in which the metal component consists essentially of magnesium, silicon, sodium and lithium, and has substantially the following formula (5): aNa ₂ O (bMgO.cLi ₂ O) [8SiO ₂ ] nH ₂ O} (5) In the formula, a, b, c and n are represented by formulas 0 <a <2, 4 <b <
This is a synthetic hectorite having a composition represented by the following formula: 6,0 <c <1 and n ≧ 2.

X-ray diffraction images of hectorite used in the present invention are shown in FIGS. FIGS. 6 and 8 show that this hectorite also shows an X-ray diffraction image specific to the smectite clay mineral.

This hectorite is also a white powder generally having a Hunter whiteness of 80% or more, particularly 90% or more, in relation to being formed only from the above-mentioned metal components.

The hectorite also has a relatively large specific surface area as a characteristic of a fine layered compound, and the BET specific surface area is generally 50 to 250 m ² /
g. For this reason, when hectorite is used, the effect of increasing the adsorptivity of harmful substances and promoting photodegradability is particularly large. Furthermore, hectorite generally has an ultraviolet absorbance of 20% or less, and has an advantage that the ultraviolet absorbance is particularly small and the degree of inhibiting the photoreaction is small.

The hectorite comprises (a) basic magnesium carbonate (4MgCO ₃ .Mg (OH) ₂ .4H ₂ O), and (b) (i)
Sodium silicate, (ii) a combination of sodium silicate and amorphous silica, (iii) a silica-sodium component selected from the group consisting of a combination of amorphous silica and sodium hydroxide, and (c) lithium hydroxide. And / or lithium carbonate at a composition ratio substantially represented by the formula (5), and the composition is synthesized by subjecting the composition to a hydrothermal treatment.

In the synthesis, it is desirable that the pH of the reaction mixture is generally in the range of 8 to 11, particularly 8.5 to 10. The pH is adjusted by adding a hydroxide or carbonate of an alkali metal to the reaction system as needed. The hydrothermal reaction is generally performed in the form of an aqueous slurry,
Solids concentration of 1 to 30% by weight, especially 5 to 15% by weight
Is advantageous in terms of operability. The hydrothermal treatment is performed by charging the above raw materials in an autoclave and heating. The reaction conditions are generally from 110 to 200
A treatment at a temperature of 0 C for 0.5 to 10 hours is sufficient. At this time, the pressure of the reaction system is maintained at 0.5 to 15.5 kg / cm ² G.

Iii) Saponite As the saponite, any of a naturally occurring saponite and a synthetic saponite can be used as long as the above conditions are satisfied.

The saponite is basically represented by the following formula (6): Na _2/3 (Mg ₆ ) (Si _2/3 Al _2/3 ) O ₂₀ (OH) _4-x F _x (6) Having a basic skeleton. Saponite
Although those containing no fluorine ions are known, those obtained practically contain almost all fluorine ions.

Saponites particularly suitable for the purposes of the present invention are:
The metal component substantially consists of magnesium, silicon, aluminum, sodium and lithium, and is substantially represented by the following formula (7): aNa ₂ O (6MgO) [bSiO ₂ · cAl ₂ O ₃ ] nH ₂ O ‥ (7) , B, c and n are represented by the expressions 0 <a <2, 6 <b <
8, a saponite having a composition represented by the following formula: c = (b-6) / 2 and n ≧ 2.

FIG. 11 shows an X-ray diffraction image of the natural saponite used in the present invention. FIG. 11 shows that this natural saponite also shows an X-ray diffraction image unique to the smectite clay mineral.

The saponite also generally has a Hunter whiteness of 8 in relation to being formed only from the above-mentioned metal components.
0% or more, especially 90% or more of white powder.

This saponite also has a relatively large specific surface area as a characteristic of a fine layered compound, and the BET specific surface area is generally 30 to 250 m ² / g.
Within the range. For this reason, when Saponite is used,
The effect of increasing the adsorptivity of harmful substances and promoting photodegradability is particularly large. Furthermore, the UV absorbance of saponite is generally 20% or less, and the UV absorbance is particularly small.
There is an advantage that the degree of inhibiting the photoreaction is small.

The saponite can be prepared by: (a) a combination of basic magnesium carbonate and (b) a combination of (i) sodium silicate, (ii) sodium silicate and amorphous silica, (iii) amorphous silica and hydroxide A silica-sodium component selected from the group consisting of sodium combinations; and (c) an alumina-sodium component selected from the group consisting of (i) sodium aluminate, (ii) sodium aluminate and amorphous alumina. Is substantially produced at a composition ratio represented by the above formula (7), and the composition is synthesized by hydrothermally treating the composition.

The pH of the reaction mixture is generally from 8 to 1
1, preferably in the range of 8.5 to 10. The pH is adjusted by adding a hydroxide or carbonate of an alkali metal to the reaction system as needed.
Prior to the hydrothermal reaction, mixing the raw materials to be used as uniformly as possible to form a homogenized aqueous slurry,
It is desirable from the viewpoint of improving yield and purity. This homogenous mixing is preferably performed under strong shear stirring, and for this purpose, a high-speed shear mixer, a ball mill, a sand mill, a colloid mill, ultrasonic irradiation, or the like can be used.

Since a small amount of sodium silicate has an effect of uniformly dispersing basic magnesium carbonate in an aqueous solution, a dispersion slurry dispersed with sodium silicate is prepared as a raw material, and the remaining raw material is added. Can also achieve the purpose of uniform mixing. The sodium silicate used in this case is desirably used in the range of 0.01 to 10% by weight based on the aqueous slurry.

The solid content concentration in the aqueous mixture is desirably in the range of generally 1 to 30% by weight, particularly preferably 5 to 15% by weight. This mixture is charged into an autoclave and subjected to hydrothermal treatment. Hydrothermal treatment conditions may be relatively mild conditions as compared with the conventional method, for example, generally 100
It is preferably carried out at a temperature of from 0 to 300 ° C., especially from 150 to 200 ° C., under a pressure of from 0 to 100 kg / cm ² G, especially from 6 to 40 kg / cm ² G. Reaction times of the order of 0.5 to 20 hours are generally sufficient.

[Photoreactive Semiconductor] In the photoreactive semiconductor used in the present invention, electron-hole pairs are generated mainly by irradiation of ultraviolet rays having a wavelength of 400 nm or less, and an odorant or the like in contact therewith is subjected to a redox reaction. Is a substance that can be decomposed by
For example, titanium oxide, tungsten oxide, zinc oxide, cerium oxide, strontium titanate, potassium niobate, and the like can be given. Among them, titanium oxide, particularly titanium oxide of the anatase type is preferred. In this case, it is considered that the strong oxidizing power of the holes is related to the deodorizing ability.

In order to further increase the oxidizing power, copper, silver, gold, zinc, vanadium, iron, cobalt, nickel, ruthenium, rhodium, copper, silver, gold, zinc, vanadium, iron, cobalt, etc. palladium,
At least one of metals such as platinum and metal oxides may be present.

These optical semiconductors are used in the form of a powder or a sol, and the primary particle diameter is preferably in the range of 5 to 50 nm. These photoreactive semiconductors can be subjected to a surface treatment with an inorganic or organic substance to such an extent that the deodorizing ability is not significantly reduced in order to improve dispersibility and insolubility.

As the inorganic material covering the surface, silica sol,
Aerosil, hydrophobic silica particles such as aerosil, calcium silicate, silicates such as magnesium silicate, calcia, magnesia, metal oxides such as titania, magnesium hydroxide, metal hydroxides such as aluminum hydroxide,
Metal carbonates such as calcium carbonate, hydrotalcite,
There are A-type, X-type, Y-type, P-type and other synthetic zeolites and fixed particles of acid-treated products or metal ion-exchanged products thereof. Organic materials include silane-based, aluminum-based, titanium-based and zirconium-based cups. A ring agent, a higher fatty acid, a metal soap or a resin acid soap, a surfactant or the like is used depending on the purpose.

[Aluminum-containing zinc phyllosilicate or siliceous composite thereof] In the present invention, the aluminum-containing zinc phyllosilicate optionally used is a tetrahedral layer of silica or silica-alumina, ZnO ₆ -AlO The octahedral layer of No. ₆ is laminated in two layers as a basic skeleton, and this basic skeleton has a structure of being laminated in the c-axis direction.

A typical aluminum-containing zinc phyllosilicate is represented by the following formula (8): (Zn _3-x Al _x ) (Si _2-x Al) O ₅ (OH) ‥ (8) It has a chemical structure represented by being a number from 1 to 1.75 and is called frypontite. Aluminum-containing zinc phyllosilicate or its siliceous composite,
It is excellent in whiteness and generally has a Hunter whiteness of 90% or more.

The aluminum-containing zinc phyllosilicate is prepared by mixing a raw material for silicic acid such as diatomaceous earth and cristobalite, a zinc raw material such as zinc oxide, and an alumina component such as boehmite gel in an aqueous solution of a water-soluble salt such as ammonium chloride. In addition,
It is manufactured by performing a hydrothermal synthesis reaction at 110 to 160 ° C. in an autoclave container.

For details of the structure, physical properties and production method of the fly-pontite type aluminum-containing zinc phyllosilicate, see JP-A-61-10021, 61-275128, and 61.
-275127.

In the present invention, it is particularly preferable to use a siliceous composite of aluminum-containing zinc phyllosilicate. More specifically, the composite comprises amorphous and porous silica or silica-alumina and an aluminum-containing zinc phyllosilicate layer formed on the surface of the primary particles.

The chemical composition as a whole is 5 to 80 mol% of SiO _{2 and} 5 to 65 mol of ZnO in a three-component composition ratio.
It is the mole%, and Al ₂ 0 ₃ 1 to 60 mol%.

The siliceous composite had substantially no peak at a plane spacing dX of 8.40 to 6.40 angstroms in X-ray diffraction, and had a plane spacing dX of 2.71 to 2.5.
6 angstroms and surface spacing dX 1.56-1.5
It has a peak at 2 Å and a specific surface area of 200
m ² / g or more, and the pore volume at a pore radius of 10 to 300 Å is 0.25 cc / g or more.

The X-ray diffraction image of this composite type aluminum-containing zinc phyllosilicate is shown in FIG. 17 of the accompanying drawings, and the particle structure thereof is shown in the scanning electron micrograph of FIG.

[Hazardous substance removing agent composition] The harmful substance removing agent of the present invention comprises (A) a water-swellable trioctahedral smectite and (B) a photoreactive semiconductor (A): (B)
= 1: 4 to 19: 1, preferably in a weight ratio of 1: 2 to 2: 1. When the content of the water-swellable trioctahedral type smectite is below the above range, the action as a binder becomes insufficient, the moldability and coatability are reduced, and the adsorptivity is also reduced, and the photodecomposition is reduced. The promoting effect also tends to decrease. On the other hand, when the content of the photoreactive semiconductor falls below the above range, the photoreactivity also decreases.

Further, (C) the aluminum-containing zinc phyllosilicate or the siliceous complex thereof is used in an amount of from 1 to 100 parts by weight based on 100 parts by weight of the total of (A) the trioctahedral smectite and (B) the photoreactive semiconductor. It is preferred to use 40 parts by weight, especially 20 to 34 parts by weight. When the amount of the aluminum-containing zinc phyllosilicate or the siliceous complex thereof is lower than the above range, the adsorption of the polar substance and the photodegradation promoting action thereby tend to be insufficient. Even if used in a large amount, there is no particular effect, and the photodegradation effect tends to be rather reduced.

The harmful substance remover composition of the present invention can be applied to various substrate surfaces and used for a photocatalyst carrier, or the composition can be granulated to form a harmful substance remover. It can also be used for applications.

In the case of a dispersion for coating a substrate, the above-mentioned harmful substance removing agent can be used by dispersing it in a solvent. As the solvent, water or an organic solvent can be used, and generally has a solid content of 0.25 to 1.5% by weight, particularly 0.5 to 1% by weight.
It is preferable to prepare an aqueous dispersion to give a percentage by weight.

[Hazardous substance removing agent and photocatalyst carrier] Examples of the substrate on which the harmful substance removing agent of the present invention is applied include molded bodies such as various honeycombs, sheets, pipes, rings, and granular materials. Honeycombs are excellent in that they have a large surface area and low pressure loss.

As the honeycomb substrate, any material having oxidation resistance may be used. For example, metal honeycombs such as aluminum, aluminum alloy, nickel, nickel alloy, steel, stainless steel and chin-free steel, alumina, zirconia , Silica, aluminum nitride, boron nitride, silicon nitride, titanium nitride, silicon carbide,
Examples include ceramic honeycombs such as boron carbide, titanium carbide, tungsten carbide, and various clay minerals.

In general, metal honeycomb structures are used in large quantities for applications such as automobile catalysts and deodorant carriers, and therefore have the advantage of being easily and inexpensively available. Metal honeycombs are easy to form and can have as thin a cell wall as possible, so that the number of cells in a unit cross-sectional area can be increased and economic efficiency is excellent. Among them, a honeycomb using aluminum is particularly preferable because of its excellent corrosion resistance.

The number of cells of the honeycomb varies depending on the honeycomb material and application, but is generally in the range of 100 to 1000 cells per unit area (in ² ), particularly in the range of 120 to 250 cells.
Is preferably within the range.

As the substrate on which the harmful substance removing agent of the present invention is supported, besides the above honeycombs, for example, glass fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, metal fiber, carbon fiber, formite group mineral Examples include sheets made of inorganic fibers such as fibers. That is, a woven fabric, a knitted fabric, a nonwoven fabric, or the like made of staple fibers or filaments of these fibers is used.

Other examples of the substrate include various inorganic particles. In general, the diameter of the inorganic particulate material is about 0.1.
It is preferably in the range of 1 to 10 mm, particularly 1 to 5 mm. Examples of the inorganic particles include glass beads, foamed glass beads, shirasu balloons, various types of zeolites or amorphous materials thereof, clay particles, granular activated carbon, and silica. Examples include beads, alumina beads, and silica-alumina beads.

The amount of the harmful substance removing agent to be carried on the honeycomb or the sheet varies depending on the use or the like, but is generally in the range of ^{2 to} 50 g / m ² , particularly 5 to 10 g / m ² per unit surface area. Is preferred. If the amount is less than the above range, the photodegradation effect is unsatisfactory in persistence. On the other hand, if the amount is more than the above range, there is no particular advantage and it is economically disadvantageous.

On the other hand, when it is carried on inorganic particulate matter,
Although it depends on the density of the granular material, generally, the granular material 10
It is preferable to support 0.1 to 100 parts by weight, particularly 1 to 10 parts by weight, per 0 parts by weight for the same reason.

The dispersion for coating is prepared as follows.
That is, water-swellable trioctahedral smectite is dispersed in water, and then the photoreactive semiconductor and, if necessary, aluminum-containing zinc phyllosilicate or a siliceous composite thereof are dispersed in the dispersion.

The dispersion is applied to the substrate by any means known per se, such as dip coating, spray coating, roll coating,
It can be performed with a doctor coat or the like. Since the harmful substance removing agent of the present invention has excellent thixotropic properties, there is an advantage that a coat layer having a constant film thickness can be surely formed by simple dip coating.

The formed support is turned into a product by drying and firing. Preferably, the final firing temperature is 250 ° C. or higher, more preferably 300 ° C. to 650 ° C., and even more preferably 300 ° C. to 450 ° C. in terms of water resistance.

As described above, the harmful substance removing agent of the present invention can be used as a harmful substance removing agent in the form of granules without being carried on a special substrate. For the production of the granular material, a granulation method known per se such as tumbling granulation, extrusion granulation, compression granulation, and spray drying granulation can be used.
Granular forms are spherical, tablet, cylindrical, prismatic,
It may be of any shape, such as a die, and its particle size may generally be in the range of 0.1 to 10 mm, especially 1 to 5 mm.

The harmful substance removing agent and the photocatalyst carrier of the present invention can be widely used for removing harmful substances in the air and water. Such harmful components include aldehydes,
Volatile hydrocarbons such as ketones, aromatic acids such as phenols, organic sulfur-containing compounds such as mercaptan, organic phosphorus compounds, organic nitrogen-containing compounds, ammonia, hydrogen sulfide, NOx
And the like.

In order to remove these harmful substances, a harmful substance remover or a photocatalyst carrier is brought into contact with a gas or liquid to be treated under irradiation of light for activating the photoreactive semiconductor. The method is not particularly limited.

The light to be applied generally has a wavelength of 400
Ultraviolet light having a wavelength of from about 200 nm to 200 nm is easily used, and a black light, a low-pressure mercury lamp, a high-pressure mercury lamp, or the like is used as a light source.

[0088]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following examples. The measuring method performed in the present example is as follows.

(1) BET specific surface area Sortomatic Series manufactured by Carlo Elba
s 1900 was used and measured by the BET method. (2) Thixotropic index and viscosity The viscosity was measured using a B-type viscometer manufactured by Toki Sangyo Co., Ltd. (3) Ultraviolet absorbance Visible ultraviolet spectrophotometer UVIDEC-6 manufactured by JASCO Corporation
The absorbance was measured using a Model 50. (4) X-ray diffraction measurement Using a RAD-IB system manufactured by Rigaku Denki,
It was measured by u-Kα. Target Cu filter Curved crystal graphite monochromator Detector SC voltage 40KV Current 20mA Count full scale 10,000c / s Smoothing point 25 Scanning speed 4 ° / min Step sampling 0.033 ° Slit DS1 ° RS0.15mm SS1 ° Illumination angle 6 ° (5 ) Scanning electron microscope observation Observation and photographing were performed using a scanning electron microscope S-570 manufactured by Hitachi, Ltd. (6) Measurement of static deodorizing ability A fixed amount of a sample was weighed in a 1.8-liter closed glass container equipped with a silicon rubber stopper for gas sampling. Next, an aldehyde gas and an ethyl mercaptan gas were respectively injected with a syringe to 50 times.
One hour after adding 0,750 ppm, the gas concentration in the container was determined by gas chromatography. (7) Measurement of dynamic deodorizing ability (adsorption capacity, decomposition rate) Each sample honeycomb (80 × 80 mm, thickness 10 mm, 12
0 cells / in ² ) were placed in a plastic container (5.5 liters). Next, aldehyde gas was injected with a syringe to 120
0 ppm was added, and the gas concentration in the container was quantified at regular intervals by gas chromatography to determine the adsorption capacity.
After one hour, black light was continuously irradiated, and the gas concentration in the container was quantified at regular intervals by gas chromatography, the adsorption capacity was determined, and the decomposition rate was calculated. (8) Measurement of expandability An appropriate amount of a coating solution was dropped on an aluminum foil and dried at 60 ° C. The state of film formation after drying was observed. The evaluation criteria were as follows. ：: Very easy to develop, a uniform and good adhesion film is formed. Δ: A film which is easy to develop and has good adhesion is formed. X: Difficult to develop, peeling is seen in the film. (9) Measurement of coating film strength An appropriate amount of the coating liquid was dropped on an aluminum plate, and a bar coater (22
After the film thickness was made constant by a mill, the sample was dried at 60 ° C. to prepare a sample. The coating strength of the obtained sample was measured by a pencil scratch value tester (load 1 kg) manufactured by Fuji Corporation. The evaluation is as follows. Hard 7H>6H>5H>4H>3H>2H>H>HB>B>2B>3B>4B>5B>6B> 7B Soft

Example 1 1 g of synthetic stevensite (ionite: 60% SiO ₂ , 30% MgO: manufactured by Mizusawa Chemical Industry) in 400 g of water and an anatase type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor )
(STS-21: manufactured by Ishihara Sangyo) 2.47 g was added, and the mixture was sufficiently stirred and mixed at room temperature to obtain a dispersion. This dispersion is
After drying at 0 ° C. for 24 hours, a white powder (sample 1-1) was obtained.
The thixotropy index, viscosity, BET specific surface area, and ultraviolet absorbance of the used synthetic stevensite are shown in Table 1, an X-ray diffraction image is shown in FIG. 1, and a scanning electron micrograph is shown in FIG.
Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 1-1. Further, the dispersion has a cell number of 250 cells / in.
^{2. A} 1-cm-thick metallic aluminum honeycomb is immersed, supported on the surface and dried at 60 ° C. for 24 hours, and then dried by a 150 ° C. constant-temperature dryer to obtain a sample honeycomb (sample 1).
-2) was obtained. Supported amount of the obtained honeycomb sample 1-2,
Table 3 shows the adsorption capacity and decomposition rate.

(Example 2) 2 g of the synthetic stevensite of Example 1 and 400 ml of water and an anatase type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor
2.47 g was added, and the mixture was sufficiently stirred and mixed at room temperature to obtain a dispersion. This dispersion was dried at 110 ° C. for 24 hours to obtain a white powder (sample 2-1). Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 2-1. Further, a metal aluminum honeycomb having a cell number of 250 cells / in ² and a thickness of 1 cm was put into the dispersion, and the honeycomb was supported on the surface and heated at 60 ° C. for 2 hours.
After drying for 4 hours, the sample was dried with a constant temperature dryer at 150 ° C. to obtain a sample honeycomb (sample 2-2). Table 3 shows the carried amount, adsorption capacity, and decomposition rate of the obtained honeycomb sample 2-2.

Example 3 1 g of the synthetic stevensite of Example 1 and 400 ml of water as an anatase type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor
4.94 g was added and sufficiently stirred and mixed to obtain a dispersion.
This dispersion was dried at 110 ° C. for 24 hours to obtain a white powder (sample 3-1). Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 3-1. Further, a metal aluminum honeycomb having a cell number of 250 cells / in ² and a thickness of 1 cm was put into this dispersion, and was carried on the surface thereof and dried at 60 ° C. for 24 hours, followed by drying at 150 ° C. constant temperature drier. A sample honeycomb (sample 3-2) was obtained. Obtained honeycomb sample 3
The supported amount, adsorption capacity, and decomposition rate of No.-2 are shown in Table 3, and the dynamic deodorizing ability is shown in FIG.

Example 4 1 g of synthetic stevensite in 400 g of water, 2.74 g of anatase-type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor, and aluminum-containing phyllosilicate-zinc silicate composite (Mizukanaito _{HP: SiO 2 50%, Al} 2 O 3 16%, Zn
O34%: manufactured by Mizusawa Chemical Industry) (0.5 g) was added and sufficiently stirred and mixed at room temperature to obtain a dispersion. 110 ° C
For 24 hours to obtain a white powder (sample 4-1). Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 4-1. Further, the dispersion has a cell number of 250 cells / i.
n ² , a 1-cm-thick honeycomb made of metallic aluminum was put, and a synthetic stevensite, anatase-type titanium oxide, and an aluminum-containing phyllosilicate-zinc silicic acid complex were supported on the surface thereof and dried at 60 ° C. for 24 hours. 150
The sample was dried by a constant temperature drier to obtain a sample honeycomb (sample 4-2). The amount of supported honeycomb sample 4-2, the adsorption capacity,
Table 3 shows the decomposition rates.

Example 5 2 g of synthetic stevensite in 400 g of water, 2.47 g of an anatase-type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor, and an aluminum-containing phyllosilicate-zinc silicate composite (Mizukanite HP: manufactured by Mizusawa Chemical Industry) 0.25 g was added,
The mixture was sufficiently stirred and mixed to obtain a dispersion. 110 ° C
For 24 hours to obtain a white powder (sample 5-1). Table 2 shows the static deodorizing ability, developability, and coating film strength of Sample 5-1. Further, the dispersion has a cell number of 250 cells / i.
n ² , a 1-cm-thick honeycomb made of metallic aluminum was put, and a synthetic stevensite, anatase-type titanium oxide, and an aluminum-containing phyllosilicate-zinc silicic acid complex were supported on the surface thereof and dried at 60 ° C. for 24 hours. 150
The sample was dried by a constant temperature drier to obtain a sample honeycomb (sample 5-2). The amount of supported honeycomb sample 5-2, the adsorption capacity,
Table 3 shows the decomposition rates.

Example 6 2 g of synthetic stevensite in 400 g of water, 1.24 g of anatase-type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor, and aluminum-containing phyllosilicate-zinc silicate composite (Mizukanite HP: manufactured by Mizusawa Chemical Industry) 0.25 g was added,
The mixture was sufficiently stirred and mixed to obtain a dispersion. 110 ° C
For 24 hours to obtain a white powder (sample 6-1). Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 6-1. Further, the dispersion has a cell number of 250 cells / i.
n ² , a 1-cm-thick honeycomb made of metallic aluminum was put, and a synthetic stevensite, anatase-type titanium oxide, and an aluminum-containing phyllosilicate-zinc silicic acid complex were supported on the surface thereof and dried at 60 ° C. for 24 hours. 150
The sample was dried by a constant temperature drier to obtain a sample honeycomb (sample 6-2). The amount of the obtained honeycomb sample 6-2 carried, the adsorption capacity,
The decomposition rate is shown in Table 3, and the dynamic deodorizing ability is shown in FIG.

(Example 7) In 400 g of water, 2 g of synthetic stevensite, g of anatase-type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor, and zinc silicate composite containing aluminum phyllosilicate (Mizukanite) (HP: manufactured by Mizusawa Chemical Industries) 0.25 g and fine powdered activated carbon
25 g was added, and the mixture was sufficiently stirred and mixed to obtain a dispersion. This dispersion was dried at 110 ° C. for 24 hours and powdered (Sample 7-1)
I got This powder was treated in the same manner as in Example 6 to obtain a sample honeycomb 7-2. The static deodorizing ability, deployability of Sample 7-1,
Table 2 shows the coating film strength. The supported amount, adsorption capacity, and decomposition rate of the obtained honeycomb sample 7-2 are shown in Table 3, and the dynamic deodorizing ability is shown in FIG.

(Examples 8 to 9) Powder samples 8-1 to 9-1 were obtained in the same manner as in Examples 3 and 6, except that the synthetic stevensite was changed to synthetic hectorite. The thixotropy index, viscosity, BET specific surface area, and ultraviolet absorbance of the used synthetic hectorite are shown in Table 1, and the X-ray diffraction image is shown in FIG. Table 2 shows the static deodorizing ability, spreadability, and coating film strength. Further, in the same manner as in Examples 3 and 6, sample honeycombs 8-2 to 9-2 were used.
I got The supported amount, adsorption capacity, and decomposition rate are shown in Table 3, and the dynamic deodorizing ability of the sample honeycomb 9-2 is shown in FIG.

(Examples 10 to 11) Powder samples 10-1 to 11-1 were obtained in the same manner as in Examples 3 and 6, except that the ionite was changed to natural hectorite. The thixotropy index, viscosity, BET specific surface area, and ultraviolet absorbance of the natural hectorite used are shown in Table 1, an X-ray diffraction image is shown in FIG. 8, and a scanning electron micrograph is shown in FIG. Table 2 shows the static deodorizing ability, spreadability, and coating film strength. Further, sample honeycombs 10-2 to 11-2 were obtained in the same manner as in Examples 3 and 6. Table 3 shows the supported amount, adsorption capacity, and decomposition rate.
FIG. 10 shows the dynamic deodorizing ability of No. 2.

(Examples 12 to 13) Powder samples 12-1 to 13-1 were obtained in the same manner as in Examples 3 and 6 except that the ionite was changed to natural saponite. The thixotropy index, viscosity, BET specific surface area, and ultraviolet absorbance of the natural saponite used are shown in Table 1, an X-ray diffraction image is shown in FIG. 11, and a scanning electron micrograph is shown in FIG. Table 2 shows the static deodorizing ability, spreadability, and coating film strength. Further, sample honeycombs 12-2 to 13-2 were obtained in the same manner as in Examples 3 and 6. Table 3 shows the supported amount, adsorption capacity, and decomposition rate.
FIG. 13 shows the dynamic deodorizing ability of No. 2.

Comparative Example 1 1 g of synthetic stevensite and 1 g of natural zeolite (average particle size: 5 μm) were added to 400 g of water, and sufficiently stirred and mixed to obtain a dispersion. This dispersion is
After drying at 10 ° C. for 24 hours, a white powder (sample 14-1) was obtained. Table 3 shows the static deodorizing ability, spreadability, and coating film strength of Sample 14-1. Further, a metallic aluminum honeycomb having a cell number of 250 cells / in ² and a thickness of 1 cm was put into the dispersion, dried on the surface at 60 ° C. for 24 hours, dried at 150 ° C., and dried at 150 ° C. to obtain a sample honeycomb ( Sample 14-
2) was obtained. Carrying amount of the obtained honeycomb sample 14-2,
Table 3 shows the adsorption capacity and decomposition rate.

(Comparative Example 2) 1 g of natural bentonite (BET specific surface area: 24 m ² / g) and 2.47 g of an anatase type titanium oxide slurry (TiO ₂ content: 40.5%) as a photoreactive semiconductor were added to 400 g of water. The mixture was sufficiently stirred and mixed at room temperature to obtain a dispersion. This dispersion was dried at 110 ° C. for 24 hours to obtain a white powder (sample 15-1). This sample 2
Table 2 shows the static deodorizing ability, developability, and coating film strength of -1.
Further, a metallic aluminum honeycomb having a cell number of 250 cells / in ² and a thickness of 1 cm was put into the dispersion, and was carried on the surface thereof and dried at 60 ° C. for 24 hours.
To obtain a sample honeycomb (sample 15-2). Table 3 shows the carried amount, adsorption capacity, and decomposition rate of the obtained honeycomb sample 15-2.

Comparative Example 3 A powder sample (sample 16-1) was obtained in the same manner as in Example 6, except that the anatase type titanium oxide slurry of Example 6 was omitted. Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 16-1. Further, a sample honeycomb 16-2 was obtained in the same manner as in Example 6. The supported amount, adsorption capacity, and decomposition rate are shown in Table 3, and the dynamic deodorizing ability is shown in FIG.

Comparative Example 4 A powder sample (sample 17-1) was obtained in the same manner as in Example 6, except that the synthetic stevensite of Example 6 was changed to polyethylene glycol (PEG20000: manufactured by Wako Pure Chemical Industries, Ltd.). Table 2 shows the static deodorizing ability, spreadability, and coating film strength of Sample 17-1. Example 6
In the same manner as in the above, a sample honeycomb 17-2 was obtained. The supported amount, adsorption capacity and decomposition rate are shown in Table 3, and the dynamic deodorizing ability is shown in FIG.
It is shown in FIG.

Comparative Example 5 The synthetic stevensite of Example 6 was replaced with natural bentonite (BET specific surface area: 24 m ² / g)
Except that the powder sample (sample 18-1) was obtained in the same manner as in Example 6. The static deodorizing ability of this sample 18-1,
Table 2 shows the developability and coating film strength. Further, a sample honeycomb 18-2 was obtained in the same manner as in Example 1. The supported amount, adsorption capacity, and decomposition rate are shown in Table 3, and the dynamic deodorizing ability is shown in FIG.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

According to the present invention, a water-swellable trioctahedral smectite is combined with a photoreactive semiconductor or, further, zinc-containing aluminum phyllosilicate or a siliceous complex thereof to produce a photoreaction. It was possible to provide a harmful substance remover which was excellent in decomposition promoting property and its persistence, and excellent in coatability to a substrate and moldability to a molded article such as a granular material. This composition can form a carrier layer having excellent coatability, adhesion, and durability to a substrate such as a honeycomb, and the carrier layer has excellent photoreactivity and durability.

[Brief description of the drawings]

FIG. 1 is a diagram showing X-ray diffraction of synthetic stevensite used in Example 1.

FIG. 2 is a scanning electron micrograph of a synthetic stevensite used in Example 1 (magnification: 5000 times).

FIG. 3 is a view showing the results of a dynamic deodorizing ability test performed in Example 3.

FIG. 4 is a view showing the results of a dynamic deodorizing ability test performed in Example 6.

FIG. 5 is a view showing the results of a dynamic deodorizing ability test performed in Example 7.

FIG. 6 is a diagram showing an X-ray diffraction of a synthetic hectorite used in Example 8.

FIG. 7 is a view showing the results of a dynamic deodorizing ability test performed in Example 9.

FIG. 8 is a diagram showing an X-ray diffraction of natural hectorite used in Example 10.

FIG. 9 is a scanning electron micrograph of a natural hectorite used in Example 10 (magnification: 5000 times).

10 is a view showing the results of a dynamic deodorizing ability test performed in Example 11. FIG.

FIG. 11 is a diagram showing an X-ray diffraction of a natural saponite used in Example 12.

FIG. 12 is a scanning electron micrograph of a natural saponite used in Example 12 (magnification: 5000 times).

13 is a view showing a result of a dynamic deodorizing ability test performed in Example 13. FIG.

14 is a view showing the results of a dynamic deodorizing ability test performed in Comparative Example 3. FIG.

FIG. 15 is a view showing the results of a dynamic deodorizing ability test performed in Comparative Example 4.

16 is a view showing the results of a dynamic deodorizing ability test performed in Comparative Example 5. FIG.

17 is a view showing an X-ray diffraction of the aluminum-containing zinc phyllosilicate siliceous composite used in Example 4. FIG.

FIG. 18 is a scanning electron micrograph of the aluminum-containing zinc phyllosilicate siliceous composite used in Example 4 (magnification: 5000 times).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Eiji Nomura 2-10-30 Fujimi, Chiyoda-ku, Tokyo Ishihara Techno Co., Ltd. Functional Materials Business Division Tokyo Business Division (72) Inventor Hiroshi Yamaguchi Ishihara, Yokkaichi-shi, Mie Prefecture No. 1 Ishihara Sangyo Co., Ltd. Yokkaichi Office

Claims (25)

[Claims] 1. A harmful substance remover comprising an inorganic composition containing (A) a water-swellable trioctahedral smectite and (B) a photoreactive semiconductor. 2. The harmful substance removing agent according to claim 1, wherein the inorganic composition further comprises (C) a zinc-containing aluminum phyllosilicate or a siliceous complex thereof. 3. The water-swellable trioctahedral smectite (A) and the photoreactive semiconductor (B) are present in a weight ratio of (A) :( B) = 1: 4 to 19: 1. The harmful substance remover according to claim 1 or 2, wherein 4. The composition according to claim 1, wherein (C) the zinc-containing aluminum phyllosilicate or the siliceous complex thereof is present in an amount of 1 to 40 parts by weight per 100 parts by weight of the total of the components (A) and (B). 2. The harmful substance remover according to 2. 5. The harmful substance removing agent according to claim 1, wherein the photoreactive semiconductor (B) is titanium oxide. 6. The (A) trioctahedral smectite is represented by the following formula (1): Tx = η ₁ / η ₂ (1) wherein η ₁ is an aqueous dispersion having a sample concentration of 2%. Is the viscosity (centipoise) measured at a rotation speed of 6 rpm using a B-type viscometer, and η ₂ was measured at a rotation speed of 60 rpm using a B-type viscometer for an aqueous dispersion having a sample concentration of 2%. The toxic substance removing agent according to any one of claims 1 to 5, wherein a thixotropy index (Tx) defined by a viscosity (centipoise) is in a range of 3 to 10. 7. The harmful substance-removing agent according to claim 1, wherein the trioctahedral smectite (A) has a BET specific surface area of 50 to 700 m ² / g. 8. The (A) trioctahedral smectite has a 60%
8. It has the following ultraviolet absorbance:
The agent for removing harmful substances according to any one of the above. 9. The agent for removing harmful substances according to claim 1, wherein the (A) trioctahedral smectite is stevensite. 10. The agent for removing harmful substances according to claim 1, wherein the (A) trioctahedral smectite is hectorite. 11. The harmful substance remover according to claim 1, wherein the (A) trioctahedral smectite is saponite. 12. A substrate and a substrate supported on the surface of the substrate.
A photocatalyst carrier comprising (A) a binder composed of water-swellable trioctahedral smectite and (B) a layer of an inorganic composition containing a photoreactive semiconductor. 13. The photocatalyst carrier according to claim 12, wherein the inorganic composition further comprises (C) aluminum-containing zinc phyllosilicate or a siliceous complex thereof. 14. The photocatalyst carrier according to claim 12, wherein the substrate is made of a honeycomb. 15. The method according to claim 12, wherein the binder (A) and the photoreactive semiconductor (B) are present in a weight ratio of (A) :( B) = 1: 4 to 19: 1. The photocatalyst carrier according to the above. 16. The method according to claim 16, wherein (C) the aluminum-containing zinc phyllosilicate or the siliceous complex thereof is present in an amount of 1 to 40 parts by weight per 100 parts by weight of the total of the components (A) and (B). Item 16. The photocatalyst carrier according to item 13 or 15. 17. The photocatalyst carrier according to claim 12, wherein the inorganic composition layer is provided in a loading amount of ^{2 to} 50 g / m ² per honeycomb surface area. 18. The photocatalyst carrier according to claim 12, wherein the photoreactive semiconductor (B) is titanium oxide. 19. The (A) trioctahedral smectite is represented by the following formula (1): Tx = η ₁ / η ₂ (1) wherein η ₁ is an aqueous dispersion having a sample concentration of 2%. Is the viscosity (centipoise) measured at a rotation speed of 6 rpm using a B-type viscometer, and η ₂ was measured at a rotation speed of 60 rpm using a B-type viscometer for an aqueous dispersion having a sample concentration of 2%. The photocatalyst carrier according to any one of claims 12 to 18, wherein a thixotropy index (Tx) defined by viscosity (centipoise) is in a range of 3 to 10. 20. The photocatalyst carrier according to claim 12, wherein the (A) trioctahedral smectite has a BET specific surface area of 50 to 700 m ² / g. 21. The (A) trioctahedral smectite having a wavelength of 400 to 250 nm,
21. The photocatalyst carrier according to claim 12, wherein the photocatalyst carrier has an ultraviolet absorbance of not more than 10%. 22. The photocatalyst carrier according to claim 12, wherein the (A) trioctahedral smectite is stevensite. 23. The photocatalyst carrier according to claim 12, wherein the (A) trioctahedral smectite is hectorite. 24. The photocatalyst carrier according to claim 12, wherein the (A) trioctahedral smectite is saponite. 25. A dispersion comprising the harmful substance removing agent according to claim 1 dispersed in a solvent.