JP2012096152A - Photocatalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocatalyst which is excellent in sterilization speed because of improved antimicrobial activity especially under visible light irradiation and further is excellent in harmful gas decomposition speed.SOLUTION: The photocatalyst comprises a first catalyst component and a second catalyst component. The first catalyst component carries 2.8 to 15 parts mass of antimicrobial activity metal species expressed in terms of metal atom with respect to a first titanium oxide compound, wherein content of titanium atoms constituting the first titanium oxide compound is 100 parts mass. The second catalyst component carries 0 to 1.5 parts mass of the antimicrobial activity metal species expressed in terms of metal atom with respect to a second titanium oxide compound, wherein content of titanium atoms constituting the second titanium oxide compound is 100 parts mass.

Description

  The present invention relates to a photocatalyst.

  Titanium oxide has long been used as a white pigment, and in recent years, it has been widely used as a sintering material used in electronic materials such as UV shielding materials for cosmetics, photocatalysts, capacitors, thermistors, and barium titanate materials. In particular, in recent years, the use as a photocatalyst has been actively attempted, and the use development of the photocatalytic reaction has been actively performed.

  This titanium oxide photocatalyst has a wide variety of uses. Generation of hydrogen by water decomposition, synthesis of organic compounds using redox reaction, exhaust gas treatment, air purification, deodorization, sterilization, antibacterial, water treatment, lighting. Numerous applications have been developed, such as preventing contamination of equipment.

  However, since titanium oxide shows a large refractive index in the wavelength region near visible light, light absorption hardly occurs in the visible light region. Considering the use under fluorescent lamps indoors, the light of fluorescent lamps is mostly visible light waves with a spectrum of 400 nm or more and cannot exhibit sufficient characteristics as a photocatalyst. Therefore, it is desired to develop a photocatalyst with higher availability that can exhibit the catalytic activity of

  In particular, in an aging society, the demand for antibacterials in facilities considering elderly people with weak resistance, or the need for antibacterial infections in hospitals is increasing. In addition, from the viewpoint of global environmental conservation, environmentally friendly antibacterial materials with low toxicity and high safety have been demanded.

  In addition, as the airtightness of buildings progresses, the number of structures with poor ventilation is increasing, and therefore the increase in indoor air pollution is becoming a problem. Demand for improving air cleanliness and eliminating odors in public facilities such as hotels and toilets is also increasing year by year.

  In response to these demands, in the prior art, a paint containing an organic or inorganic sterilizing agent having a strong sterilizing power is applied to indoor walls or the like, or VOC (volatile organic compound) gas is used. In some cases, paints are used in which these disinfectants are loaded on a carrier that has the ability to adsorb odor gases.

  However, organic germicides are highly toxic and have a safety problem, and inorganic germicides have a problem that they are not effective due to the generation of resistant bacteria to the germicidal component. Furthermore, even when these conventional antibacterial agents are sterilized, the problem that the toxins and dead bodies of the bacteria remain cannot be solved. Further, the effect of the carrier adsorption capacity for VOC gas is limited.

  On the other hand, pure titanium oxide exhibits antibacterial action, air cleaning action, and deodorizing action due to the photocatalytic effect under ultraviolet light irradiation, but high demand is expected for the above-mentioned elderly facilities, hospitals, hotels, toilets, etc. Since most of the usage environments are indoor environments with little ultraviolet light, conventional titanium oxide cannot exhibit the expected effects.

  Therefore, the present applicant has developed a highly usable titanium oxide photocatalyst that can exhibit catalytic activity as a photocatalyst even with light from an indoor fluorescent lamp.

  For example, the applicant of the present invention is a titanium oxide compound in which a sulfur atom is introduced into a titanium site, and a titanium oxide compound in which a metal species such as an iron compound is incorporated into a sulfur atom-introduced titanium oxide (hereinafter referred to as “iron compound-containing sulfur atom-introduced titanium oxide compound” (Refer to Patent Document 1).

  When this iron-containing sulfur atom-introduced titanium oxide compound is applied to or coated on indoor building materials or walls, it exhibits antibacterial, air-cleaning and deodorizing effects even under fluorescent light irradiation, It can also break down toxins and dead bacteria, and its effects can last as long as there is no physical detachment.

  However, under the objectives of antibacterial, deodorant, and air purification, it is required that the effect be manifested as soon as possible, and those that can achieve further superior sterilization rates and harmful gas decomposition rates than conventional ones. Further, there is a demand for a photocatalyst that is excellent in the sterilization rate and the harmful gas decomposition rate, and that can exhibit antibacterial, deodorizing, and air cleaning effects at a high level.

International Publication No. 2008/081957

  Under such circumstances, an object of the present invention is to provide a photocatalyst which has an improved antibacterial activity and an excellent sterilization rate and an excellent harmful gas decomposition rate, particularly under visible light irradiation.

In order to solve the above technical problems, the present inventor conducted intensive studies and found that antibacterial active metal species such as a copper compound and a silver compound (antibacterial) against a titanium oxide compound such as an iron compound-containing sulfur atom-introduced titanium oxide compound. It has been found that by carrying a predetermined amount of the active metal compound), the sterilization rate is remarkably improved by the synergistic effect of the antibacterial effect of the active metal species and the photocatalytic effect of the titanium oxide compound. However, when the amount of the antibacterial active metal species supported exceeds a certain level, the surface of the titanium oxide compound covered with the antibacterial active metal species increases, and visible light is absorbed by the antibacterial active metal species. It has been found that the photocatalytic effect of the titanium oxide compound decreases, for example, the harmful gas decomposition rate decreases.
Based on the above findings, the present inventors have further investigated, and as a result, a photocatalyst comprising a first catalyst component and a second catalyst component, each having a different amount of antibacterial active metal species supported on the titanium oxide compound. The present inventors have found that the above technical problem can be solved and have completed the present invention.

That is, the present invention
(1) A photocatalyst comprising a first catalyst component and a second catalyst component,
When the content of titanium atoms constituting the first titanium oxide compound is 100 parts by mass with respect to the first titanium oxide compound, the first catalyst component converts the antibacterial active metal species in terms of metal atoms. 2.8 to 15 parts by mass supported,
When the content of titanium atoms constituting the second titanium oxide compound is 100 parts by mass with respect to the second titanium oxide compound, the second catalyst component converts the antibacterial active metal species in terms of metal atoms. 0 to 1.5 parts by weight of a supported photocatalyst,
(2) When the total content of the first titanium oxide compound and the second titanium oxide compound is 100% by mass,
The content of the first titanium oxide compound is 7.5 to 72% by mass,
The photocatalyst according to (1) above, wherein the content of the second titanium oxide compound is 28 to 92.5% by mass,
(3) When the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The photocatalyst according to (1) or (2) above, wherein the total amount of the antibacterial active metal species
(4) The first titanium oxide compound or the second titanium oxide compound is sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, sulfur atom-introduced titanium oxide containing an iron compound or nitrogen-introduced oxidation containing an iron compound In the photocatalyst according to any one of the above (1) to (3), which is titanium, and (5) the first catalyst component or the second catalyst component, the antibacterial active metal species is a copper compound, a silver compound and a metal The photocatalyst according to any one of the above (1) to (4), which is at least one selected from silver;
Is to provide.

The photocatalyst of the present invention comprises a first catalyst component and a second catalyst component having different loadings of antibacterial active metal species. The photocatalytic action and the action that inhibits the metabolic function of bacteria (mainly the antibacterial action of active metal species) function efficiently as a synergistic effect, so it is particularly visible compared to the photocatalyst that uniformly supports the antibacterial active metal compound. Under light irradiation, the antibacterial activity is improved and bacteria can be completely sterilized in a shorter time, and the harmful gas decomposition performance (photocatalytic action of titanium oxide) can be functioned without being greatly impaired.
For this reason, according to the present invention, it is possible to provide a photocatalyst which has an improved antibacterial activity and an excellent sterilization rate and an excellent harmful gas decomposition rate, particularly under visible light irradiation.

It is a figure which shows the antibacterial performance evaluation result of the photocatalyst obtained by the Example and comparative example of this invention. It is a figure which shows the harmful gas decomposition | disassembly performance evaluation result of the photocatalyst obtained by the Example and comparative example of this invention. It is a figure which shows the antibacterial performance evaluation result of the photocatalyst obtained by the Example and comparative example of this invention.

  The photocatalyst of the present invention is a photocatalyst comprising a first catalyst component and a second catalyst component, wherein the first catalyst component is a first titanium oxide compound with respect to the first titanium oxide compound. When the content of titanium atoms constituting the compound is 100 parts by mass, the antibacterial active metal species is supported by 2.8 to 15 parts by mass in terms of metal atoms, and the second catalyst component is When the content of titanium atoms constituting the second titanium oxide compound is 100 parts by mass with respect to the second titanium oxide compound, 0 to 1.5 parts by mass of the antibacterial active metal species in terms of metal atoms is supported. It is characterized by being made.

(Titanium oxide compound)
The photocatalyst of the present invention comprises a first catalyst component and a second catalyst component. The first catalyst component and the second catalyst component are the first titanium oxide compound and the second catalyst component, respectively. The titanium oxide compound is included.
In the present invention, the first titanium oxide compound and the second titanium oxide compound may be the same or different.

In the present invention, as the first titanium oxide compound or the second titanium oxide compound, specifically, titanium oxide such as rutile type titanium oxide, anatase type titanium oxide, brookite type titanium oxide, sulfur atom-introduced titanium oxide, nitrogen, etc. Atom-introduced titanium oxide, carbon-atom-introduced titanium oxide, phosphorus-atom-introduced titanium oxide, etc. In titanium oxide, iron compounds such as Fe ₂ O ₃ and Fe ₃ O ₄ , WO ₃ , V ₂ O ₅ , Bi ₂ O ₃ , Nb ₂ O ₃ , ZnO, ZrO ₂ , PtO ₂ , PdO, In ₂ O ₃ , PbO, FeTiO ₃ , SrTiO ₃ , BaTiO ₃ , CaTiO ₃ , KTaO ₃ , SnO ₂ , MnO ₂ , from a group consisting of metal compounds such as Cr ₂ O ₃ , Co ₃ O ₄ , Y ₂ O ₃ , Mo ₂ O ₃ , and Cr, V, Cu, Fe, Mg, Ag, Pd, Ni, Mn, and Pt It may contain one or more selected metal ions. Among these titanium oxide compounds, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, sulfur atom-introduced titanium oxide containing an iron compound, or nitrogen-introduced titanium oxide containing an iron compound is preferable.

(Titanium oxide)
When the first titanium oxide compound or the second titanium oxide compound is a titanium oxide such as a rutile type titanium oxide or an anatase type titanium oxide, in this application document, the rutile type titanium oxide is a rutile type in the formula described below. It means titanium oxide having a conversion rate of 90% or more, and anatase titanium oxide means titanium oxide having a rutile conversion rate of 10% or less in the formula described below.

Further, in the present application documents, the rutile ratio is measured by X-ray diffraction according to the method of ASTM D3720-84, the peak area (Ir) of the strongest diffraction line (surface index 110) of rutile-type crystalline titanium oxide, The peak area (Ia) of the strongest diffraction line (surface index 101) of the crystalline titanium oxide is obtained, and it is obtained by the following formula.
Rutile conversion rate (%) = 100-100 / (1 + 1.2 × Ir / Ia)
In the formula, the peak area (Ir) and the peak area (Ia) indicate the area of the portion protruding from the base line in the corresponding diffraction line of the X-ray diffraction spectrum, and the calculation may be performed by a known method. Techniques such as computer calculation and approximate triangulation can be used.

When the first titanium oxide compound or the second titanium oxide compound is a titanium oxide such as a rutile type titanium oxide or an anatase type titanium oxide, as a method for producing a rutile type titanium oxide or an anatase type titanium oxide,
(1) A method of reacting a titanium salt with an alkali compound in the presence of chloride ions or hydrolyzing the titanium salt,
(2) A method of oxidizing or hydrolyzing titanium chloride gas in a gas phase can be mentioned.

  In the case of producing titanium oxide by a method in which (1) the titanium salt is reacted with an alkali compound in the presence of chloride ions or the titanium salt is hydrolyzed, examples of the titanium salt include organometallic compounds such as titanium alkoxide. Or, inorganic salts such as titanium chlorides such as titanium tetrachloride and titanium trichloride, and sulfates such as titanyl sulfate and titanium sulfate can be used. Of these, titanium tetrachloride, titanyl sulfate, and titanium sulfate are preferable as the titanium salt in view of handling and economy.

  When preparing titanium oxide by reacting a titanium salt with an alkali compound, the alkali reaction of the titanium salt is carried out by preparing an aqueous solution in which the titanium salt is dissolved in water and mixing the alkali while stirring the aqueous solution. And the method of making the said titanium salt and an alkali contact is mentioned.

Specifically, for example,
(Alkali reaction method 1) A method of dropping an aqueous alkali solution into an aqueous solution of a titanium salt and bringing them into contact with each other,
(Alkali reaction method 2) A method of dropping an aqueous solution of titanium salt into an aqueous solution of alkali and bringing them into contact with each other,
(Alkaline reaction method 3) A method in which water whose pH is adjusted is put in a reaction vessel, and an aqueous solution of a titanium salt and an aqueous solution of an alkali are dropped therein, and both are brought into contact with each other.
Can be mentioned.

The alkali is not particularly limited, and examples thereof include ammonia and aqueous ammonia. Among these, ammonia or ammonia water is preferable for controlling the photocatalytic activity of the obtained titanium oxide in the visible light region because it does not contain a metal component.
In the alkali reaction method 1 to alkali reaction method 3, the reaction temperature is preferably −5 to 80 ° C., more preferably 0 to 60 ° C. When the reaction temperature is less than 0 ° C., the reaction hardly occurs. When the reaction temperature exceeds 60 ° C., it becomes difficult to obtain an alkaline reactant having a small average particle size and a large specific surface area.

  The rutile rate of the resulting titanium oxide can be controlled by the time or rate of hydrolysis or alkali neutralization of the aqueous titanium chloride solution. For example, when neutralizing a titanium tetrachloride aqueous solution with ammonia water, etc., neutralization in a short time yields titanium oxide with a low anatase-rich rutile ratio, and slowing the neutralization reaction results in an oxidation with a high rutile ratio. Titanium can be obtained. Moreover, the rutile ratio of titanium oxide obtained can also be controlled by the pH of the reaction system when neutralizing or hydrolyzing the aqueous titanium chloride solution. For example, after titanium oxide powder is precipitated, the aging reaction is performed in a low pH atmosphere. As a result, the rutile ratio is improved and a mixed crystal of rutile type and anatase type can be obtained.

  Next, the slurry obtained by bringing the titanium salt and alkali into contact with each other in the alkali reaction method 1 to the alkali reaction method 3 is decanted and solid-liquid separated as necessary, and then pure water is added again to disperse the slurry. The solid reactant can be obtained by washing the reactant and finally separating the reactant produced by a method such as filtration or centrifugation, or by removing the solvent by evaporation. Titanium oxide can be obtained by washing, drying or heat-treating the obtained reaction product as necessary.

  During the drying or heat treatment, the treatment temperature is usually 50 to 150 ° C., and the drying atmosphere is an oxidizing atmosphere such as air or oxygen gas, an inert gas atmosphere such as nitrogen gas or argon gas, A vacuum atmosphere etc. are mentioned. Moreover, although drying or heat processing time is suitably adjusted with processing temperature, 1 to 24 hours are preferable. The rutile ratio can also be controlled by the heat treatment temperature. If the treatment temperature is high, the rutile type is likely to be generated, and if the temperature is low, the anatase type is likely to be generated.

  As an example of the production method of titanium oxide by the alkali reaction method 3, for example, water whose pH is adjusted to 3.0 to 4.5 is put in a reaction vessel, and a titanium tetrachloride aqueous solution and an alkali aqueous solution are put therein. Then, after dropping and reacting for 1.5 to 7.5 hours so as to maintain a pH of 3.0 to 5.0 and a temperature of 5 ° C. to 60 ° C., the conductivity of the obtained slurry is decantated or the like. It can be manufactured by washing with pure water until 500 to 2000 mS / m and drying or heat-treating it. The drying or heat treatment is usually performed in an atmosphere of an oxidizing gas such as air or oxygen gas or in an atmosphere of an inert gas such as nitrogen gas or argon gas at a temperature of 50 to 450 ° C. for 1 hour. It can be performed by treating for up to 24 hours.

  Thus, in the present invention, when titanium oxide obtained by reacting a titanium salt with an alkali compound is used as the first titanium oxide compound or the second titanium oxide compound, the reaction conditions of the titanium salt during the production of titanium oxide. The crystal form can be controlled by appropriately selecting (pH, temperature, alkali compound addition rate, etc.) and heat treatment conditions (heat treatment temperature, heat treatment time, etc.) of the reactant.

  When titanium oxide obtained by hydrolysis reaction of a titanium salt is used as the first titanium oxide compound or the second titanium oxide compound, the titanium oxide is a solution of the above titanium salt, for example, an organic metal such as titanium alkoxide. Give water to compounds, inorganic chlorides such as titanium chloride such as titanium tetrachloride and titanium trichloride, and sulfates such as titanyl sulfate and titanium sulfate, and heat them as necessary. Can do. For example, a method of hydrolyzing a titanium organometallic compound by adding water to an organic solvent solution of an organometallic compound such as titanium alkoxide, titanium chloride such as titanium tetrachloride or titanium trichloride, titanyl sulfate or titanium sulfate It can be produced by heating or pressurizing an aqueous solution of an inorganic salt such as sulfate.

  Thus, in the present invention, when using titanium oxide obtained by hydrolyzing a titanium salt as the first titanium oxide compound or the second titanium oxide compound, the conditions for hydrolysis of the titanium salt during the production of titanium oxide are used. (PH, hydrolysis rate, hydrolysis temperature, etc.), separation of solids from slurry, or processing conditions such as washing and drying performed as necessary to obtain solids, heat treatment conditions for reactants ( A desired titanium oxide can be obtained by appropriately selecting a heat treatment temperature, a heat treatment time, and the like.

In addition, when producing titanium oxide by a method of oxidizing or hydrolyzing the above (2) titanium chloride gas in a gas phase, specifically,
(Gas Phase Method 1) A method in which titanium tetrachloride gas and oxygen gas are brought into contact with each other and reacted.
(Gas phase method 2) A method of bringing titanium tetrachloride gas into contact with oxygen gas and hydrogen gas and reacting them,
(Gas phase method 3) A method in which titanium tetrachloride gas and water vapor are brought into contact with each other and reacted, or
(Gas Phase Method 4) A method in which titanium tetrachloride gas is brought into contact with hydrogen gas, oxygen gas and water vapor and reacted to hydrolyze or oxidize titanium tetrachloride in a gas phase state.

In the titanium oxide production method of the gas phase method 1 to the gas phase method 4, titanium tetrachloride gas is supplied to the reaction part, and is contacted with oxygen gas or oxygen gas and hydrogen gas in the reaction part. Contact with water vapor or contact with hydrogen gas, oxygen gas and water vapor, but oxidize all titanium tetrachloride with the total supply amount of oxygen and water vapor relative to the supply amount of titanium tetrachloride gas to the reaction section. It is desirable to make it more than the chemical equivalent.
In particular, when the supply amount of water vapor is equal to or higher than the chemical equivalent of oxidizing all titanium tetrachloride, the titanium oxide production reaction is uniformly performed, so that it is easy to control the crystal of the produced titanium oxide, and the high specific surface area. It becomes easy to obtain a rutile type titanium oxide powder having a high rutile ratio (rutile content) and an anatase type titanium oxide powder having a high specific surface area. Here, the chemical equivalent that oxidizes all titanium tetrachloride means the chemical equivalent of oxygen or water vapor when titanium tetrachloride is reacted with oxygen or water vapor. In the case of oxygen, titanium tetrachloride (TiCl ₄ ) gas 1 In the case of 1 mol of oxygen (O ₂ ) gas and water vapor with respect to mol, water vapor (H ₂ O) is 2 mol with respect to 1 mol of titanium tetrachloride gas.

  Moreover, the rutile-ization rate (rutile content rate) of the titanium oxide to produce | generate can be controlled by controlling the preheating temperature and reaction temperature of each supply gas. When producing an anatase-type titanium oxide powder having a low rutile ratio such as a rutile ratio of 10% or less, the preheating temperature is 500 to 800 ° C and the reaction temperature is 550 to 800 ° C. On the other hand, when producing a rutile type titanium oxide powder having a high rutile ratio such as a rutile ratio of 90% or more, the preheating temperature is 800 to 900 ° C and the reaction temperature is 850 to 900 ° C.

  In the present invention, when the first titanium oxide compound or the second titanium oxide compound is brookite-type titanium oxide, a method for producing a titanium oxide compound containing brookite-type titanium oxide is described in, for example, JP-A-11-43327. Has been. For example, hydrolyzing titanium compounds such as titanium tetrachloride and titanium alkoxide compounds to obtain a water-dispersed titanium oxide sol containing a small amount of alcohol, and adding HCl or the like to make the chlorine ion concentration in the range of 50 to 10,000 ppm. Is also possible. As the titanium compound, it is preferable to use titanium tetrachloride which generates hydrogen chloride by hydrolysis. Moreover, when hydrolyzing titanium tetrachloride, it is preferable to carry out hydrogen chloride produced in the hydrolysis while preventing escape from the reaction vessel.

(Sulfur atom-introduced titanium oxide)
In the present invention, the first titanium oxide compound or the second titanium oxide compound may be a sulfur atom-introduced titanium oxide, and the sulfur atom-introduced titanium oxide has a sulfur atom in a part of the titanium site of titanium oxide. What is introduced is preferable.

Sulfur atom-introduced titanium oxide can be produced by various methods. Specifically,
(Production Method 1 of Sulfur Atom-Introduced Titanium Oxide) Method of Firing a Mixture of Titanium Oxide and Sulfur Compound,
(Production Method 2 of Sulfur Atom-Introduced Titanium Oxide) A method of mixing and firing a titanium salt such as titanium alkoxide and a sulfur compound such as thioureas (for example, a method described in JP-A No. 2004-143032),
(Production method 3 of sulfur atom-introduced titanium oxide) A method of firing ammonium sulfate ammonium,
(Production Method 4 of Sulfur Atom-Introduced Titanium Oxide) A method of neutralizing or hydrolyzing a titanium salt aqueous solution containing a sulfur compound such as thioureas, and then firing the obtained neutralized product or hydrolyzate,
And so on.

Among the above-mentioned sulfur atom-introduced titanium oxide production method 1 to sulfur atom-introduced titanium oxide production method 4, production method 1 of sulfur atom-introduced titanium oxide will be described in detail.
In the manufacturing method 1 of the said sulfur atom introduction | transduction titanium oxide, first, the mixture of a titanium oxide and a sulfur compound is produced.
Examples of the titanium oxide include the various titanium oxides described above. Titanium oxide obtained by neutralization reaction of the titanium salt with an alkali compound or titanium oxide obtained by hydrolysis of the titanium salt is preferable. Is 100 to 450 m ² / g, the half-width of the diffraction peak of the (101) plane of anatase by X-ray diffraction analysis is 2θ = 1.0 ° or more, preferably 1.5 ° or more, and the crystal structure is anatase type Titanium oxide or titanium hydroxide is preferred.

As the sulfur compound to be mixed with titanium oxide, an organic sulfur compound is preferable, and thioureas are particularly preferable.
For example, 1-acetyl-2-thiourea (CH ₃ CONHCSNH ₂ ), amidinothiourea (C ₂ H ₆ N ₄ S), thiourea (H ₂ NCSNH ₂ ), 1- (1-naphthyl) -2-thiourea _{(C 11 H 10 N 2 S} ), phenyl ethyl thiourea _{(C 9 H 12 N 2 S} ), Maroniruchio urea _{(C 4 H 4 N 2 O} 2 S), N- methylthiourea _{(C 2} H _{6 N 2} S ), Thiourea dioxide (H ₂ NC (NH) SO ₂ H), and the like can be used.

In order to produce sulfur atom-introduced titanium oxide by introducing sulfur atoms into the titanium site of titanium oxide, as a sulfur compound to be reacted with titanium oxide, it is decomposed by heat and SO ₂ gas or SO ₃ gas is decomposed in the decomposition process. Sulfur compounds having sulfur atoms in the molecule that can be generated are preferable, sulfur compounds that are solid or liquid at room temperature are more preferable, and as these sulfur compounds, for example, sulfur-containing organic compounds, sulfur-containing inorganic compounds, metal sulfides, Sulfur and the like can be mentioned, and specifically, thiourea, thiourea derivatives, sulfate and the like can be mentioned. Of these, cyclic and acyclic thioureas, particularly thiourea, are particularly preferable because they completely decompose at 400 to 500 ° C. and do not remain in the resulting titanium oxide compound.

The method for mixing titanium oxide and sulfur compound is not particularly limited, for example,
(Sulfur Compound Mixing Method 1) A method of mixing the sulfur compound powder in a dry manner by a stirring mixing method or the like with respect to the titanium oxide powder,
(Sulfur Compound Mixing Method 2) A method of removing the solvent after dispersing titanium oxide in a solution in which the sulfur compound powder is dissolved,
(Sulfur Compound Mixing Method 3) A method in which an aqueous solution in which a sulfur compound powder is dissolved is added to and stirred in a slurry in which titanium oxide is dispersed in water.
(Sulfur Compound Mixing Method 4) A method in which a slurry in which a sulfur compound powder is dissolved is sprayed in a fluidized layer of titanium oxide and then dried.
(Sulfur Compound Mixing Method 5) A method of supporting a sulfur compound powder on a fluidized layer of titanium oxide by a vapor deposition method,
And so on.
Among these mixing methods, the sulfur compound mixing method 1 in which titanium oxide and a sulfur compound are mixed in a dry manner is preferable from the viewpoint of operability.

  The mixing amount of the sulfur compound is preferably 0.5 to 120 parts by mass in terms of sulfur atom, based on 100 parts by mass of the total titanium atoms contained in the titanium oxide, and 2 to 80 parts by mass. More preferably, it is more preferably 3 to 50 parts by mass.

  When the mixing amount of the sulfur compound is 100 parts by mass of the total titanium atoms contained in the titanium oxide, the photocatalyst in the visible light region is 0.5 to 120 parts by mass in terms of sulfur atoms. It becomes easy to provide sulfur atom-introduced titanium oxide having good activity. In particular, by setting the mixing amount of the sulfur compound in the above range, when the amount of all titanium atoms contained in the titanium oxide is 100 parts by mass, a part of the titanium site of the titanium oxide is 0.005 to 0. It is easy to obtain sulfur atom-introduced titanium oxide having a good photocatalytic activity in the visible light region, which is substituted with 20 parts by mass of a sulfur atom, and an iron compound having a good photocatalytic activity in the visible light region as described later. It can serve as a raw material for sulfur atom-introduced titanium oxide containing.

Firing of the mixture of titanium oxide and sulfur compound is preferably performed in a state where the mixture of titanium oxide and sulfur compound is put into a firing container and covered. When the mixture is completely opened, the gas generated from the sulfur compound does not stagnate when it is completely opened. Therefore, it is preferable to perform the firing with the gap slightly opened. When the mixture is baked and the sulfur compound is decomposed by the generated heat, SO ₂ gas is generated in the decomposition process, sulfur atoms in the SO ₂ gas are taken into titanium oxide, and the titanium atoms of titanium oxide It is considered to be replaced with a part. Therefore, it is preferable to fire the mixture while retaining the SO ₂ gas generated by the decomposition of the sulfur compound in the atmosphere.

  The firing is preferably performed in the presence of an oxygen-containing gas such as air. When the supply flow rate of the oxygen-containing gas is appropriately adjusted, complete decomposition of the sulfur compound is promoted, and when the amount of all titanium atoms contained in the titanium oxide is 100 parts by mass, Titanium oxide in which parts are substituted with 0.005 to 0.20 parts by mass of sulfur atoms can be obtained.

  The firing temperature of the mixture is preferably 300 to 600 ° C, and more preferably 400 to 500 ° C. When the firing temperature when firing the mixture of titanium oxide and sulfur compound is in the range of 300 to 600 ° C., the photocatalytic activity in the visible light region of the resulting metal oxide-containing titanium oxide compound is improved. The firing time of the mixture is preferably 0.5 to 10 hours, and more preferably 1 to 5 hours.

  Moreover, after baking, in order to remove the component adhering to the surface of baking products, it is preferable to wash with water. More preferably, if the surface of the fired product is washed with an alkali such as sodium hydroxide or aqueous ammonia, the washing efficiency is good and higher activity may be obtained.

  In the obtained sulfur atom-introduced titanium oxide, when the amount of all titanium atoms contained in the titanium oxide is 100 parts by mass, a part of the titanium sites of the titanium oxide are 0.005 to 0.20 parts by mass of sulfur atoms. What is substituted is preferable, and one in which a part of the titanium site of titanium oxide is substituted with 0.01 to 0.10 parts by mass of a sulfur atom is more preferable. Since the amount of sulfur atoms introduced into the titanium sites of titanium oxide is within the above range, the photocatalytic activity of the sulfur atom-introduced titanium oxide in the visible light region can be increased, and a sulfur atom-introduced titanium oxide containing an iron compound described later. When used as a raw material, the photocatalytic activity in the visible light region can be enhanced.

Confirmation that a part of the titanium site of titanium oxide is substituted with a sulfur atom can be performed by X-ray photoelectron spectroscopy (XPS) analysis. When a part of the titanium site of titanium oxide is substituted with a sulfur atom, a characteristic peak near 169 eV derived from S ⁴⁺ is confirmed.

Sulfur atom introduced titanium oxide preferably has a specific surface area of 50~120m ² / g, more preferably 60~95m ² / g, anatase constituting a sulfur atom introduced titanium oxide by X-ray diffraction analysis The half width of the diffraction peak of the (101) plane of the crystal is 1.40 ° or less, preferably 0.20 to 0.90 °, and the crystal structure is preferably anatase type. When the specific surface area and the full width at half maximum are within the above ranges, the photocatalytic activity in the visible light region of the obtained metal oxide-containing titanium oxide compound can be increased.

(Nitrogen atom-introduced titanium oxide)
In the present invention, the first titanium oxide compound or the second titanium oxide compound may be nitrogen atom-introduced titanium oxide.
When nitrogen atom-introduced titanium oxide is used as the first titanium oxide compound or the second titanium oxide compound, the half-width of the diffraction peak on the (101) plane by X-ray diffraction analysis is 1. Although it is not particularly limited as long as it is 40 ° or less, a nitrogen atom is present at a part of the oxygen site of titanium oxide in which the half-value width of the diffraction peak of (101) plane by X-ray diffraction analysis is 1.40 ° or less. What is introduced is preferable. This nitrogen atom-introduced titanium oxide can also be produced by various methods. Specifically, in the production method 1 of the above-described sulfur atom-introduced titanium oxide, The method of baking the mixture of these can be mentioned.

  Examples of the titanium oxide mixed with the nitrogen compound include the same titanium oxide mixed with the sulfur compound. Further, instead of titanium oxide, a precursor of titanium oxide may be used. Examples of the precursor of titanium oxide include titanyl sulfate, titanium sulfate, titanium chloride, and an organic titanium compound.

  Examples of the organic titanium compound include titanium alkoxide, acetylacetonate, and the like, such as tetraisopropoxy titanium, titanium butoxide, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate, tetraoctyl titanate, titanium chelate, titanium Acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium acylate, polyhydroxy titanium stearate, titanium lactate, titanium triethanolamate tetra-i-propoxytitanium, di-i- Propoxy bis (ethyl acetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy Scan (acetylacetone) titanium, and the like.

Examples of nitrogen compounds to be mixed with titanium oxide include urea, urea dioxide, thiourea dioxide, melamine, guanidine, cyanuric acid, biuret, uracil and the like.
The method for mixing the titanium oxide and the nitrogen compound is not particularly limited. For example, a method similar to the above-described sulfur compound mixing methods 1 to 5 is adopted except that the nitrogen compound is used instead of the sulfur compound. A method of mixing titanium oxide and a nitrogen compound in a dry method is preferable from the viewpoint of operability.

  The mixing amount of the nitrogen compound is preferably 0.5 to 120 parts by mass in terms of nitrogen atom when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass, and 1 to 100 parts by mass. More preferably.

  As a method for firing a mixture of titanium oxide and a nitrogen compound, a method similar to the method for firing the above mixture of titanium oxide and a sulfur compound can be used except that a nitrogen compound is used instead of the sulfur compound. The firing temperature is preferably 200 to 500 ° C. When the firing temperature is in the range of 200 to 500 ° C., it becomes easy to obtain nitrogen atom-introduced titanium oxide having improved photocatalytic activity in the visible light region, and more visible light is supported when an iron compound described later is supported. The photocatalytic activity in the region can be improved. The firing time of the mixture is preferably 0.5 to 10 hours.

  Also, after the heat treatment, washing the reaction residue on the surface with an acid such as sulfuric acid, hydrochloric acid or nitric acid, an alkali such as sodium hydroxide or aqueous ammonia, or high-temperature steam may result in higher activity, which may be necessary. It is preferable to process accordingly.

  In the present invention, in the case where the first titanium oxide compound or the second titanium oxide compound is nitrogen atom-introduced titanium oxide, a peak can be confirmed in the vicinity of 395 eV to 397 eV in the measurement spectrum by X-ray photoelectron spectroscopy (XPS). It exhibits high photocatalytic activity under visible light irradiation and is suitable. The nitrogen atom-introduced titanium oxide is considered to have a chemical bond between the titanium atom of the titanium oxide and the nitrogen atom, and has a structure in which a part of the oxygen atom of the titanium oxide is substituted with the nitrogen atom. It is thought that.

(Carbon atom-introduced titanium oxide)
In the present invention, the first titanium oxide compound or the second titanium oxide compound may be a carbon atom-introduced titanium oxide. When the first titanium oxide compound or the second titanium oxide compound is a carbon atom-introduced titanium oxide, the carbon atom-introduced titanium oxide has a half-value width of the diffraction peak of the (101) plane by X-ray diffraction analysis of 1.40. There is no particular limitation as long as it is less than or equal to °.

The carbon atom-introduced titanium oxide can be obtained, for example, by heat-treating titanium carbide in an oxidizing atmosphere. In this case, the heat treatment temperature is preferably 300 ° C to 700 ° C, more preferably 450 ° C to 600 ° C.
In addition, the above-mentioned titanium oxide or titanium oxide precursor is put in a reaction vessel, and a carbon-containing gas such as methane is sealed in a state where the degree of vacuum is lower than atmospheric pressure and irradiated with electromagnetic waves, thereby introducing titanium atoms. Can also be produced. At this time, the pressure in the reaction ^vessel, preferably in the range of ^0.1 -10 ^Torr, more preferably in the range of 0.5 -5 Torr. Further, for example, when the frequency of electromagnetic waves is 2.45 GHz, handling is relatively easy. In addition, if a reducing gas such as hydrogen or ammonia gas is enclosed in the reaction vessel at the same time, the production time can be adjusted according to this ratio.
In addition, titanium oxide into which carbon atoms have been introduced can also be obtained by heating and crystallizing a mixture of a TiC compound and a titanium oxide precursor at 100 to 1000 ° C.

(Phosphorus atom-introduced titanium oxide)
In the present invention, the first titanium oxide compound or the second titanium oxide compound may be phosphorus atom-introduced titanium oxide. When phosphorus atom-introduced titanium oxide is used as the first titanium oxide compound or the second titanium oxide compound, the half-width of the diffraction peak of the (101) plane by X-ray diffraction analysis is 1. If it is 40 degrees or less, it will not restrict | limit in particular. This phosphorus atom-introduced titanium oxide is, for example, a method of heat-treating the above-described titanium oxide or a titanium oxide precursor in an atmosphere containing a phosphorus compound gas, or a mixture of a TiP compound and the above-described titanium oxide precursor in a range of 100 to 1000. It can be produced by a method of heat crystallization at 0 ° C. or a method of neutralizing, hydrolyzing or thermally decomposing a titanium oxide precursor containing phosphorus.

(Titanium oxide containing iron compounds)
In the present invention, as the first titanium oxide compound or the second titanium oxide compound, the above titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide, phosphorus atom-introduced titanium oxide, , Fe ₂ O ₃ , Fe ₃ O _{4 and} other iron compounds, WO ₃ , V ₂ O ₅ , Bi ₂ O ₃ , Nb ₂ O ₃ , ZnO, ZrO ₂ , PtO ₂ , PdO, In ₂ O ₃ , PbO , FeTiO ₃ , SrTiO ₃ , BaTiO ₃ , CaTiO ₃ , KTaO ₃ , SnO ₂ , MnO ₂ , Cr ₂ O ₃ , Co ₃ O ₄ , Y ₂ O ₃ , Mo ₂ O _{3 and} other metal compounds, Cr, V , Cu, Fe, Mg, Ag, Pd, Ni, Mn and Pt may contain one or more metal ions selected from the group consisting of these, Among the titanium oxide compounds, sulfur atom-introduced titanium oxide containing an iron compound or nitrogen atom-introduced titanium oxide containing an iron compound is preferable. When the first titanium oxide compound or the second titanium oxide compound contains one or more selected from the above iron compounds, metal compounds, and metal ions, the photocatalytic activity of titanium oxide can be improved.

  The aspect in which the titanium oxide, the sulfur atom-introduced titanium oxide, the nitrogen atom-introduced titanium oxide, the carbon atom-introduced titanium oxide, the phosphorus atom-introduced titanium oxide contains a metal compound such as the above iron compound or a metal ion is not particularly limited, but the above oxidation It is preferable that a metal compound such as the iron compound or a metal ion is supported on the surface of titanium or the like.

When the first titanium oxide compound or the second titanium oxide compound contains a metal compound such as the above iron compound or a metal ion, the method for producing these titanium oxide compounds is not particularly limited. ,
(Metal compound or metal ion introduction method 1) Titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide or phosphorus atom-introduced titanium oxide and metal compound are mixed in an aqueous medium and slurry And adjusting the pH of the slurry by adding alkali to the resulting slurry,
(Method 2 of introducing metal compound or metal ion) Titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide or phosphorus atom-introduced titanium oxide and metal compound are mixed in an aqueous medium to form a slurry. And adding sodium borohydride to the resulting slurry,
(Metal compound or metal ion introduction method 3) After dispersing titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide or phosphorus atom-introduced titanium oxide in the liquid, the metal compound is dissolved. Adding the solution, removing the solvent, and drying in an oxidizing atmosphere, a reducing atmosphere, an inert atmosphere,
(Method 4 of introducing metal compound or metal ion) Spraying a solution in which a metal compound is dissolved in a fluidized layer of titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide or phosphorus atom-introduced titanium oxide And how to dry,
(Method 5 of introducing metal compound or metal ion) Titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide or phosphorous atom-introduced titanium oxide in the gas phase A method of supporting by vapor deposition,
(Metal compound or metal ion introduction method 6) After producing titanium oxide, sulfur atom-introduced titanium oxide, nitrogen atom-introduced titanium oxide, carbon atom-introduced titanium oxide or phosphorus atom-introduced titanium oxide, sulfur compound or nitrogen compound, etc. In mixing, a method of simultaneously mixing and firing a metal compound can be exemplified.

Examples of the metal compound used in the above “method 6 of introducing metal compound or metal ion” include iron compounds having the form of inorganic salts such as iron oxide, iron hydroxide, iron chloride, sulfate, and nitrate. Organic iron compounds and the like are preferable.
Specifically, Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH), FeCl ₂ , FeCl ₃ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , Fe (NO ₃ ) ₃ , FeI ₂ , FeI ₃ , Iron citrate, iron ammonium sulfate, ferric ammonium sulfate, ammonium iron citrate, iron sulfide, iron phosphate, ammonium iron oxalate, iron oxalate, iron 2-ethylhexanoate, iron naphthenate, iron acetylacetonate, iron methoxide Iron ethoxide, iron i-propoxide, bis (cyclopentadienyl) iron, bis (ethylcyclopentadienyl) iron, iron acetate, iron tartrate, iron fumarate and the like. Among these iron compounds, especially iron (II) sulfate heptahydrate and iron (II) oxalate dihydrate have no deliquescence, good dry mixing, and excellent photocatalytic properties. It is preferable in terms of expressing. In addition, iron (II) sulfate heptahydrate is widely distributed as a food additive, so it is superior to other iron compounds in terms of safety, stability and inexpensiveness. Highly useful.

  In the present invention, when the content of titanium atoms constituting the first titanium oxide compound is 100 parts by mass with respect to the first titanium oxide compound, the first catalyst component is an antibacterial active metal species. 2.8 to 15 parts by mass in terms of atoms are supported, and the second catalyst component has a content of titanium atoms constituting the second titanium oxide compound with respect to the second titanium oxide compound. When the amount is 100 parts by mass, 0 to 1.5 parts by mass of the antibacterial active metal species is supported in terms of metal atoms.

In the present invention, the antibacterial active metal species supported on the first titanium oxide compound and the second titanium oxide compound may be the same or different.
In the present invention, the antibacterial active metal species include copper oxides such as Cu ₂ O and CuO, copper hydroxides such as Cu (OH) ₂ , copper basic salts such as CuCl ₂ .3Cu (OH) ₂ , or Copper compounds such as compounds composed of one or more atoms selected from Cu atom and O (oxygen) atom, H (hydrogen) atom, N (nitrogen) atom, S (sulfur) atom, Cl (chlorine) atom, and metallic silver And at least one selected from silver compounds such as Ag ₂ O, AgCl, AgI, silver sulfide, silver acetate, silver nitrate, silver sulfate and organic silver compounds, and constitutes these antibacterial active metal species Metal ions may be supported.

As a method of supporting the antibacterial active metal species for the first titanium oxide compound and the second titanium oxide compound, for example,
(Support method 1) The first titanium oxide compound or the second titanium oxide compound and the antibacterial active metal species are mixed in an aqueous medium to form a slurry, and alkali is added to the obtained slurry to adjust the pH of the slurry. how to,
(Supporting method 2) A method in which the first titanium oxide compound or the second titanium oxide compound and the antibacterial active metal species are mixed and slurried in an aqueous medium, and sodium borohydride is added to the resulting slurry.
(Supporting method 3) After the first titanium oxide compound or the second titanium oxide compound is dispersed in the liquid, the liquid in which the antibacterial active metal species is dissolved is added, the solvent is removed, the oxidizing atmosphere, the reducing atmosphere, A method of drying in an active atmosphere,
(Supporting method 4) A method of spraying and drying a liquid in which an antibacterial active metal species is dissolved in a fluidized bed of the first titanium oxide compound or the second titanium oxide compound,
(Supporting method 5) A method of supporting the antibacterial active metal species or the metal constituting the antibacterial active metal species on the fluidized bed of the first titanium oxide compound or the second titanium oxide compound by a vapor deposition method,
(Supporting method 6) After preparing titanium oxide, when mixing this titanium oxide and a sulfur compound or a nitrogen compound etc., the method of mixing and baking an antimicrobial active metal seed | species simultaneously can be mentioned.
Of the above loading methods 1 to 6, the loading method 1 is preferable because the metal compound can be stably and uniformly supported.

Hereinafter, taking the case where the antibacterial active metal species is a copper compound as an example, the supporting method 1 will be described in detail.
Examples of the aqueous medium in which the titanium oxide compound and the copper compound are mixed include water or a material containing water as a main component and a water-soluble organic solvent, and is preferably water.

The pH of the slurry obtained by mixing the titanium oxide compound and the copper compound in an aqueous medium is usually in the range of 1.5 to 3.5, but an aqueous ammonia solution or the like is added to this slurry to adjust the pH to 6 It is preferable to adjust to ~ 9.
By the pH adjustment, the copper compound or copper ion in the slurry is deposited and adhered to the surface of the first titanium oxide compound or the second titanium oxide compound as the carrier.

  Thereafter, the slurry is washed with pure water until the conductivity of the slurry becomes 50 mS / m or less by a method such as a decantation method, and then dried to obtain a titanium oxide compound carrying the target copper compound. it can.

Further, when a silver compound is used instead of the copper compound, it may be supported by the same method, preferably supported by the above support method 2 to support method 5, and more preferably supported by support method 2.
In the supporting method 2, when the first titanium oxide compound or the second titanium oxide compound and the silver compound are brought into contact with each other and reduced with a reducing agent such as sodium borohydride, the same procedure as in the supporting method 1 is performed. It is preferable to wash by a decantation method or the like, and then dry.

  In this way, the first catalyst component or the second catalyst component can be obtained.

  In the present invention, when the content of titanium atoms constituting the first titanium oxide compound is 100 parts by mass with respect to the first titanium oxide compound, the first catalyst component is an antibacterial active metal species. 2.8 to 15 parts by mass supported in terms of atoms, preferably 3.5 to 10 parts by mass, preferably 4.8 to 10 parts by mass. It is more preferable to support 4.8 to 7 parts by mass.

  In the present invention, when the content of titanium atoms constituting the second titanium oxide compound is 100 parts by mass with respect to the second titanium oxide compound, the second catalyst component is an antibacterial active metal species. It is carried by 0 to 1.5 parts by mass in terms of atoms, preferably 0 to 1.0 parts by mass, preferably 0 to 0.5 parts by mass. It is more preferable.

  In the present invention, when the content of titanium atoms constituting the second titanium oxide compound is 100 parts by mass, the metal atom equivalent amount (mass of the antibacterial active metal species supported by the second titanium oxide compound) Part) is a metal atom equivalent amount (parts by mass) of the antibacterial active metal species supported by the first titanium oxide compound when the content of titanium atoms constituting the first titanium oxide compound is 100 parts by mass. Less than 1.3 to 15 parts by mass.

  In the present invention, when the supported amount of the antibacterial active metal species in the first catalyst component and the second catalyst component is within the above range, the photocatalytic action of titanium oxide that decomposes bacterial and viral constituents and bacterial metabolism The function of inhibiting the function functions efficiently, and it becomes easy to provide a photocatalyst excellent in sterilization rate and decomposition rate of harmful gas.

In the present invention, when the total content of the first titanium oxide compound and the second titanium oxide compound constituting the photocatalyst is 100% by mass, the content of the first titanium oxide compound is 7.5 to 72% by mass. %, More preferably 20 to 45% by mass, and even more preferably 10 to 45% by mass.
In the present invention, when the total content of the first titanium oxide compound and the second titanium oxide compound constituting the photocatalyst is 100% by mass, the content of the second titanium oxide compound is 28 to 92. It is preferably 5% by mass, more preferably 55-90% by mass, and still more preferably 55-80% by mass.
In the present invention, when the content ratio of the first titanium oxide compound and the second titanium oxide compound (the content ratio of the first catalyst component and the second catalyst component) is within the above range, the photocatalytic activity and the antibacterial performance It is easy to provide an excellent photocatalyst.

In the present invention, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species is preferably 10 parts by mass or less, more preferably 0.5 parts by mass to 7 parts by mass, and 2 parts by mass to 7 parts by mass. Further preferred.
When the supported amount of the antibacterial active metal species is within the above range, it becomes easy to provide a photocatalyst excellent in photocatalytic activity and antibacterial performance.

  The photocatalyst of the present invention preferably has an average particle size D50 (50% particle size in the integrated particle size distribution) of 500 nm or less as measured using a laser light scattering diffraction particle size analyzer, What is 300 nm or less is more preferable.

The photocatalyst of the present invention can be produced by mixing the first catalyst component and the second catalyst component.
In the method for producing the photocatalyst of the present invention, as a means for mixing the first catalyst component and the second catalyst component, it is possible to use a stirrer having a normal stirring blade, a stirrer such as a V mixer or a corn mixer. it can.

  Moreover, in the method for producing the photocatalyst of the present invention, it is preferable to further crush the mixture. The crushing is preferably performed using a crushing apparatus that uses an impact action, a shearing action or a grinding action. Specifically, the crushing apparatus using impact action, shear action and grinding action is emulsification / dispersion such as high-speed rotary crusher, jet mill, bead mill, hammer mill, vibration mill, meteor type ball mill, homogenizer, etc. The crushing apparatus which consists of a machine etc. can be mentioned.

When a high-speed rotary pulverizer is used as the crushing device, the high-speed rotary pulverizer is a device that rotates a pin, a blade, or the like at high speed and pulverizes the powder by impact or shearing action. Examples of the high-speed rotary pulverizer include a pin mill.
When a high-speed rotary pulverizer is used as the crusher, the peripheral speed during rotation of the pins and blades is preferably 100 to 200 m / second, and more preferably 150 to 200 m / second. Moreover, it is preferable that the supply amount of the to-be-processed object with respect to a high-speed rotary crusher is 200 kg / h or less, It is more preferable that it is 30-200 kg / h, It is further more preferable that it is 30-100 kg / h. When the supply amount of the object to be processed to the high-speed rotary pulverizer exceeds 200 kg / h, sufficient pulverization processing becomes difficult. Further, if the supply amount is less than 30 kg / h, it becomes difficult to perform efficient pulverization. In addition, in the type of pulverizer in which the object to be processed circulates in the high-speed rotary pulverizer, the processing time (pulverization time) in the pulverizer is preferably 1 minute or more.

A jet mill is an apparatus that pulverizes powder by pulverizing powder into a gas such as air jetted from a nozzle at high pressure, and colliding between particles or particles and an impact plate.
When using a jet mill as a crushing apparatus, it is preferable that processing pressure (gas pressure injected from a nozzle) is 0.5-1.0 MPa. The supply amount of the object to be processed to the jet mill is preferably 300 kg / h or less, more preferably 10 to 300 kg / h, and further preferably 10 to 100 kg / h. If the supply amount of the object to be processed exceeds 300 kg / h with respect to the jet mill, sufficient crushing processing becomes difficult. Further, if the supply amount is less than 10 kg / h, it becomes difficult to perform efficient pulverization.

  When a bead mill is used as the crushing device, the peripheral speed of the rotating part is preferably 4 to 10 m / s.

When using an emulsifying-dispersing machine such as a homogenizer as crushing device, the rotational speed of the rotary portion is preferably from 3000～10000Min ^-1, and more preferably 5000~8000min ^-1.

The crushing process may be performed using a plurality of crushers sequentially.
The crushing treatment may be performed in a state where the object to be treated is dispersed in a solvent such as water or an organic solvent, or the object to be treated may be performed in a dry (powdered) form. When the material to be treated is pulverized in a state of being dispersed in a solvent, it is preferable to appropriately separate the solvent after pulverization.
The crushing treatment is performed so that the average particle diameter D50 (50% of the accumulated particle size in the volume accumulated particle size distribution) is 500 nm or less when measured using a laser light scattering diffraction particle size analyzer. Is preferable, and it is more preferable to carry out so as to be 300 nm or less.

  The photocatalyst of the present invention comprises a first catalyst component and a second catalyst component having different loadings of antibacterial active metal species. The photocatalytic action) and the action that inhibits the metabolic function of bacteria (mainly the antibacterial action of active metal species) function efficiently as a synergistic effect, and especially visible light compared to the photocatalyst carrying the antibacterial active metal compound uniformly. Under irradiation, the antibacterial activity is improved and the bacteria can be completely sterilized in a shorter time, and the harmful gas decomposition performance (photocatalytic action of titanium oxide) can be functioned without significant loss. For this reason, according to the present invention, it is possible to provide a photocatalyst which has an improved antibacterial activity and an excellent sterilization rate and an excellent harmful gas decomposition rate, particularly under visible light irradiation.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all by the following examples.
In the following examples and comparative examples, crystal type identification, specific surface area measurement, sulfur content measurement, photocatalytic performance test (antibacterial performance (antibacterial activity against Staphylococcus aureus), harmful gas decomposition performance (acetaldehyde gas The decomposition ability)) was performed by the following method.

<Crystal type identification method>
Using the following apparatus, the crystal form was specified under the following conditions.
X-ray diffractometer RINT / Ultima + (Rigaku Corporation)
X-ray tube Cu
Tube voltage / tube current 40kV, 20mA
Slit DS-SS: 1 degree, RS: 0.3 mm
Scanning speed 5 ° / min.
Measurement range 20 ° -40 °
Monochromator Graphite Measurement interval 0.02 degree Counting method Constant clock method In addition, in the obtained titanium oxide, titanium oxide compound or active metal-supported titanium oxide compound, X of rutile type crystalline titanium oxide constituting each of these compounds The peak area (Ir) of the strongest interference line (surface index 110) in the line diffraction pattern and the peak area of the strongest interference line (surface index 101) in the X-ray diffraction pattern of the anatase-type titanium oxide powder constituting the titanium oxide compound. (Id) was calculated, the rutile ratio was calculated by the following formula, and an anatase type having a rutile ratio of 10% or less was obtained.
Rutile ratio (%) = 100-100 / (1 + 1.2 × Ir / Id)

<Measurement of specific surface area>
It was measured by the BET method. The degassing conditions for the pretreatment were 110 ° C. and 30 minutes.

<Measurement of sulfur content>
The content of sulfur was measured by ICP emission spectroscopy (measuring device: SII Nanotechnology-SPS-3100, manufactured by SII Nanotechnology Inc.).

<Evaluation of average particle size>
The particle size distribution (average particle size D50 (particle size of 50% in the volume cumulative particle size distribution) was measured using a particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) in a 0.2% aqueous solution of sodium hexametaphosphate. A measurement sample was put in, and the dispersion was treated for 3 minutes using an ultrasonic dispersion device (output 30 W—range 5) with built-in LA-920.

<Antibacterial performance (antibacterial activity against Staphylococcus aureus) evaluation test method>
Inoculated test bacteria (Staphylococcus aureus) on normal agar medium, cultured at 35 ° C for 24 hours, and then prepared using physiological saline so that the number of bacteria was about 10,000,000 cells / mL Was used as a test bacterial solution. Moreover, what was produced so that the density | concentration of each photocatalyst might be 10 mg / mL using purified water was made into the test sample liquid.
After putting 10 mL of the above test sample solution into each L-shaped test tube, inoculate 1 mL of the above test bacterial solution, culturing with shaking at 25 ° C. under light irradiation and in the dark, and determining the number of viable bacteria for a predetermined culture time. Measurement was performed using a dilution culture method. The light irradiation was performed at an illuminance of 1800 Lx under completely visible light in which a UV light filter (“UV guard” manufactured by Fuji Film Co., Ltd.) manufactured by FUJIFILM Corporation was attached to a fluorescent lamp and light having a wavelength of 410 nm or less was cut.
The irradiation time is 1.5 hours, 3 hours, 4 hours, 5 hours, 7 hours, 9 hours, and 11 hours, and the number of viable bacteria at each time is evaluated, and the detection limit of the number of viable bacteria is 10 (cfu / mL) or less was defined as the complete sterilization (completion) time. The initial viable cell count when 2 mL of the test bacterial solution was inoculated into 10 mL of the test sample solution was 220,000 (cfu / mL).

<Toxic gas decomposition performance (decomposition ability of acetaldehyde gas) evaluation test method>
0.10 g of each measurement sample is placed in a dish with a diameter of 100 mm and dispersed in a tedra bag with a capacity of about 0.5 L, and then irradiated with ultraviolet light for 85 hours to initially adhere to the powder surface. The organic matter was decomposed. After exhausting the gas in the tedlar bag, 0.3 L of acetaldehyde gas concentration of 25 ppm was sealed in the tedlar bag. This was allowed to stand in a dark place for 5 hours, and after the gas was adsorbed to the powder in the dark place, the acetaldehyde concentration and carbon dioxide concentration in the Tedra bag were measured to obtain the initial concentration. Thereafter, irradiation with a fluorescent lamp was started from the outside of the Tedra bag, and the acetaldehyde concentration and the carbon dioxide concentration were measured every 20 minutes.
As a condition for irradiating the fluorescent lamp, the light source is an 18W fluorescent tube (manufactured by Panasonic Electric Works Co., Ltd., FL20SS / ENW / 18X) equipped with an ultraviolet cut filter (“UV guard” manufactured by Fuji Film Co., Ltd.), and has a wavelength of 410 nm. The following rays containing ultraviolet light were cut. Further, the distance from the fluorescent tube was adjusted so that the illuminance on the upper surface of the dish was 6000 Lx. The acetaldehyde gas concentration and the carbon dioxide gas concentration were measured using a gas monitor device (manufactured by INNOVA, photoacoustic gas monitor).
When 25 ppm of acetaldehyde is completely decomposed, 50 ppm of carbon dioxide that is twice this amount is generated, and no more carbon dioxide is generated. Therefore, the light irradiation time until the value obtained by subtracting the measured concentration of carbon dioxide from the initial concentration reached 50 ppm and stabilized was evaluated as the complete acetaldehyde decomposition time.

Example 1
(1) Preparation of titanium oxide Titanium oxide powder was manufactured by the following method.
In a storage tank equipped with a stirrer, a titanium tetrachloride aqueous solution (titanium concentration: 5.7% by mass) was used as a starting solution, and a volume of 19 L adjusted to pH 3.8 ± 0.5, an acidic aqueous solution having a liquid temperature of 10 ° C. Prepared.
While stirring with a stirrer, an aqueous solution of titanium tetrachloride (titanium concentration: 5.75% by mass) and an aqueous ammonia solution (ammonia concentration: 5.75% by mass) were respectively added to the storage tank at a flow rate of about 89 g / The titanium oxide-containing slurry was produced by continuously adding and reacting for 5 minutes at a rate of about 81 g / min. At this time, the temperature of the reaction solution to which the titanium tetrachloride aqueous solution and the ammonia aqueous solution were added was maintained at 5 to 25 ° C. During the addition for 5 hours, the flow rate of each solution was appropriately adjusted so that the pH of the reaction solution was in the range of 3.8 ± 0.5.
After completion of the addition, stirring was continued for 1 hour, and then an aqueous ammonia solution having an ammonia concentration of 5.8% was added to adjust the pH of the slurry to 5. The slurry is allowed to settle, the solid content is settled and the supernatant is extracted, and then the washing operation by decantation in which pure water at 10 to 30 ° C. is added and stirred again is performed so that the conductivity of the supernatant is 500 to 2000 mS / m. Repeat until. The cake obtained by filtering the washed slurry was placed in a titanium vat, dried at 110 ° C. for 24 hours with a dryer, and then crushed to obtain titanium oxide powder.
The obtained powder has a chlorine concentration of 0.45 mass%, a specific surface area of 355 m ² / g, and, as a result of X-ray diffraction, the half-value width 2θ of the peak of (101) of anatase-type titanium oxide is 2.1 °, The rutile rate was 0%.

(2) Preparation of iron-containing sulfur atom-introduced titanium oxide compound (sulfur atom-introduced titanium oxide compound containing iron compound) To the titanium oxide powder obtained in (1) above, thiourea (special grade) (manufactured by Kanto Chemical Co., Inc.) ) And iron (II) oxalate dihydrate were added and mixed to obtain a mixture of titanium oxide, thiourea and iron oxalate. At this time, the mixing amount of thiourea is adjusted to be 6.8 parts by mass in terms of sulfur atoms constituting thiourea when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass. did. Further, the mixing amount of iron (II) oxalate dihydrate is 0. 0 in terms of iron atoms constituting iron oxalate when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass. It adjusted so that it might become 05 mass parts ([Fe atom / Ti atom] is 0.05 mass% in percentage).
Specifically, 120 g of the above titanium oxide powder, 11.8 g of thiourea powder, and 0.12 g of iron (II) oxalate dihydrate were weighed, and these were dry-ground and mixed in a mortar.
This mixture was placed in a titanium container, and an upper lid with a vent was put on it. Then, the mixture was loaded in an electric furnace and heated to 460 ° C. During the temperature rise, the flow rate of intake air into the furnace was adjusted so that the atmosphere flows into the furnace at a flow rate of 5 to 100 mL / min. After reaching 460 ° C, the flow rate into the furnace is adjusted to 250 to 2000 mL / min, held and fired at 460 ° C for 1 hour, cooled to room temperature, taken out from the furnace, and fired (iron-containing sulfur atom introduced) Titanium oxide compound) was obtained.

(3) Preparation of iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 7.5 g of the fired product obtained in the above (2) was fractionated, and this was treated with 190 g of pure water And stirred to obtain a suspension slurry of the fired product. On the other hand, an aqueous copper chloride solution in which 0.81 g of copper (II) chloride dihydrate was dissolved in 7 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.6. Thereafter, 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. The compound was precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 6.7 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 92.5 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) is fractionated, and this is iron-containing sulfur atom-introduced titanium oxide carrying the copper compound obtained in (3) above. To the compound slurry, 2310 g of pure water was added and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 310 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 7.5% by mass, and the content of the second titanium oxide compound is 92.5% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 0.5 parts by mass.
The photocatalyst has a sulfur content of 0.40% by mass, a specific surface area of 71 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 7 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 14 hours.

(Example 2)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound carrying an antibacterial active metal (copper) compound 22.4 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and this Was put into 560 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 2.42 g of copper (II) chloride dihydrate was dissolved in 22 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.6. Thereafter, 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0, and a copper compound is precipitated on the surface of the particles. And supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 6.7 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 77.6 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). A slurry of titanium compound was added to 1940 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 350 nm was obtained.

The slurry was dried and pulverized to obtain a powdery photocatalyst.
In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 22.4% by mass and the content of the second titanium oxide compound is 77.6% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 1.5 parts by mass.
The photocatalyst has a sulfur content of 0.45% by mass, a specific surface area of 68 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powder photocatalyst, the complete sterilization time was 5 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 16 hours.

(Example 3)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 41.8 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated. Was added to 1045 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution prepared by dissolving 4.51 g of copper (II) chloride dihydrate in 40 g of pure water was added to the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 6.7 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 58.2 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added together with 1455 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out the time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component having an average particle diameter of 340 nm and the second catalyst component was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 41.8% by mass, and the content of the second titanium oxide compound is 58.2% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 2.8 parts by mass.
The photocatalyst has a sulfur content of 0.53% by mass, a specific surface area of 67 m ² / g, a half-width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 3 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 23 hours.

Example 4
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound supporting antibacterial active metal (copper) compound 71.6 g of iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and this Was put into 1790 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 7.72 g of copper (II) chloride dihydrate was dissolved in 70 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 6.7 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 28.4 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added and mixed with 710 g of pure water. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out the time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 370 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 71.6% by mass, and the content of the second titanium oxide compound is 28.4% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 4.8 parts by mass.
The photocatalyst has a sulfur content of 0.56% by mass, a specific surface area of 66 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.49 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 4 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above- The complete decomposition time was 36 hours.

(Example 5)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 10.0 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated. Was put into 250 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 2.42 g of copper chloride (II) dihydrate was dissolved in 22 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.6. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 15.0 parts by mass in terms of copper atoms ( [Cu atom / Ti atom] is 15.0 mass% in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 90 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and this was added to the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (3) above. The slurry was added to 2250 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 350 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 10.0% by mass, and the content of the second titanium oxide compound is 90.0% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 1.5 parts by mass.
The photocatalyst has a sulfur content of 0.48% by mass, a specific surface area of 70 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 7 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 18 hours.

(Example 6)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound carrying an antibacterial active metal (copper) compound 18.7 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and this Was put into 470 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 4.52 g of copper (II) chloride dihydrate was dissolved in 40 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 15.0 parts by mass in terms of copper atoms ( [Cu atom / Ti atom] is 15.0 mass% in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 81.3 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). A slurry of titanium compound was added and mixed with 2030 g of pure water. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 390 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 18.7% by mass, and the content of the second titanium oxide compound is 81.3% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 2.8 parts by mass.
The photocatalyst has a sulfur content of 0.53% by mass, a specific surface area of 67 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.49 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powder photocatalyst, the complete sterilization time was 5 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 24 hours.

(Example 7)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 32 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and 800 g Was put into pure water and stirred to obtain a suspension slurry. On the other hand, an aqueous copper chloride solution in which 7.73 g of copper (II) chloride dihydrate was dissolved in 70 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 15.0 parts by mass in terms of copper atoms ( [Cu atom / Ti atom] is 15.0 mass% in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 68 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and this was added to the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (3) above. Into this slurry, 1700 g of pure water was added and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 350 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 32.0% by mass, and the content of the second titanium oxide compound is 68.0% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 4.8 parts by mass.
The photocatalyst has a sulfur content of 0.58% by mass, a specific surface area of 65 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 3 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 28 hours.

(Example 8)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound carrying an antibacterial active metal (copper) compound 44.7 g of iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, Was put into 1120 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 10.8 g of copper (II) chloride dihydrate was dissolved in 100 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.6. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 15.0 parts by mass in terms of copper atoms ( [Cu atom / Ti atom] is 15.0 mass% in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 55.3 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added to 1380 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 390 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 44.7% by mass, and the content of the second titanium oxide compound is 55.3% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 6.7 parts by mass.
The photocatalyst has a sulfur content of 0.58% by mass, a specific surface area of 64 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 3 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above- The complete decomposition time was 41 hours.

Example 9
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound carrying an antibacterial active metal (copper) compound 66.7 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated. Was put into 1670 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 16.1 g of copper (II) chloride dihydrate was dissolved in 145 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 15.0 parts by mass in terms of copper atoms ( [Cu atom / Ti atom] is 15.0 mass% in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 33.3 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) was fractionated, and this was iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added and mixed with 830 g of pure water. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 380 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 66.7% by mass, and the content of the second titanium oxide compound is 33.3% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 10.0 parts by mass.
The photocatalyst has a sulfur content of 0.67% by mass, a specific surface area of 61 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powder photocatalyst, the complete sterilization time was 4 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above- The complete decomposition time was 49 hours.

(Example 10)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound carrying an antibacterial active metal (copper) compound 53.6 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and this Was put into 1340 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution in which 2.42 g of copper chloride (II) dihydrate was dissolved in 22 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.7. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 2.8 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 2.8 mass% in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 46.4 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added together with 1160 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 350 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 53.6% by mass, and the content of the second titanium oxide compound is 46.4% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 1.5 parts by mass.
The photocatalyst has a sulfur content of 0.43% by mass, a specific surface area of 72 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powder photocatalyst, the complete sterilization time was 5 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 21 hours.

(Example 11)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).

(3) Preparation of slurry of iron-containing sulfur atom-introduced titanium oxide compound carrying antibacterial active metal (copper) compound 10 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and 250 g Was put into pure water and stirred to obtain a suspension slurry. On the other hand, an aqueous copper chloride solution prepared by dissolving 0.45 g of copper (II) chloride dihydrate in 4 g of pure water was added to the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.7. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 2.8 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 2.8 mass% in percentage).

(4) Preparation of Slurry of Sulfur Atom-Introduced Titanium Oxide Compound Supported with Antibacterial Active Metal (Copper) Compound In Example 1 (2), the conditions except that iron (II) oxalate dihydrate was not added Similarly, a fired product (a sulfur atom-introduced titanium oxide compound) was obtained.
90 g of the above sulfur atom-introduced titanium oxide compound was fractionated, put into 2250 g of pure water, and stirred to obtain a suspension slurry of the sulfur atom-introduced titanium oxide compound. On the other hand, an aqueous solution of copper chloride in which 2.17 g of copper (II) chloride dihydrate was dissolved in 20 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.9. Thereafter, 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. The compound was precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid, thereby obtaining a slurry of a sulfur atom-introduced titanium oxide compound carrying a copper compound.
When the mass of all titanium atoms constituting the sulfur atom-introduced titanium oxide compound supporting the copper compound, which is the solid content of the slurry, is 100 parts by mass, the iron compound contained in the compound is converted to iron atoms. 0 parts by mass ([Fe atom / Ti atom] is 0% by mass), and the supported copper compound is 1.5 parts by mass in terms of copper atom ([Cu atom / Ti atom ] Is 1.5% by mass as a percentage).

(5) An iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and a sulfur atom-introduced titanium oxide compound (second catalyst) carrying an antibacterial active metal (copper) compound Mixing with the component) Using the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in the above (3) as a first catalyst component, introducing the sulfur atom carrying the copper compound obtained in the above (4) The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component using the titanium oxide compound as the second catalyst component.
Specifically, the total amount of the slurry obtained in the above (3) and the total amount of the slurry obtained in the above (4) are mixed, and the pH of the mixed slurry is maintained at 7.5 to 8.0. The solid content was washed until the conductivity of the slurry was 50 mS / m or less by repeating the decantation with pure water while adding an aqueous ammonia solution. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out the time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 370 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, a titanium oxide compound (first titanium oxide compound) constituting an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound, and a titanium oxide constituting a sulfur atom-introduced titanium oxide compound carrying a copper compound When the total content of the compound (second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 10.0% by mass, and the content of the second titanium oxide compound is 90%. It was 0.0 mass%. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 1.63 parts by mass.
The photocatalyst has a sulfur content of 0.45% by mass, a specific surface area of 68 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 4 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 18 hours.

(Example 12)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) Preparation of iron-containing sulfur atom-introduced titanium oxide compound (sulfur atom-introduced titanium oxide compound containing iron compound) To the titanium oxide powder obtained in (1) above, thiourea (special grade) (Kanto Chemical Co., Ltd.) Product) and iron (II) oxalate dihydrate were added and mixed to obtain a mixture of titanium oxide, thiourea and iron oxalate. At this time, the mixing amount of thiourea is adjusted to be 6.8 parts by mass in terms of sulfur atoms constituting thiourea when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass. did. Further, the mixing amount of iron (II) oxalate dihydrate is 0. 0 in terms of iron atoms constituting iron oxalate when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass. It adjusted so that it might become 10 mass parts.
Specifically, 120 g of the above titanium oxide powder, 11.8 g of thiourea powder, and 0.23 g of iron (II) oxalate dihydrate were weighed, and these were dry-ground and mixed in a mortar.
This mixture was placed in a titanium container, and an upper lid with a vent was put on it. Then, the mixture was loaded in an electric furnace and heated to 460 ° C. During the temperature rise, the flow rate of intake air into the furnace was adjusted so that the atmosphere flows into the furnace at a flow rate of 5 to 100 mL / min. After reaching 460 ° C, the flow rate into the furnace is adjusted to 250 to 2000 mL / min, held and fired at 460 ° C for 1 hour, cooled to room temperature, taken out from the furnace, and fired (iron-containing sulfur atom introduced) Titanium oxide compound) was obtained.

(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 41.8 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated. Was added to 1045 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution prepared by dissolving 4.51 g of copper (II) chloride dihydrate in 40 g of pure water was added to the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
When the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound that is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.10 parts by mass ([Fe atom / Ti atom] is 0.10% by mass), and the supported copper compound is 6.7 parts by mass in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 58.2 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added together with 1455 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 330 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 41.8% by mass, and the content of the second titanium oxide compound is 58.2% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 2.8 parts by mass.
The photocatalyst has a sulfur content of 0.48% by mass, a specific surface area of 70 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 3 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 24 hours.

(Example 13)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) Preparation of iron-containing sulfur atom-introduced titanium oxide compound (sulfur atom-introduced titanium oxide compound containing iron compound) To the titanium oxide powder obtained in (1) above, thiourea (special grade) (Kanto Chemical Co., Ltd.) Product) and iron (II) oxalate dihydrate were added and mixed to obtain a mixture of titanium oxide, thiourea and iron oxalate. At this time, the mixing amount of thiourea is adjusted to be 6.8 parts by mass in terms of sulfur atoms constituting thiourea when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass. did. Further, the mixing amount of iron (II) oxalate dihydrate is 0. 0 in terms of iron atoms constituting iron oxalate when the amount of all titanium atoms contained in titanium oxide is 100 parts by mass. It adjusted so that it might become 25 mass parts.
Specifically, 120 g of the above titanium oxide powder, 11.8 g of thiourea powder, and 0.58 g of iron (II) oxalate dihydrate were weighed, and these were dry-ground and mixed in a mortar.
This mixture was placed in a titanium container, and an upper lid with a vent was put on it. Then, the mixture was loaded in an electric furnace and heated to 460 ° C. During the temperature increase, the flow rate of intake air into the furnace was adjusted so that the atmosphere flows into the furnace at a flow rate of 5 to 100 mL / min. After reaching 460 ° C, the flow rate into the furnace is adjusted to 250 to 2000 mL / min, held and fired at 460 ° C for 1 hour, cooled to room temperature, taken out from the furnace, and fired (iron-containing sulfur atom introduced) Titanium oxide compound) was obtained.

(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 41.8 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated. Was added to 1045 g of pure water and stirred to form a suspension slurry. On the other hand, an aqueous copper chloride solution prepared by dissolving 4.51 g of copper (II) chloride dihydrate in 40 g of pure water was added to the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.5. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated twice to wash the solid matter, thereby obtaining a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.25 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.25 mass% in percentage), and the supported copper compound is 6.7 parts by mass in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).

(4) Mixing of an iron-containing sulfur atom-introduced titanium oxide compound (first catalyst component) carrying an antibacterial active metal (copper) compound and an iron-containing sulfur atom-introduced titanium oxide compound (second catalyst component) (3 The iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound obtained in (1) is used as the first catalyst component, and the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above is used as the second catalyst component. The target photocatalyst was prepared by mixing the first catalyst component and the second catalyst component.
Specifically, 58.2 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in the above (2) is fractionated, and this is iron-containing sulfur atom-introduced oxidation carrying the copper compound obtained in the above (3). The slurry of titanium compound was added together with 1455 g of pure water and mixed. Further, decantation with pure water is repeated while adding an aqueous ammonia solution so that the pH of the mixed slurry is maintained at 7.5 to 8.0, and the solid content is washed until the conductivity of the slurry becomes 50 mS / m or less. did. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry-like photocatalyst obtained by mixing the first catalyst component and the second catalyst component having an average particle diameter of 350 nm was obtained.
The slurry was dried and pulverized to obtain a powdery photocatalyst.

In the obtained photocatalyst, the titanium oxide compound (first titanium oxide compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound carrying the copper compound and the titanium oxide compound (first compound) constituting the iron-containing sulfur atom-introduced titanium oxide compound When the total content of the second titanium oxide compound) is 100% by mass, the content of the first titanium oxide compound is 41.8% by mass, and the content of the second titanium oxide compound is 58.2% by mass. %Met. Further, when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass, the first titanium oxide compound and the second titanium oxide compound are supported. The total amount of metal atoms constituting the antibacterial active metal species was 2.8 parts by mass.
The photocatalyst has a sulfur content of 0.52% by mass, a specific surface area of 68 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, and is mainly composed of anatase. It was a crystal (rutile degree: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 3 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 29 hours.
The results obtained in Examples 1 to 13 are shown in Tables 1 to 3.

(Comparative Example 1)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 100 g of the iron-containing sulfur atom-introduced titanium oxide compound obtained in (2) above was fractionated, and 2500 g It was put into pure water and stirred to obtain a suspension slurry of the fired product. On the other hand, an aqueous copper chloride solution in which 0.81 g of copper (II) chloride dihydrate was dissolved in 7 g of pure water was prepared, and this was put into the suspension slurry of the fired product and stirred for 30 minutes. The pH of the slurry during stirring was 2.6. Thereafter, a 2.8% aqueous ammonia solution is added dropwise to the stirring slurry over a period of about 1 hour until the pH of the slurry becomes 7.2 to 8.0. Precipitated and supported. Thereafter, decantation using pure water was repeated, and the solid content was washed until the conductivity of the slurry became 50 mS / m or less. After adjusting the amount of the supernatant extracted so that the final slurry becomes 1000 g, this mixed slurry was mixed with a disperser (trade name: TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)) at 5000 rpm. By carrying out time dispersion treatment, a slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound having an average particle diameter of 350 nm was obtained.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass part in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 0.5 mass part in terms of copper atom ( [Cu atom / Ti atom] is 0.5 mass% in percentage).
The slurry was dried and pulverized to obtain a powdery photocatalyst.
The photocatalyst has a sulfur content of 0.41% by mass, a specific surface area of 71 m ² / g, an X-ray diffraction analysis (101) peak half width of 0.48 °, anatase-based crystals ( Rutile conversion rate: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 11 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 24 hours.

(Comparative Example 2)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 0.81 g of copper (II) chloride dihydrate for the copper compound condition to be added in Comparative Example 1 (3) A copper chloride aqueous solution in which 2.42 g of copper (II) chloride dihydrate was dissolved in 22 g of pure water was prepared instead of the copper chloride aqueous solution in which the product was dissolved in 7 g of pure water. A slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound having an average particle size of 370 nm was obtained in the same manner as in Comparative Example 1 (3) except that it was added to the slurry.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 parts by mass ([Fe atom / Ti atom] is 0.05% by mass), and the supported copper compound is 1.5 parts by mass in terms of copper atom ( [Cu atom / Ti atom] is 1.5 mass% in percentage).
The slurry was dried and pulverized to obtain a powdery photocatalyst.
The photocatalyst has a sulfur content of 0.44% by mass, a specific surface area of 67 m ² / g, an X-ray diffraction analysis (101) peak half width of 0.48 °, anatase-based crystals ( (Rutylation rate: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 9 hours, and when the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 31 hours.

(Comparative Example 3)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 0.81 g of copper (II) chloride dihydrate for the copper compound condition to be added in Comparative Example 1 (3) Instead of the copper chloride aqueous solution in which the product was dissolved in 7 g of pure water, a copper chloride aqueous solution in which 4.51 g of copper (II) chloride dihydrate was dissolved in 40 g of pure water was prepared. A slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound having an average particle size of 350 nm was obtained in the same manner as in Comparative Example 1 (3) except that it was added to the slurry.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 2.8 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 2.8 mass% in percentage).
The slurry was dried and pulverized to obtain a powdery photocatalyst.
The photocatalyst has a sulfur content of 0.52% by mass, a specific surface area of 66 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, an anatase-based crystal ( (Rutylation rate: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 7 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 46 hours.

(Comparative Example 4)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 0.81 g of copper (II) chloride dihydrate for the copper compound condition to be added in Comparative Example 1 (3) A copper chloride aqueous solution in which 7.73 g of copper (II) chloride dihydrate was dissolved in 70 g of pure water was prepared instead of the copper chloride aqueous solution in which the product was dissolved in 7 g of pure water. A slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound having an average particle size of 390 nm was obtained in the same manner as in Comparative Example 1 (3) except that it was added to the slurry.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass parts in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 4.8 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 4.8 mass% in percentage).
The slurry was dried and pulverized to obtain a powdery photocatalyst.
The photocatalyst has a sulfur content of 0.56% by mass, a specific surface area of 62 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, an anatase-based crystal ( (Rutylation rate: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powder photocatalyst, the complete sterilization time was 5 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 52 hours.

(Comparative Example 5)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 0.81 g of copper (II) chloride dihydrate for the copper compound condition to be added in Comparative Example 1 (3) Instead of the copper chloride aqueous solution in which the product was dissolved in 7 g of pure water, a copper chloride aqueous solution in which 10.8 g of copper (II) chloride dihydrate was dissolved in 100 g of pure water was prepared. A slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound having an average particle size of 370 nm was obtained in the same manner as in Comparative Example 1 (3) except that it was added to the slurry.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 parts by mass ([Fe atom / Ti atom] is 0.05% by mass), and the supported copper compound is 6.7 parts by mass in terms of copper atom ( [Cu atom / Ti atom] is 6.7% by mass in percentage).
The slurry was dried and pulverized to obtain a powdery photocatalyst.
The photocatalyst has a sulfur content of 0.67% by mass, a specific surface area of 59 m ² / g, a half-value width of the peak of (101) by X-ray diffraction analysis of 0.48 °, an anatase-based crystal ( (Rutylation rate: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powder photocatalyst, the complete sterilization time was 5 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above-described method, The complete decomposition time was 67 hours.

(Comparative Example 6)
(1) Titanium oxide was prepared in the same manner as in Example 1 (1).
(2) An iron-containing sulfur atom-introduced titanium oxide compound was prepared in the same manner as in Example 1 (2).
(3) Preparation of an iron-containing sulfur atom-introduced titanium oxide compound slurry carrying an antibacterial active metal (copper) compound 0.81 g of copper (II) chloride dihydrate for the copper compound condition to be added in Comparative Example 1 (3) Instead of the copper chloride aqueous solution in which the product was dissolved in 7 g of pure water, a copper chloride aqueous solution in which 16.1 g of copper (II) chloride dihydrate was dissolved in 145 g of pure water was prepared. A slurry of an iron-containing sulfur atom-introduced titanium oxide compound carrying a copper compound having an average particle size of 370 nm was obtained in the same manner as in Comparative Example 1 (3) except that it was added to the slurry.
In addition, when the mass of all titanium atoms constituting the iron-containing sulfur atom-introduced titanium oxide compound supporting the copper compound which is the solid content of the slurry is 100 parts by mass, the iron compound contained in the compound is an iron atom. It is 0.05 mass part in terms of conversion ([Fe atom / Ti atom] is 0.05 mass% in percentage), and the supported copper compound is 10.0 mass parts in terms of copper atom ( [Cu atom / Ti atom] is 10.0% by mass).
The slurry was dried and pulverized to obtain a powdery photocatalyst.
The photocatalyst has a sulfur content of 0.80% by mass, a specific surface area of 55 m ² / g, an X-ray diffraction analysis (101) peak half width of 0.48 °, anatase-based crystals ( (Rutylation rate: 0%). Furthermore, when the powdery photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS), a characteristic peak near 169 eV derived from S ⁴⁺ was observed, so that sulfur was partially contained in titanium sites constituting titanium oxide. It was confirmed that atoms were introduced.
When the antibacterial performance was evaluated by the above-described method using the powdery photocatalyst, the complete sterilization time was 7 hours, and the decomposition performance of harmful gas (acetaldehyde gas) was evaluated by the above- The complete decomposition time was 120 hours or more.
The results obtained in Comparative Examples 1 to 6 are shown in Table 4.

Based on the results obtained in Examples 1 to 9 and Comparative Examples 1 to 6, a summary of the antibacterial performance evaluation test results is shown in FIG. 1 and the harmful gas decomposition performance (acetaldehyde gas decomposition ability) evaluation test results. A summary of these is shown in FIG.
FIG. 1 shows the mass percentage of the total mass part of metal atoms constituting the antibacterial active metal species supported when the total amount of titanium atoms constituting the photocatalyst is 100 parts by mass (Cu atom / Ti atom). ) Is a plot of complete sterilization time.
FIG. 2 shows the mass percentage of the total mass part of metal atoms constituting the antibacterial active metal species supported when the total amount of titanium atoms constituting the photocatalyst is 100 mass parts (mass percentage of (Cu atoms / Ti atoms)) ) Is a plot of the complete decomposition time of acetaldehyde.

<Antimicrobial evaluation comparison test>
Using the photocatalysts obtained in Example 3 and Comparative Example 3, the antibacterial properties in the dark were evaluated in the same manner as in the above antibacterial performance (antibacterial activity against Staphylococcus aureus) evaluation test instead of under 1800 Lx light irradiation. .
Moreover, the test was done similarly using physiological saline as a blank (control) sample.
Table 5 and FIG. 3 show changes in the number of viable bacteria under light irradiation and under dark conditions with respect to time transition during the antibacterial performance evaluation test. In Table 5 and FIG. 3, the antibacterial evaluation result under 1800 Lx light irradiation is also described.

From FIG. 1, the photocatalysts obtained in Examples 1 to 9 comprise a first catalyst component and a second catalyst component having different amounts of supported antibacterial active metal species. It can be seen that the antibacterial activity is improved and the bacteria can be completely sterilized in a shorter time than the photocatalyst uniformly supporting the antibacterial active metal compound obtained in 1 to Comparative Example 6.
This is because the photocatalyst comprises the first catalyst component and the second catalyst component, thereby decomposing bacteria and virus components (photocatalytic action of titanium oxide) and bacterial metabolic function. This is considered to be because the action (mainly the antibacterial action of the active metal species) that inhibits the function efficiently as a synergistic effect. In FIG. 3, the photocatalyst obtained in Comparative Example 3 is not much different in the number of viable bacteria under the light irradiation of 1,800 Lx and in the dark (contribution due to the photocatalytic action of titanium oxide). However, the photocatalyst obtained in Example 3 significantly decreased the number of viable bacteria under 1,800 Lx light irradiation compared to the dark place (contribution by the photocatalytic action of titanium oxide was large). This can also be explained.
Moreover, from FIG. 2, the photocatalyst obtained in Example 1 to Example 9 is the same as the photocatalyst obtained in Comparative Example 1 to Comparative Example 6, and the supported amount of antibacterial active metal is the same. It can be seen that the acetaldehyde gas can be completely decomposed in a shorter time.

  According to the present invention, it is possible to provide a photocatalyst which has an improved antibacterial activity and an excellent sterilization rate and an excellent harmful gas decomposition rate, particularly under visible light irradiation.

Claims (5)

A photocatalyst comprising a first catalyst component and a second catalyst component,
When the content of titanium atoms constituting the first titanium oxide compound is 100 parts by mass with respect to the first titanium oxide compound, the first catalyst component converts the antibacterial active metal species in terms of metal atoms. 2.8 to 15 parts by mass supported,
When the content of titanium atoms constituting the second titanium oxide compound is 100 parts by mass with respect to the second titanium oxide compound, the second catalyst component converts the antibacterial active metal species in terms of metal atoms. A photocatalyst characterized by being supported by 0 to 1.5 parts by mass. When the total content of the first titanium oxide compound and the second titanium oxide compound is 100% by mass,
The content of the first titanium oxide compound is 7.5 to 72% by mass,
The photocatalyst according to claim 1, wherein the content of the second titanium oxide compound is 28 to 92.5 mass%.   Antibacterial activity carried on the first titanium oxide compound and the second titanium oxide compound when the total amount of titanium atoms constituting the first titanium oxide compound and the second titanium oxide compound is 100 parts by mass The photocatalyst according to claim 1 or 2, wherein the total amount of metal atoms constituting the metal species is 10 parts by mass or less.   The first titanium oxide compound or the second titanium oxide compound is a sulfur atom introduced titanium oxide, a nitrogen atom introduced titanium oxide, a sulfur atom introduced titanium oxide containing an iron compound or a nitrogen atom introduced titanium oxide containing an iron compound. The photocatalyst according to any one of claims 1 to 3.   The photocatalyst according to any one of claims 1 to 4, wherein in the first catalyst component or the second catalyst component, the antibacterial active metal species is at least one selected from a copper compound, a silver compound and metal silver. .

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