JP2016113417A - Antiviral composition, antiviral agent, photocatalyst and virus deactivation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiviral composition that expresses an excellent antiviral property in a bright place, and an antiviral agent and a photocatalyst, and a virus deactivation method.SOLUTION: An antiviral composition according to the present invention comprises silica-coated titanium oxide carrying BiVO, and a divalent copper compound. A virus deactivation method according to the present invention deactivates virus by using the antiviral composition, the antiviral agent or the photocatalyst according to the present invention.SELECTED DRAWING: None

Description

  The present invention relates to an antiviral composition that inactivates a virus, an antiviral agent, a photocatalyst, and a virus inactivating method including the antiviral composition.

  In recent years, new viruses have been discovered that adversely affect human health, and there is a strong concern about the spread of infection. A photocatalyst has attracted attention as a material for preventing the spread of such viral infections (see, for example, Patent Documents 1 and 2).

Patent Document 1 describes a phage virus inactivating agent comprising anatase-type titanium oxide containing copper in the range of CuO / TiO ₂ (mass% ratio) = 1.0 to 3.5. By finding that titanium oxide containing copper inactivates phage viruses, the inactivation agent of the invention described in Patent Document 1 has been completed. Patent Document 2 describes that platinum-supported tungsten oxide particles exhibit antiviral activity under visible light irradiation.

Bismuth vanadate (hereinafter referred to as “BiVO ₄ ”) is widely known as an excellent visible light responsive water-splitting photocatalyst (see, for example, Non-Patent Documents 1 and 2). The band gap is about 2.3 eV, which is smaller than the band gap of titanium oxide, which is 3.0 to 3.2 eV. That is, light (visible light) on a longer wavelength side can be effectively used for the photocatalyst as compared with titanium oxide, which is well known as a photocatalytic material. The urea hydrolysis method described in Patent Document 3 is widely known as a method for producing BiVO ₄ fine powder that is responsive to visible light at low pressure under atmospheric pressure.

Titanium oxide is widely known as an excellent carrier (for example, Non-Patent Document 4). In recent years, it has also been found that a composition containing titanium oxide carrying BiVO ₄ in a highly dispersed state and a divalent copper compound has extremely high antiviral activity. Furthermore, it is also known that the antiviral activity is improved as BiVO ₄ is more finely supported.

Japanese Patent No. 4646210 JP 2011-136984 A Japanese Patent No. 3790189

J. et al. Phys. Chem. B2006, 110, pp11352-11360 J. et al. Am. Chem. Soc. 1999, 121, pp11459-11467 Photofunctional Materials Study Group, Newsletter Photocatalyst vol. 37, p.31-32 (2012) Nakazawa Yoshihiko (2008). Catalyst Handbook, Kodansha Co., Ltd.

In Patent Document 1, a sample of CuO / TiO ₂ is antiviral under ultraviolet irradiation (Examples 1 to 4, Comparative Examples 3 to 4), under visible light irradiation (Comparative Example 2), and in the dark (Comparative Example 1). We are conducting sex assessment. Under the visible light irradiation (Comparative Example 2) and in the dark (Comparative Example 1), there was no phage / virus inactivating effect. By the way, the light of the white LED fluorescent lamp which has spread rapidly in recent years does not include ultraviolet light. The phage / virus inactivating agent described in Patent Document 1 has no antiviral activity even in the dark and under visible light irradiation, and therefore is expected to have no antiviral activity even under a white LED fluorescent lamp. Is done. For this reason, the application to the interior material of the phage virus inactivating agent described in Patent Document 1 is extremely limited.
On the other hand, the platinum-supported tungsten oxide particles described in Patent Document 2 exhibit antiviral properties under visible light irradiation, but platinum and tungsten oxide are extremely rare and expensive. The above use is difficult.

In addition, when the method described in Patent Document 3 is applied and BiVO ₄ is supported on titanium oxide having a BET specific surface area of less than 25 m ² / g and a divalent copper compound is further contained, antiviral is extremely high in a bright place. Activity is expressed. However, if the BET specific surface area is less than 25 m ² / g, the dispersibility when slurried and the transparency when applied to the material are not good. Therefore, when trying to support BiVO ₄ on titanium oxide having a BET specific surface area of 25 m ² / g or more, the reaction at the time of supporting BiVO ₄ does not proceed well. As a result, even when a divalent copper compound is contained, anti-phage Little activity was expressed.
As described above, conventionally, no practical antiviral composition has been provided in a bright place including visible light.

  The present invention has been made to solve the above-described problems, and an antiviral composition capable of expressing excellent antiviral properties even in a bright place without ultraviolet light, and an antiviral composition containing the antiviral composition. It is an object of the present invention to provide a virus agent, a photocatalyst containing the antiviral composition, and a virus inactivation method.

The inventors of the present invention show that a composition containing a silica-coated titanium oxide carrying BiVO ₄ and a divalent copper compound exhibits excellent antiviral activity under visible light irradiation, and silica-coated oxidation as a carrier. By using titanium, it is possible to carry BiVO ₄ on titanium oxide having a BET specific surface area of 25 m ² / g or more, and further, an antiviral composition containing silica-coated titanium oxide carrying BiVO ₄ and a divalent copper compound. The present inventors have found that an antiviral composition, an antiviral agent, and a photocatalyst that express excellent antiviral properties in a bright place without ultraviolet light can be obtained using the product, and the present invention has been completed.
That is, the present invention provides the following inventions [1] to [18].

[1] An antiviral composition containing a silica-coated titanium oxide carrying BiVO ₄ and a divalent copper compound.
[2] The antiviral composition according to the above [1], wherein the silica-coated titanium oxide has a BET specific surface area of 25 m ² / g or more.
[3] The antiviral composition according to the above [1] or [2], wherein the silica-coated titanium oxide is produced by a gas phase method.
[4] The antiviral composition according to any one of [1] to [3], wherein the proportion of silica is 1 to 30% by mass with respect to 100 parts by mass of the silica-coated titanium oxide.
[5] The antiviral composition according to any one of the above [1] to [4], wherein the mass of BiVO ₄ is 1 to 20 parts by mass with respect to 100 parts by mass of the silica-coated titanium oxide.
[6] The above [1] to [5], wherein the ratio of copper element in the divalent copper compound is 0.01 to 20 parts by mass with respect to 100 parts by mass in total of the silica-coated titanium oxide and BiVO ₄ . The antiviral composition according to any one of the above.
[7] The divalent copper compound includes (a) the general formula (1):
Cu ₂ (OH) ₃ X (1)
(In the formula, X represents an anion)
(B) Divalent copper halide, (c) Divalent copper inorganic acid salt, (d) Divalent copper organic acid salt, (e) Cupric oxide Any one of the above [1] to [6], which is one or more selected from the group consisting of: (f) copper sulfide, (g) copper (II) azide, and (h) copper silicate 2. The antiviral composition according to 1.
[8] In the above [7], X in the general formula (1) is one or more selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of an inorganic acid, and an OH group. The antiviral composition as described.
[9] In the above [7] or [8], X in the general formula (1) is one selected from the group consisting of Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 . The antiviral composition as described.
[10] The antibacterial device according to [7], wherein the (b) divalent copper halide is one or more selected from the group consisting of copper chloride, copper fluoride, and copper bromide. Viral composition.
[11] (c) Divalent copper inorganic acid salts include copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium sulfate copper, amide copper sulfate, ammonium copper chloride, The antiviral composition according to [7] above, which is one or more selected from the group consisting of copper pyrophosphate and copper carbonate.
[12] The antiviral composition according to [7] above, wherein the organic salt of (d) divalent copper is a divalent copper carboxylate.
[13] The antiviral composition according to [7] or [8] above, wherein the divalent copper compound is a hydroxyl group-containing divalent copper compound represented by the general formula (1).
[14] The antiviral composition according to any one of the above [1] to [13], which has a virus inactivating ability of 99.0% or more after 60 minutes of visible light irradiation with an illuminance of 800 lux.
[15] The silica-coated oxide on which BiVO ₄ obtained by heating an acidic suspension composed of silica-coated titanium oxide, bismuth ions, vanadate ions, urea, and water under atmospheric pressure is supported. The antiviral composition according to any one of [1] to [14], comprising titanium and the divalent copper compound.
[16] An antiviral agent comprising the antiviral composition according to any one of [1] to [15].
[17] A photocatalyst containing the antiviral composition according to any one of [1] to [15].
[18] Virus inactivation using the antiviral composition according to any one of [1] to [15] above, the antiviral agent according to [16] above, or the photocatalyst according to [17] above A virus inactivation method.

  ADVANTAGE OF THE INVENTION According to this invention, the antiviral composition, the antiviral agent, photocatalyst, and virus inactivation method which express the outstanding antiviral property in the bright place without an ultraviolet light can be provided.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments. In this specification, “a bright place without ultraviolet light (sometimes simply referred to as“ light place ”) is a place where visible light having a wavelength of 400 nm or more exists but ultraviolet light is not substantially present. That means.

[Antiviral composition]
The antiviral composition of the present invention is a composition comprising a silica-coated titanium oxide carrying BiVO ₄ and a divalent copper compound, and exhibits excellent antiviral properties in a light place.

<Silica-coated titanium oxide>
By using silica-coated titanium oxide, BiVO ₄ can be supported on titanium oxide having a BET specific surface area of 25 m ² / g or more. When BiVO ₄ is supported, a step of dispersing titanium oxide in a solvent and adding bismuth ions and vanadate ions is generally assumed. At that time, when a titanium oxide having a BET specific surface area of 25 m ² / g or more is used, since the surface energy of titanium oxide is high, bismuth ions and vanadate ions are quickly and strongly adsorbed on the titanium oxide surface, and the subsequent steps It is considered that BiVO ₄ is hardly precipitated even after passing through. On the other hand, when silica-coated titanium oxide is used, the surface energy of titanium oxide is reduced by silica, bismuth ions and vanadate ions are hardly adsorbed, and BiVO ₄ is gradually formed on the silica-coated titanium oxide through the subsequent steps. It is thought that it precipitates.

The silica-coated titanium oxide of the present invention is not particularly limited as long as it can carry BiVO ₄ . As a method for coating silica with titanium oxide, for example, a method prepared by a liquid phase method as described in Japanese Patent No. 5181408, or a gas phase as described in Japanese Patent Application Laid-Open No. 2004-231952, for example. And those prepared by the method.
Among these, silica-coated titanium oxide produced by a vapor phase method is preferable from the viewpoint of production cost.

The titanium oxide of the silica-coated titanium oxide is preferably titanium dioxide (TiO ₂ ), and its crystal form is preferably anatase type titanium oxide, rutile type titanium oxide or brookite type titanium oxide, more preferably anatase type titanium oxide or rutile type titanium oxide type. preferable. Silica of the silica-coated titanium oxide is preferably silicon dioxide (SiO ₂ ).

The BET specific surface area (value before supporting BiVO ₄ ) of the silica-coated titanium oxide used in the present invention is preferably 25 m ² / g or more, more preferably 25 to 1000 m ² / g, and further preferably 30. ~500m a ² / g, particularly preferably 40 to 300 m ² / g. When the BET specific surface area of the silica-coated titanium oxide is 25 m ² / g or more, the dispersibility when slurried and the transparency when applied to the material are improved. When the BET specific surface area of the silica-coated titanium oxide is 1000 m ² / g or less, handling of the antiviral composition becomes easy in application of the antiviral composition such as coating of the antiviral composition. Here, the BET specific surface area is a specific surface area measured by a BET three-point method by nitrogen adsorption.

The ratio of silica in the silica-coated titanium oxide used in the present invention is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and further preferably 5 to 25% by mass in the silica-coated titanium oxide. is there. When the amount of silica is 1% by mass or more, the reaction for supporting BiVO ₄ proceeds favorably, and when the amount of silica is 30% by mass or less, the amount of relatively expensive silica raw material used can be suppressed. Is.

<BiVO ₄ >
BiVO ₄ supported on silica-coated titanium oxide of the present invention exhibits high photocatalytic activity in the visible light region. Examples of the method of supporting BiVO ₄ on silica-coated titanium oxide include a solid phase method and a liquid phase method. Any of them can be used for the antiviral composition of the present invention, but a liquid phase method is preferred, and a urea hydrolysis method (see Patent Document 3) is more preferred. The method of manufacturing the known BiVO _4, for example, in the manufacturing method described above of BiVO _4, the BiVO ₄ by adding silica-coated titanium oxide in BiVO ₄ synthesis can be carried on the silica-coated titanium oxide.

The mass ratio of BiVO ₄ is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 3 to 10 parts by mass with respect to 100 parts by mass of the silica-coated titanium oxide. When the mass of BiVO ₄ is 1 to 20 parts by mass with respect to 100 parts by mass of silica-coated titanium oxide, the antiviral properties in the light place of the antiviral composition are improved, and the antiviral composition is Presenting a bright yellow color can be suppressed. Moreover, the ratio of Bi and V elements in the composition can be reduced, which is economical.

<Divalent copper compound>
The divalent copper compound used in the present invention is a copper compound having a copper valence of 2. A divalent copper compound alone does not exhibit antiviral properties in the light. However, when combined with silica-coated titanium oxide supporting BiVO ₄ , antiviral properties in a light place are expressed in the divalent copper compound. The divalent copper compound is not particularly limited as long as it is a copper compound having a copper valence of 2. For example, the divalent copper compound is (a) the following general formula (1):
Cu ₂ (OH) ₃ X (1)
(In the formula, X represents an anion)
(B) Divalent copper halide, (c) Divalent copper inorganic acid salt, (d) Divalent copper organic acid salt, (e) Cupric oxide , (F) copper sulfide, (g) copper (II) azide, and (h) one or more selected from the group consisting of copper silicate.

Preferred X (anions) of general formula (1) are halogens such as Cl, Br and I, conjugated bases of carboxylic acids such as CH ₃ COO, NO ₃ and inorganic acids such as (SO ₄ ) _1/2. One selected from the group consisting of a conjugated base and an OH group. More preferable X in the general formula (1) is one selected from the group consisting of Cl, CH ₃ COO, NO ₃ , (SO ₄ ) _1/2 , and an OH group. Among these, halogen is more preferable, and Cu ₂ (OH) ₃ Cl is most preferable.

  The preferred (b) divalent copper halide is one or more selected from the group consisting of copper chloride, copper fluoride, and copper bromide. More preferred is copper chloride.

  Preferred inorganic salt of (c) divalent copper is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium sulfate copper, amide copper sulfate, ammonium chloride copper, pyrophosphate One or more selected from the group consisting of copper and copper carbonate. More preferred is copper sulfate.

  (D) A divalent copper organic acid salt is preferably a divalent copper carboxylate. Preferred divalent copper carboxylates include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, misty acid Copper, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, melittic acid Copper, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetylacetone, copper ethylacetoacetate, isoyoshichi Copper herbate, copper β-resorcylate, copper diacetoacetate, copper formyl succinate, copper salicylamate, copper bis (2-ethylhexanoate), copper sebacate, and naphthenic acid One or more ones selected from the group consisting of and the like. More preferred is copper acetate.

  Other preferred divalent copper compounds are selected from the group consisting of copper oxine, copper acetylacetone, copper ethylacetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, and copper dimethyldithiocarbamate. 1 type or 2 types or more to be mentioned.

  The divalent copper compound of the present invention is preferably (a) a hydroxyl group-containing divalent copper compound represented by the general formula (1), (b) a divalent copper halide, and (c) an inorganic divalent copper. And (d) an organic acid salt of divalent copper. Moreover, since there are few impurities and cost does not start, the divalent copper compound of this invention is still more preferably a hydroxyl group-containing divalent copper compound represented by the above general formula (1). The (a) hydroxyl group-containing divalent copper compound represented by the general formula (1) may be an anhydride or a hydrate.

The copper element mass (mass ratio of Cu) in the divalent copper compound contained in the antiviral composition of the present invention is preferably 0.01 with respect to a total of 100 parts by mass of silica-coated titanium oxide and BiVO _4. It is -20 mass parts, More preferably, it is 0.1-20 mass parts, More preferably, it is 0.1-15 mass parts, Most preferably, it is 0.3-10 mass parts. When the mass of copper element in the divalent copper compound is 0.01 parts by mass or more with respect to 100 parts by mass of the total of silica-coated titanium oxide and BiVO ₄ , antiviral properties and antibacterial properties in a bright place are improved. Further, when the mass of copper element in the divalent copper compound is 20 parts by mass or less with respect to 100 parts by mass in total of the silica-coated titanium oxide and BiVO ₄ , the surface of the silica-coated titanium oxide supporting BiVO ₄ is 2 It is prevented from being covered with a valent copper compound, the photocatalytic activity of the antiviral composition can be increased, and the virus can be inactivated with a small amount of the antiviral composition, which makes it economical.

Here, copper element mass in divalent copper compound to the total 100 parts by weight of the silica-coated titanium oxide and BiVO ₄ can be calculated in the bivalent copper compound precursor, the charged amount of the silica-coated titanium oxide and BiVO ₄ . The antiviral composition of the present invention was heated in a hydrofluoric acid solution and completely dissolved to prepare a solution. Then, using an ICP emission analyzer (manufactured by Shimadzu Corporation, model number ICPS-7500), the extract extracted from the solution can be analyzed by the ICP method to determine the amount of copper element.

In the antiviral composition, the divalent copper compound may be supported on silica-coated titanium oxide and / or BiVO ₄ . In the antiviral composition, the divalent copper compound may be dispersed in silica-coated titanium oxide and BiVO ₄ without being supported on silica-coated titanium oxide and / or BiVO ₄ .

As described above, the antiviral composition of the present invention contains, as essential components, silica-coated titanium oxide on which BiVO ₄ is supported and a divalent copper compound, but within a range that does not impair the object of the present invention. Other optional components may be contained. However, from the viewpoint of improving antiviral properties, the total content of the silica-coated titanium oxide carrying BiVO ₄ and the divalent copper compound in the antiviral composition is the total mass of the antiviral composition. Is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass.

  The antiviral composition of the present invention can be a composition having a virus inactivating ability of 99.0% or more in 60 minutes of irradiation with visible light having an illuminance of 800 lux.

Further, the antiviral composition of the present invention is a BiVO obtained by heating an acidic suspension comprising silica-coated titanium oxide, bismuth ions, vanadate ions, urea and water under atmospheric pressure. ₄ is a composition containing silica-coated titanium oxide supporting ₄ and a divalent copper compound. Specifically, it can be produced by the method described in the examples.

[Antiviral agents and photocatalysts]
The antiviral agent and photocatalyst of the present invention include the antiviral composition of the present invention. Thereby, the antiviral agent and photocatalyst of the present invention have excellent antiviral properties in the light.

[Usage form of antiviral composition, antiviral agent and photocatalyst]
The usage forms of the antiviral composition, antiviral agent and photocatalyst of the present invention (hereinafter sometimes referred to as “antiviral composition of the present invention”) are not particularly limited.
For example, the antiviral composition of the present invention may be used in a solid form such as fine powder and granules. In this case, for example, the antiviral composition of the present invention is used by filling a predetermined container. Alternatively, the antiviral composition of the present invention may be used in a usage form in which the antiviral composition of the present invention is contained on the surface and / or inside of a predetermined substrate. In general, the latter form of use is preferred. Examples of the base material include a single base material made of general members such as fibers, metals, ceramics, and glass, and a composite base material made of two or more members of the above-described members. However, the substrate is not limited to these.

  The antiviral composition of the present invention may be contained in a coating agent such as floor polish that can be peeled off by an appropriate means. Further, the antiviral composition or the like of the present invention may be immobilized on a predetermined film, and the antiviral composition or the like of the present invention may be exposed on the surface of the continuous film. In addition, the antiviral composition of the present invention may be used in the form of a paint prepared using a solvent in which the antiviral composition of the present invention is dispersed.

  For the material in which the antiviral composition or the like of the present invention is immobilized on the substrate surface, the antiviral composition or the like of the present invention is immobilized on the substrate surface by using a general immobilization means such as a binder. Materials that have been converted into materials. Either an organic binder or an inorganic binder can be used as a binder for immobilizing the antiviral composition of the present invention, but it is preferable to use an inorganic binder in order to avoid decomposition of the binder by a photocatalytic substance. . The kind of binder is not particularly limited. Examples of the inorganic binder include silica-based inorganic binders that are usually used for fixing the photocatalytic substance to the substrate surface. Examples of the organic binder include a polymer binder that can form a thin film by polymerization and solvent volatilization.

  For the material containing the antiviral composition or the like of the present invention in the base material, for example, the antiviral composition or the like of the present invention is dispersed in a resin to prepare a dispersion, and the dispersion is cured. The material obtained by is mentioned. As the resin for dispersing the antiviral composition of the present invention, both natural resins and synthetic resins can be used. Synthetic resins include, for example, acrylic resins, phenol resins, polyurethane resins, acrylonitrile / styrene copolymer resins, acrylonitrile / butadiene / styrene copolymer (ABS) resins, polyester resins, and epoxy resins. It is not limited.

  The place where the antiviral composition of the present invention is used is not particularly limited. Further, the antiviral composition or the like of the present invention can be used in the presence of water (for example, in water and seawater), in a dry state (for example, in a low humidity state in winter, etc.), in a high humidity state, or in an organic matter. Even in the presence of coexistence, it has excellent virus inactivating properties and can inactivate viruses continuously. For example, the antiviral composition of the present invention can be placed on walls, floors, ceilings, and the like. Also, any object such as hospitals and factories such as buildings, machine tools, measuring devices, interiors and parts of electrical appliances (for example, interiors of refrigerators, washing machines, dishwashers, etc. and filters of air cleaners) The antiviral composition of the present invention can be applied to the product.

  Conventionally, as a countermeasure against influenza, an air cleaning machine has been proposed in which a ceramic filter or a nonwoven fabric filter is coated with titanium oxide and a light source for irradiating the filter with ultraviolet light is incorporated. However, when the antiviral composition or the like of the present invention is used for a filter of an air cleaner, an ultraviolet light source is not necessary, thereby reducing the cost of the air cleaner and increasing the safety of the air cleaner. it can.

[Virus inactivation method]
The present invention provides a virus inactivation method, wherein a virus is inactivated using the antiviral composition of the present invention, the antiviral agent of the present invention or the photocatalyst of the present invention. As described above, since the antiviral composition of the present invention exhibits antiviral properties, it is possible to inactivate viruses using the antiviral composition of the present invention. Moreover, since the antiviral agent and photocatalyst of this invention contain the antiviral composition of this invention, a virus can be inactivated using the antiviral agent or photocatalyst of this invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. Samples of Examples 1 to 4 and Comparative Examples 1 to 4 were produced as follows.

Silica-coated titanium oxide A (F-4S05, anatase type manufactured by Showa Denko Ceramics Co., Ltd.), silica-coated titanium oxide B (F-4S20, anatase type manufactured by Showa Denko Ceramics Co., Ltd.) used in the following examples Table 1 shows the silica amount and BET specific surface area of Titanium Oxide A and T-4 (manufactured by Showa Denko Ceramics Co., Ltd., F-4, anatase type). The silica amount of the silica-coated titanium oxide A is quantified by high-frequency inductively coupled plasma emission spectroscopy, and is mass% as silica (SiO ₂ ) in the silica-coated titanium oxide. The BET specific surface area was measured by the BET three-point method by nitrogen adsorption.

<Example 1>
A suspension was prepared by suspending 10.000 g of silica-coated titanium oxide A (manufactured by Showa Denko Ceramics Co., Ltd., product number F-4S05) in 300 mL of distilled water. Next, _{Bi (NO} 3) of 0.752g 3 · _5H 2 O (manufactured by Kanto Chemical Co.) and 0.182g _NH 4 VO ₃ 3.0mL and was dissolved (Kanto Chemical Co., Ltd.) each 4.0 mL of a 5.0 mol / L HNO ₃ solution was prepared, and a suspension of an HNO ₃ solution in which Bi (NO ₃ ) ₃ .5H ₂ O was dissolved and an HNO ₃ solution in which NH ₄ VO ₃ was dissolved were in this order. I put it in. Then, stirring and mixing were performed for 30 minutes at a rotational speed of 400 rpm with a magnetic stirrer. The obtained suspension was filtered and dried to prepare a sample for measuring Bi and V adsorption amount of the antiviral composition.

<Example 2>
A sample of Example 2 was produced in the same manner as in Example 1 except that silica-coated titanium oxide A was changed to silica-coated titanium oxide B (manufactured by Showa Denko Ceramics Co., Ltd., product number F-4S20).

<Example 3>
Suspension was prepared by suspending 10.000 g of silica-coated titanium oxide A in 300 mL of distilled water, and the pH of the suspension was adjusted to 1.3 with 5 mol / L HNO ₃ aqueous solution. Next, _{Bi (NO} 3) of 0.752g 3 · _5H 2 O (manufactured by Kanto Chemical Co.) and 0.182g _NH 4 VO ₃ 3.0mL and was dissolved (Kanto Chemical Co., Ltd.) each prepare HNO ₃ solution 5 mol / L of _{4.0mL, Bi (NO 3) 3} · 5H 2 HNO 3 solution O was dissolved, in suspension in the order of HNO ₃ solution of _NH 4 VO ₃ I put it in. Thereafter, 10.000 g of urea (manufactured by Kanto Chemical Co., Inc.) was put into the suspension, heated to a temperature of 80 ° C. on a hot stirrer, and maintained at a temperature of 80 ° C. for 8 hours. The obtained suspension was filtered and dried to obtain BiVO ₄ / silica-coated titanium oxide A (supported by 5 parts by mass as BiVO _{4 with} respect to 100 parts by mass of silica-coated titanium oxide).

Distilled water 100mL to suspend the BiVO ₄ / silica-coated titanium oxide powder A of 6.000g suspension prepared by, 0.081 g (copper per 100 parts by weight of BiVO ₄ / silica-coated titanium oxide powder A 0.5 parts by mass) of CuCl ₂ .2H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added to the suspension and stirred for 10 minutes. A 1.0 mol / L aqueous solution of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added so that the pH of the suspension was 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry. The slurry was filtered, and the resulting powder was washed with pure water, dried at 80 ° C., and crushed with a mixer. A sample was prepared in the same manner as in Example 1. CuCl ₂ .2H ₂ O is hydrolyzed to Cu ₂ (OH) ₃ Cl. The pH meter was used using D-51 manufactured by Horiba, Ltd.

<Example 4>
A sample of Example 4 was produced in the same manner as in Example 3 except that silica-coated titanium oxide A was changed to silica-coated titanium oxide B.

<Comparative Example 1>
A sample of Comparative Example 1 was prepared in the same manner as in Example 1 except that the silica-coated titanium oxide A was changed to titanium oxide A (manufactured by Showa Denko Ceramics Co., Ltd., product number F-4).

<Comparative Example 2>
A sample of Comparative Example 2 was produced in the same manner as in Example 3 except that the silica-coated titanium oxide A was changed to titanium oxide A.

<Comparative Example 3>
A suspension was prepared by suspending 10.000 g of silica-coated titanium oxide B in 300 mL of distilled water, and the pH of the suspension was adjusted to 1.3 with a 5.0 mol / L HNO ₃ aqueous solution. Next, _{Bi (NO} 3) of 0.752g 3 · _5H 2 O (manufactured by Kanto Chemical Co.) and 0.182g _NH 4 VO ₃ 3.0mL and was dissolved (Kanto Chemical Co., Ltd.) each 4.0 mL of a 5.0 mol / L HNO ₃ solution was prepared, and a suspension of an HNO ₃ solution in which Bi (NO ₃ ) ₃ .5H ₂ O was dissolved and an HNO ₃ solution in which NH ₄ VO ₃ was dissolved were in this order. I put it in. Thereafter, 10.000 g of urea (manufactured by Kanto Chemical Co., Inc.) was put into the suspension, heated to a temperature of 80 ° C. on a hot stirrer, and maintained at a temperature of 80 ° C. for 8 hours. The sample of Comparative Example 3 was produced by filtering and drying the obtained suspension. The pH meter was used using D-51 manufactured by Horiba, Ltd.

<Comparative example 4>
Suspension is prepared by suspending 6.000 g of silica-coated titanium oxide B powder in 100 mL of distilled water, and 0.081 g (100 parts by mass of silica-coated titanium oxide A powder is 0.5 parts by mass of copper) CuCl ₂ .2H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added to the suspension and stirred for 10 minutes. A 1 mol / L aqueous solution of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added so that the pH of the suspension was 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry. The slurry was filtered, and the obtained powder was washed with pure water, dried at 80 ° C., and crushed with a mixer to prepare a sample of Comparative Example 4.

  Table 2 shows the amounts of Bi and V adsorbed on the silica-coated titanium oxide and titanium oxide of Examples 1 and 2 and Comparative Example 1. The mass parts of adsorbed Bi and V are values with respect to 100 parts by mass of Bi or V input. A method of measuring the adsorption amounts of Bi and V will be described later.

The compositions of the samples of Examples 3 and 4 and the samples of Comparative Examples 2 to 4 are shown in Table 3 below together with the evaluation results. _Further, Cu 2 _(OH) 3 Cl in parts by weight, per 100 parts by weight of the silica-coated titanium oxide or titanium oxide and BiVO _4, which is parts by weight when converted into Cu. Details of the measurement method will be described later.

<Evaluation method>
In addition, the composition and evaluation about the samples of Examples 1-4 and Comparative Examples 1-4 described in Tables 1 to 3 were measured by the following methods.

(High-frequency inductively coupled plasma emission spectroscopy)
The mass% of Bi and V adsorbed on titanium oxide and silica-coated titanium oxide in Bi and V charged in Examples 1 and 2 and Comparative Example 1 was quantified by high frequency inductively coupled plasma optical emission spectrometry. Specifically, each sample was heated in a hydrofluoric acid solution and completely dissolved to prepare a solution. Then, using an ICP emission analyzer (manufactured by Shimadzu Corporation, model number ICPS-7500), the extract extracted from the solution was analyzed, and Bi and V in the composition were quantified. The results are shown in Table 2.

(X-ray diffraction measurement)
X-ray diffraction measurement was performed on the samples of Examples 3 and 4 and the samples of Comparative Examples 2 and 3, and the compounds consisting of Bi and V present in the samples were identified. “X'pertPRO” manufactured by PANalytical is used as a measuring apparatus, a copper target is used, a Cu-Kα1 wire is used, a tube voltage of 45 kV, a tube current of 40 mA, a measurement range 2θ = 20 to 100 deg, a sampling width of 0. X-ray diffraction measurement was performed under the conditions of 0167 deg and a scanning speed of 3.3 deg / min. The results are shown in Table 3.

(BET specific surface area)
The BET specific surface area of silica-coated titanium oxide A, silica-coated titanium oxide B, and titanium oxide A was measured using a fully automatic BET specific surface area measuring device “Macsorb, HM model-1208” manufactured by Mountec Co., Ltd. Was measured using nitrogen. The results are shown in Table 1.

(Evaluation of antiviral properties under irradiation with visible light: measurement of LOG (N / N ₀ ))
The antiviral properties of the samples of Examples 3 and 4 and Comparative Examples 2 to 4 were confirmed by the following method by model experiments using bacteriophages. A method of using the inactivation ability against bacteriophage as a model of antiviral properties is described in, for example, Appl. Microbiol Biotechnol. 79, pp. 127-133 (2008), and it is known that reliable results can be obtained by this method. This measurement is based on JIS R 1706.

Specifically, the samples of Examples 3 and 4 and the samples of Comparative Examples 2 to 4 were each applied on a glass plate (50 mm × 50 mm × 1 mm) to prepare evaluation samples. 2.5 mg of the samples of Examples 3 and 4 and the samples of Comparative Examples 2 to 4 were applied on the glass plate to prepare an evaluation sample having a coating amount per unit area of 1.0 g / m ² .

A filter paper was laid in the deep petri dish, and a small amount of sterilized water was added. The sample for evaluation described above was placed on the filter paper. On top of this, 1/500 NB was used to prepare a bacteriophage infectious titer of about 6.7 × 10 ⁶ to about 2.6 × 10 ⁷ pfu / ml, and 100 μL of Qβ phage (NBRC20012) suspension was added dropwise. Then, a PET (polyethylene terephthalate) film was covered to bring the sample surface into contact with the phage. This deep petri dish covered with a glass plate was used as a measurement set. A plurality of similar measurement sets were prepared.

  Further, a 15 W white fluorescent lamp (manufactured by Panasonic Corporation, full white fluorescent lamp, FL15N) attached to an ultraviolet cut filter (Nitto Resin Kogyo Co., Ltd., N-113) was used as a light source. A plurality of sets for measurement were allowed to stand at a position where the illuminance was 800 lux (illuminance meter: measured by Topcon Corporation, IM-5). After 60 minutes from the start of light irradiation, the phage concentration of the sample on the glass plate was measured. In addition, the illuminance of the room at the time of measurement was set to be 200 lux or less. The elapsed time from the start of light irradiation was measured using a commercially available stopwatch.

The phage concentration was measured by the following method. The sample on the glass plate was infiltrated into 9.9 ml of phage recovery solution (SCDLP medium) and shaken for 10 minutes with a shaker.
This phage recovery solution was appropriately diluted with physiological saline containing peptone. Separately cultured 5.0 × 10 ^{8 to} 2.0 × 10 ⁹ cells / ml Escherichia coli (NBRC106373) culture solution and calcium added LB soft agar medium were mixed with 1 ml of the above diluted solution. After the addition and mixing, this solution was spread on a calcium-added LB agar medium and cultured at 37 ° C. for 15 hours, and then the number of phage plaques was visually measured. The phage concentration N was determined by multiplying the number of plaques obtained by the dilution factor of the phage recovery solution.

The phage relative concentration (LOG (N / N ₀ )) was determined from the initial phage concentration N ₀ and the phage concentration N after a predetermined time. Note that the smaller the value of LOG (N / N ₀ ), that is, the greater the absolute value, the better the antiviral properties of the sample. The results are shown in Table 3.

<Result>
The results obtained in the above examples and comparative examples will be described.

(High-frequency inductively coupled plasma emission spectroscopy)
From the results shown in Table 2 of the high frequency inductively coupled plasma emission spectroscopic analysis, it was found that silica-coated titanium oxide hardly adsorbs bismuth ions and vanadate ions compared to titanium oxide.

(X-ray diffraction measurement)
From the results shown in Table 3 of the XRD diffraction measurement, it was found that the compound composed of Bi and V present in the samples of Examples 3 and 4 and Comparative Example 3 was BiVO ₄ . The sample of Comparative Example 2 was weak in peak intensity and could not be identified.

(Evaluation of antiviral properties under irradiation with visible light: measurement of LOG (N / N ₀ ))
As shown in Table 3, the antiviral properties under visible light irradiation show high antiviral activity in Examples 3 and 4 of the combination of silica-coated titanium oxide, BiVO ₄ and divalent copper compound. I understood that.

From the comparison of Examples 1 and 2 and Comparative Example 1 in Table 1, it became clear that silica-coated titanium oxide hardly adsorbs bismuth ions and vanadate ions, and that the effect becomes higher as the silica coating amount increases. The samples of Examples 3 and 4 were found to have a virus inactivation ability of 99.0% or more in 60 minutes of visible light irradiation with an illuminance of 800 lux. From the comparison between Examples 3 and 4 and Comparative Example 2 in Table 3, it was confirmed that as the silica coating amount was increased, BiVO ₄ was more easily carried, and as a result, the antiviral activity was improved. Furthermore, from the comparison between Example 4 and Comparative Examples 3 and ₄ , it was confirmed that the combination of silica-coated titanium oxide, BiVO ₄ , and a divalent copper compound was important in order to develop antiviral activity.

Claims (18)

An antiviral composition comprising silica-coated titanium oxide carrying BiVO ₄ and a divalent copper compound. The antiviral composition according to claim 1, wherein the silica-coated titanium oxide has a BET specific surface area of 25 m ² / g or more.   The antiviral composition according to claim 1 or 2, wherein the silica-coated titanium oxide is produced by a gas phase method.   The antiviral composition of any one of Claims 1-3 whose ratio of a silica is 1-30 mass% in 100 mass parts of silica covering titanium oxides. The proportion of BiVO ₄ is, the silica-coated is 1 to 20 parts by weight with respect to the titanium oxide to 100 parts by mass, the antiviral composition according to any one of claims 1-4. The elemental copper mass in divalent copper compound, wherein 0.01 to 20 parts by weight per 100 parts by weight of the silica-coated titanium oxide and BiVO _4, according to any one of claims 1 to 5 Antiviral composition. The divalent copper compound includes (a) the general formula (1):
Cu ₂ (OH) ₃ X (1)
(In the formula, X represents an anion)
(B) Divalent copper halide, (c) Divalent copper inorganic acid salt, (d) Divalent copper organic acid salt, (e) Cupric oxide Or (f) copper sulfide, (g) copper (II) azide and (h) one or more selected from the group consisting of copper silicate. The antiviral composition as described.   The antiviral property according to claim 7, wherein X in the general formula (1) is one or more selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of an inorganic acid, and an OH group. Composition. X in the general formula (1) _may, Cl, CH 3 COO, NO is ₃ and _{(SO 4)} 1 kind selected from the group consisting of _1/2, antiviral composition according to claim 7 or 8 object.   The antiviral composition according to claim 7, wherein the halide of (b) divalent copper is one or more selected from the group consisting of copper chloride, copper fluoride, and copper bromide. .   (C) Divalent copper inorganic acid salt is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium sulfate, copper amidosulfate, copper chloride ammonium, copper pyrophosphate The antiviral composition according to claim 7, wherein the composition is one or more selected from the group consisting of copper carbonate.   The antiviral composition according to claim 7, wherein the organic salt of (d) divalent copper is a divalent copper carboxylate.   The antiviral composition according to claim 7 or 8, wherein the divalent copper compound is a hydroxyl group-containing divalent copper compound represented by the general formula (1).   The antiviral composition according to any one of claims 1 to 13, which has a virus inactivating ability of 99.0% or more in 60 minutes of irradiation with visible light having an illuminance of 800 lux. Silica-coated titanium oxide, bismuth ions, vanadate ions, urea, and the silica-coated titanium oxide supporting BiVO ₄ obtained by heating an acidic suspension composed of water under atmospheric pressure; The antiviral composition according to any one of claims 1 to 14, comprising the divalent copper compound.   The antiviral agent containing the antiviral composition of any one of Claims 1-15.   The photocatalyst containing the antiviral composition of any one of Claims 1-15.   A virus inactivating method comprising inactivating a virus using the antiviral composition according to any one of claims 1 to 15, the antiviral agent according to claim 16, or the photocatalyst according to claim 17. .