TW201632071A - Antiviral composition, antiviral agent, photo-catalyst, and virus inactivation process - Google Patents

Abstract

This invention provides an antiviral composition, an antiviral agent, a photo-catalyst and a virus inactivation process. The antiviral composition of this invention comprises titania covered by silica carrying BiVO4 and a bivalent copper compound. The virus inactivation process of this invention uses the antiviral composition, the antiviral agent or the photo-catalyst of this invention to inactivate the virus.

Description

Antiviral composition, antiviral agent, photocatalyst and virus inertization method

The present invention relates to an antiviral composition which makes a virus inert, an antiviral agent containing the antiviral composition, a photocatalyst, and a virus inactivation method.

In recent years, new viruses that have a bad influence on human health have been found, and there is a strong concern about the expansion of the infection. Photocatalysts are attracting attention as materials for preventing the expansion of such viral infections (for example, refer to Patent Documents 1 and 2).

Patent Document 1 describes an bacteriophage ‧ virus inerting agent made of anatase-type titanium oxide containing copper in a range of CuO/TiO ₂ (% by mass) = 1.0 to 3.5. The bacteriophage ‧ virus was made inert by the copper-containing titanium oxide, and the inerting agent of the invention described in Patent Document 1 was completed.

Patent Document 2 discloses that platinum-supported tungsten oxide particles exhibit antiviral activity under visible light irradiation.

It is known that bismuth vanadate (hereinafter referred to as "BiVO ₄ ") can be widely used as an excellent visible light responsive type water-decomposable photocatalyst (see, for example, Non-Patent Documents 1 and 2). The band gap is about 2.3 eV, which is relatively small compared to the band gap of 3.0 to 3.2 eV of titanium oxide. In other words, light (visible light) on the long wavelength side can be more effectively utilized for the photocatalyst than titanium oxide which is widely known as a photocatalyst material. A urea hydrolysis method described in Patent Document 3 is known as a method for producing a visible light responsive BiVO ₄ fine powder at a low pressure.

Titanium oxide is widely known as an excellent carrier (for example, Non-Patent Document 4). In recent years, it has been known that a composition containing titanium oxide and a divalent copper compound supported by BiVO ₄ in a high dispersion has extremely high antiviral activity. Further, it is known that BiVO ₄ is more finely supported to enhance the antiviral activity.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4646210

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-136984

[Patent Document 3] Japanese Patent No. 3790189

[Non-patent literature]

[Non-Patent Document 1] J. Phys. Chem. B2006, 110, pp11352-11360

[Non-Patent Document 2] J. Am. Chem. Soc. 1999, 121, pp11459 -11467

[Non-Patent Document 3] Photonic Materials Research Society, Reporting Photocatalyst vol. 37, p. 31-32 (2012)

[Non-Patent Document 4] Nakazawa Yoshihiko (2008). Catalysts, Lectra Corporation

In Patent Document 1, the sample of CuO/TiO ₂ was irradiated with ultraviolet rays (Examples 1 to 4, Comparative Examples 3 to 4), under visible light irradiation (Comparative Example 2), and in a dark place (Comparative Example 1). Perform an antiviral assessment. Under visible light irradiation (Comparative Example 2) and in the dark (Comparative Example 1), there was no bacteriophage ‧ virus inactivation effect at all. Therefore, the light of the white LED fluorescent lamp which has been rapidly popularized in recent years does not contain ultraviolet light.

The bacteriophage ‧ virus inerting agent described in Patent Document 1 is completely anti-viral activity even under a white LED fluorescent lamp because it has no antiviral activity in the dark and under visible light. Therefore, the application of the bacteriophage ‧ virus inerting agent described in Patent Document 1 to the interior material 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. However, since platinum and tungsten oxide are extremely rare, they are expensive, and the industrial use of platinum-supported tungsten oxide particles is difficult.

Further, according to the method described in Patent Document 3, BiVO ₄ is supported on titanium oxide having a BET specific surface area ratio of 25 m ² /g, and when a divalent copper compound is contained, extremely high antiviral activity can be exhibited in a bright place. However, when the BET specific surface area is less than 25 m ² /g, the dispersibility at the time of slurry formation and the transparency at the time of application to a material are not good. Therefore, when BiVO ₄ is supported on titanium oxide having a BET specific surface area of 25 m ² /g or more, the reaction in carrying BiVO ₄ does not proceed smoothly, and as a result, the anti-phage activity is hardly exhibited even if the divalent copper compound is contained.

As described above, in the past, in the bright place containing visible light, a practical antiviral composition was not provided.

In order to solve the above problems, the present invention provides an antiviral composition which exhibits excellent antiviral properties even in a bright place where no ultraviolet light is present, an antiviral agent containing the antiviral composition, and the like. Photocatalysts for antiviral compositions are also intended to provide a virus-inert method.

The present inventors have found that a composition containing a cerium oxide-coated titanium oxide and a divalent copper compound carrying BiVO ₄ exhibits excellent antiviral activity under visible light irradiation, and is coated with cerium oxide by use as a carrier. In the case of titanium oxide, it is also possible to carry BiVO ₄ on titanium oxide having a BET specific surface area of 25 m ² /g or more, and to use a titanium oxide-coated titanium oxide and a divalent copper compound containing the BiVO ₄ . The toxic composition can be obtained by an antiviral agent or a photocatalyst which exhibits excellent antiviral properties in the absence of ultraviolet light.

That is, the present invention provides the inventors of the following [1] to [18].

[1] An antiviral composition comprising titanium dioxide coated with cerium oxide carrying BiVO ₄ and a divalent copper compound.

[2] The antiviral composition according to the above [1], wherein the titanium oxide-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 titanium oxide coated with cerium oxide is produced by a vapor phase method.

[4] The antiviral composition according to any one of the above [1], wherein the ratio of cerium oxide is 1 to 30 in terms of 100 parts by mass of titanium oxide coated with cerium oxide. quality%.

[5] The antiviral composition according to any one of the above [1], wherein the mass of the BiVO ₄ is 1 part by mass based on 100 parts by mass of the titanium oxide coated with cerium oxide. 20 parts by mass.

[6] The antiviral composition according to any one of the above [1], wherein the ratio of the copper element in the divalent copper compound to the titanium oxide coated with cerium oxide and BiVO a total of 100 parts by mass of ₄ in terms of 0.01 to 20 parts by mass.

[7] The antiviral composition according to any one of the above [1], wherein the divalent copper compound is selected from the group consisting of (a) general formula (1): Cu ₂ (OH) ₃ X (1) (wherein X represents an anion) a divalent copper compound containing a hydroxyl group, (b) a halogen of a divalent copper, (c) a mineral acid salt of divalent copper, and (d) an organic organic compound of divalent copper One or more of a group of acid salts, (e) copper oxide, (f) copper sulfide, (g) copper azide (II), and (h) copper ruthenate.

[8] The antiviral composition according to [7] above, wherein the general formula X of (1) is one or more selected from the group consisting of a conjugate base of a halogen, a carboxylic acid, a conjugate base of a mineral acid, and an OH group.

[9] The antiviral composition according to the above [7] or [8] wherein X in the above general formula (1) is selected from the group consisting of Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 One group of people.

[10] The antiviral composition according to the above [7], wherein the (b) divalent copper halide is one selected from the group consisting of copper chloride, copper fluoride, and copper bromide or Two or more types.

[11] The antiviral composition according to [7] above, wherein (c) the inorganic acid salt of divalent copper is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate. And one or more of a group of ammonium sulphate, copper sulphate, copper ammonium chloride, copper pyrophosphate, and copper carbonate.

[12] The antiviral composition according to [7] above, wherein (d) the organic acid salt of divalent copper is a divalent copper carboxylate.

[13] The antiviral composition according to [7] or [8] wherein the divalent copper compound is a divalent copper compound containing a hydroxyl group represented by the general formula (1).

[14] The antiviral composition according to any one of the above [1] to [13] wherein, in the case of ultraviolet light having an illuminance of 800 lux, it is irradiated for 60 minutes and has a virus inertness of 99.0% or more.

[15] [1] to [14] described in any one antiviral composition, which comprises as carrying BiVO ₄ in the silicon dioxide-coated titanium oxide and the divalent copper compound, The supported BiVO ₄ is obtained by heating an acidic suspension of titanium oxide, cerium ions, vanadic acid ions, urea, and water coated with cerium oxide under atmospheric pressure.

[16] An antiviral agent, which comprises the antiviral composition according to any one of the above [1] to [15].

[17] A photocatalyst comprising the antiviral composition according to any one of the above [1] to [15].

[18] A method for inactivating a virus, which comprises the antiviral composition according to any one of the above [1] to [15], the antiviral agent according to [16] above, or the above [17] The photocatalyst described is inert to the virus.

According to the present invention, there is provided an antiviral composition, an antiviral agent, a photocatalyst and a virus inertization method which can exhibit excellent antiviral properties in a bright place without ultraviolet light.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments. In addition, in the present specification, "the bright portion where no ultraviolet light is present (maybe only indicated by "bright place")" means that there is visible light having a wavelength of 400 nm or more, but there is substantially no place where ultraviolet light is present.

[antiviral composition]

The antiviral composition of the present invention containing a supported BiVO ₄ in a silicon dioxide-coated titanium oxide composition of a divalent copper compound, can be manifested in a bright place by excellent antiviral.

<Titanium oxide coated with cerium oxide>

Titanium oxide having a BET specific surface area of 25 m ² /g or more can also carry BiVO ₄ by using titanium oxide coated with cerium oxide. When BiVO ₄ is supported, the titanium oxide is dispersed in a solvent, and the steps of adding cerium ions and vanadate ions are generally contemplated. In this case, when titanium oxide having a BET specific surface area of 25 m ² /g or more is used, since the surface energy of the titanium oxide is high, the cerium ions and the vanadic acid ions are rapidly and strongly adsorbed on the surface of the titanium oxide, even after that. The steps of BiVO _{4 are} also difficult to precipitate. On the other hand, when titanium oxide coated with cerium oxide is used, the surface energy of titanium oxide is lowered as compared with cerium oxide, and cerium ions and vanadate ions are hardly adsorbed, and the subsequent steps are followed by oxidation. BiVO ₄ precipitates slowly on the ruthenium-coated titanium oxide.

The titanium dioxide coated with cerium oxide of the present invention is not particularly limited as long as it can carry BiVO ₄ . The method of coating the ruthenium dioxide with the titanium oxide is, for example, produced by the liquid phase method described in Japanese Patent No. 5,181,408, or the gas phase described in JP-A-2004-231952. Law makers, etc.

The titanium oxide coated with cerium oxide produced by the vapor phase method is preferable from the viewpoint of production cost.

Titanium oxide coated with cerium oxide is preferably titanium dioxide (TiO ₂ ), and as the crystal form, anatase titanium oxide, rutile titanium oxide, and brookite titanium oxide are preferred. Titanium ore type titanium oxide and rutile type titanium oxide are preferred. The cerium oxide of titanium oxide coated with cerium oxide is preferably cerium oxide (SiO ₂ ).

The BET specific surface area (value before carrying BiVO ₄ ) of the cerium oxide-coated titanium oxide used in the present invention is preferably 25 m ² /g or more, more preferably 25 to 1000 m ² /g, more preferably 30~500m ² /g, especially 40~300m ² /g. When the BET specific surface area of the titanium oxide coated with cerium oxide is 25 m ² /g or more, the dispersibility at the time of slurry formation and the transparency at the time of application to a material are good. When the BET specific surface area of the titanium oxide coated with cerium oxide is 1000 m ² /g or less, when the antiviral composition such as coating of the antiviral composition is applied, the treatment of the antiviral composition becomes easily. Here, the BET specific surface area is a specific surface area measured by a BET three-point method by nitrogen adsorption.

The proportion of the cerium oxide coated with cerium oxide coated with cerium oxide in the present invention is preferably 1 to 30% by mass, preferably 2 to 25% by mass, based on the cerium oxide-coated titanium oxide. More preferably 5 to 25% by mass. When the amount of cerium oxide is at least 1% by mass, the reaction for carrying BiVO ₄ can be favorably carried out. When the amount of cerium oxide is 30% by mass or less, the use amount of the relatively high-priced cerium oxide raw material can be suppressed, which is economical. .

<BiVO ₄ >

The BiVO ₄ of the present invention supported on titanium oxide coated with cerium oxide exhibits high photocatalytic activity in the visible light region. The method of supporting BiVO ₄ on titanium oxide coated with cerium oxide includes, for example, a solid phase method and a liquid phase method. Any of these may be used for the antiviral composition of the present invention, but a liquid phase method is preferred, and a urea hydrolysis method is preferred (see Patent Document 3). The known method for producing BiVO _4, for example of the method for manufacturing the BiVO _4, with silicon dioxide-coated titanium oxide will be added to the synthesis BiVO _4, BiVO ₄ may be carried on to coated silicon dioxide Titanium oxide.

The mass ratio of BiVO ₄ is preferably from 1 to 20 parts by mass, more preferably from 2 to 15 parts by mass, even more preferably from 3 to 10 parts by mass, per 100 parts by mass of the titanium oxide coated with cerium oxide. BiVO ₄ for the mass to 100 parts by mass of silicon dioxide coated titanium oxide in terms of 1 to 20 parts by mass, the antiviral composition antiviral properties become in a bright place in the good, and can suppress resistance The toxic composition exhibits a bright yellow color. Further, it is also economical to reduce the ratio of Bi and V elements in the composition.

<2-valent copper compound>

The divalent copper compound used in the present invention is a copper compound having a copper valence of 2.

The divalent copper compound alone does not exhibit antiviral properties in the bright place. However, when combined with cerium oxide-coated titanium oxide carrying BiVO ₄ , the antiviral property in a bright place can exhibit a divalent copper compound. The divalent copper compound is only a copper compound having a copper valence of 2, and is not particularly limited. For example, the divalent copper compound is a divalent copper compound containing a hydroxyl group represented by (a) the following general formula (1): Cu ₂ (OH) ₃ X (1) (wherein, X represents an anion), and (b) a halogen of a divalent copper, (c) a mineral acid salt of divalent copper, (d) an organic acid salt of divalent copper, (e) copper oxide, (f) copper sulfide, (g) copper azide (II) And (h) one or more of a group of copper citrate.

The preferred X (anion) of the general formula (1) is selected from the group consisting of a halogen such as Cl, Br and I, a conjugate base of a carboxylic acid such as CH ₃ COO, a mineral acid such as NO ₃ and (SO ₄ ) _1/2 . Any of a group of conjugate bases and OH groups. In general, the general formula (1) is preferably one selected from the group consisting of Cl, CH ₃ COO, NO ₃ , (SO ₄ ) _1/2 , and OH groups. Among these, halogen is preferred, and Cu ₂ (OH) ₃ Cl is preferred.

Preferably, the halogen of the (b) divalent copper is one or more selected from the group consisting of copper chloride, copper fluoride, and copper bromide. Copper chloride is preferred.

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

Preferably, the organic acid salt of (d) divalent copper is a divalent copper carboxylate. The carboxylate of divalent copper is preferably selected from the group consisting of copper formate, copper acetate, copper propionate, copper butyrate, copper gimate, copper hexanoate, copper heptate, copper octoate, copper ruthenate, and ruthenium. Copper acid, copper myristate, copper palmitate, copper heptaate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, isophthalic acid Copper formate, copper terephthalate, copper salicylate, copper benzene hexate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, glycol Copper acid, copper glycerate, copper gluconate, copper tartrate, copper acetonitrile, ethyl ethyl acetonitrile Copper acid, copper isomethacrylate, copper β-dihydroxybenzoate, copper diacetate, copper methyl decyl succinate, copper salicylate, copper bis(2-ethylhexane), bismuth One or more of a group of copper acid and copper naphthenic acid. Preferred is copper acetate.

The other preferable divalent copper compound is selected from the group consisting of copper hydroxyquinolate, copper acetonate, copper ethyl acetoacetate, copper triflate, copper phthalocyanine, copper ethoxide, and copper isopropoxide. And one or more of a group of copper oxychloride and copper dimethyldithiocarbamate.

The divalent copper compound of the present invention is preferably a divalent copper compound containing a hydroxyl group represented by the above formula (1), (b) a halogen of a divalent copper, and (c) a mineral acid salt of a divalent copper. And (d) an organic acid salt of divalent copper. In addition, the divalent copper compound of the present invention is more preferably a divalent copper compound having a hydroxyl group represented by the above general formula (1), from the viewpoint of less impurities and lower cost. Further, the divalent copper compound having a hydroxyl group represented by the above formula (1) in the general formula (1) may be an anhydride (anhydride) or a hydrate.

The mass of the copper element (mass ratio of Cu) in the divalent copper compound of the antiviral composition of the present invention is 0.01% by weight based on 100 parts by mass of the total of titanium oxide coated with cerium oxide and BiVO ₄ 20 parts by mass is preferred, preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, particularly preferably 0.3 to 10 parts by mass. When the amount of the copper element in the bismuth copper compound is 0.01 parts by mass or more based on 100 parts by mass of the total of the cerium oxide-coated titanium oxide and the BiVO ₄ , the antiviral property and the antibacterial property in the bright portion become good. . In addition, when the amount of the copper element in the divalent copper compound is 20 parts by mass or less based on 100 parts by mass of the total of the titanium oxide-coated titanium oxide and the BiVO ₄ , the BiVO _4- supporting ruthenium dioxide can be prevented from being coated. The surface of the coated titanium oxide is coated with a divalent copper compound, and the photocatalytic activity of the antiviral composition can be improved, and the virus is inert and economical under a small amount of the antiviral composition.

In the case where 100 parts by mass of the titanium oxide-coated titanium oxide and BiVO ₄ are used, the quality of the copper element in the divalent copper compound may be a raw material of a divalent copper compound or a titanium oxide coated with cerium oxide. The amount of BiVO ₄ is calculated. The antiviral composition of the present invention is heated in a hydrofluoric acid solution, and completely dissolved to prepare a solution. Using an ICP emission spectrometer (model ICPS-7500 manufactured by Shimadzu Corporation), the amount of copper element can be determined by analyzing the extract extracted from the solution by the ICP method.

For the antiviral composition, the divalent copper compound may be supported on titanium oxide and/or BiVO ₄ coated with cerium oxide. Further, in the antiviral composition, the divalent copper compound may be not supported on titanium oxide and/or BiVO ₄ coated with cerium oxide, and may be dispersed in titanium oxide coated with cerium oxide and BiVO ₄ .

As described above, the antiviral composition of the present invention contains, as an essential component, a titanium dioxide-coated titanium oxide and a divalent copper compound carrying BiVO ₄ , but does not inhibit the object of the present invention. It may contain any other ingredients. However, from the viewpoint of improvement in antiviral properties, the total content of the cerium oxide-coated titanium oxide and the divalent copper compound carrying BiVO ₄ in the antiviral composition is antiviral composition. The total mass is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, and particularly preferably 100% by mass.

The antiviral composition of the present invention is a composition having a virus inertness of 99.0% or more after being irradiated with visible light of 800 lux for 60 minutes.

Further, the antiviral composition of the present invention may comprise a supported BiVO ₄ obtained by heating an acidic suspension of titanium oxide coated with cerium oxide, cerium ions, vanadic acid ions, urea and water under atmospheric pressure. A composition of titanium oxide coated with cerium oxide and a divalent copper compound. Specifically, it is produced by the method described in the examples.

[Antiviral agents and photocatalysts]

The antiviral agent and photocatalyst of the present invention contain the antiviral composition of the present invention.

Thereby, the antiviral agent and photocatalyst of the present invention have excellent antiviral properties in a bright place.

[Forms of antiviral composition, antiviral agent and photocatalyst]

The form of use of the antiviral composition, the antiviral agent, and the photocatalyst (hereinafter sometimes referred to as "the antiviral composition of the present invention") of the present invention is not particularly limited.

For example, the antiviral composition of the present invention or the like can be used in the form of a solid such as fine powder or granules. In this case, for example, the antiviral composition of the present invention or the like is filled in a predetermined container and used. Alternatively, the surface of the predetermined substrate and/or the interior thereof may contain the use form of the antiviral composition of the present invention. In the state, the antiviral composition of the present invention or the like is used. Generally, the use form of the latter is better. Further, examples of the substrate include a single substrate made of a general member such as fiber, metal, ceramic, and glass, and a composite substrate made of two or more members of the member. However, the substrate is not limited to this.

A coating agent such as a floor polish which can be peeled off by a suitable method may contain the antiviral composition of the present invention and the like. Further, the antiviral composition of the present invention or the like may be immobilized on a predetermined film, and the antiviral composition of the present invention or the like may be exposed to the surface of the continuous film. Moreover, the antiviral composition of the present invention or the like can be used in the form of a coating prepared by dispersing a solvent such as the antiviral composition of the present invention.

The material for immobilizing the antiviral composition of the present invention on the surface of the substrate, for example, a material which fixes the antiviral composition of the present invention or the like on the surface of the substrate by a general immobilization method such as a binder. Wait. Both the organic binder and the inorganic binder can be used as a binder for immobilizing the antiviral composition of the present invention, and it is preferred to use an inorganic binder in order to avoid decomposition of the binder of the photocatalyst. The type of the binder is not particularly limited. In the inorganic binder, for example, an inorganic binder such as cerium oxide which is generally used to immobilize a photocatalyst substance on the surface of a substrate can be mentioned. The organic binder may, for example, be a polymer binder which can form a film by polymerization or solvent evaporation.

The antiviral composition or the like of the present invention is contained in a material inside the substrate, and for example, the antiviral composition of the present invention or the like is dispersed in a resin to prepare a dispersion, and the dispersion is cured. Know the material material. Any of a natural resin and a synthetic resin can be used for the resin which disperses the antiviral composition of the present invention. Examples of the synthetic resin include an acrylic resin, a phenol resin, a polyurethane resin, an acrylonitrile/styrene copolymer resin, an acrylonitrile/butadiene/styrene copolymerization (ABS) resin, and a polyester resin. And epoxy resin, etc., but it is not limited to these resins.

The case of using the antiviral composition of the present invention or the like is not particularly limited. Further, the antiviral composition of the present invention has excellent virus inertness in the presence of water (for example, in water and sea water), in a dry state (for example, in a low humidity state such as winter), in a high humidity state, or in the presence of an organic substance. Characteristics that continuously make the virus inert. For example, the antiviral composition of the present invention or the like can be disposed on a wall, a floor, a ceiling, or the like. In addition, it is applicable to any object such as a building, a work machine, a measuring device, an electrochemical product, and parts (for example, a refrigerator, a washing machine, a food washing machine, etc., and a filter for an air cleaner). The antiviral composition of the present invention and the like.

In the past, as one of the countermeasures against influenza, it has been proposed to apply a titanium oxide to a ceramic filter or a non-woven filter, and to install an air cleaner to which a light source to be irradiated with ultraviolet light is attached. However, when the antiviral composition of the present invention or the like is used in a filter of an air cleaner, an ultraviolet light source is not required, whereby the cost of the air cleaner can be reduced, and the safety of the air cleaner can be improved.

[Virus Inactivation Method]

The present invention provides an antiviral composition using the present invention, and the present invention The antiviral agent or the photocatalyst of the present invention is a virus inerting method which makes the virus inert.

As described above, since the antiviral composition of the present invention exhibits antiviral properties, the antiviral composition of the present invention can be used to make the virus inert. Further, since the antiviral agent and photocatalyst of the present invention contain the antiviral composition of the present invention, the virus can be made inert using the antiviral agent or photocatalyst of the present invention.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the following examples. Samples of Examples 1 to 4 and Comparative Examples 1 to 4 were produced as follows.

Titanium oxide A coated with cerium oxide (made by Showa Denko Ceramics Co., Ltd., F-4S05, anatase type) and titanium oxide B coated with cerium oxide (Showa Electric Ceramics) used in the following examples The amount of cerium oxide and the BET specific surface area of (manufacturing), F-4S20, anatase type, and titanium oxide A (made by Showa Electric Ceramics Co., Ltd., F-4, anatase type) are shown in Table 1. Show. And the amount of cerium oxide of titanium oxide A coated with cerium oxide is quantified by high-frequency inductively coupled plasma luminescence spectrometry as cerium oxide (SiO ₂ ) in titanium oxide coated with cerium oxide. quality%. The BET specific surface area can be measured by nitrogen adsorption by the BET 3 point method.

<Example 1>

Into 300 mL of distilled water, 10.000 g of titanium oxide A coated with cerium oxide (Model F-4S05, manufactured by Showa Denko Ceramics Co., Ltd.) was suspended to prepare a suspension. Next, 0.752 g of Bi(NO ₃ ) ₃ ‧5H ₂ O (manufactured by Kanto Chemical Co., Ltd.) and 0.182 g of NH ₄ VO ₃ (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 3.0 mL and 4.0 mL each. A 5.0 mol/L HNO ₃ solution was added to the suspension in the order of a solution of Bi(NO ₃ ) ₃ ‧5H ₂ O HNO _{3 and a} solution of NH ₄ VO ₃ dissolved in HNO ₃ . Thereafter, the mixture was stirred and mixed by a magnetic stirrer at a rotation speed of 400 rpm for 30 minutes. The obtained suspension was filtered and dried to prepare a sample for measuring the adsorption amount of Bi and V of the antiviral composition.

<Example 2>

An example was produced in the same manner as in Example 1 except that the titanium oxide A coated with cerium oxide was replaced by titanium oxide B coated with cerium oxide (Model F-4S20, manufactured by Showa Denko Ceramics Co., Ltd.). 2 samples.

<Example 3>

A suspension was prepared by suspending 10.000 g of cerium oxide-coated titanium oxide A in 300 mL of distilled water, and the pH of the suspension was adjusted to 1.3 in a 5 mol/L HNO ₃ aqueous solution. Next, 3.052 mL of each of 0.752 g of Bi(NO ₃ ) ₃ ‧5H ₂ O (manufactured by Kanto Chemical Co., Ltd.) and 0.182 g of NH ₄ VO ₃ (manufactured by Kanto Chemical Co., Ltd.) and 5 mL of 4.0 mL were prepared. / L of HNO ₃ solution, to dissolve the _{Bi (NO 3) 3 ‧5H 2} O of the HNO ₃ solution, the order of NH ₄ VO ₃ was dissolved HNO ₃ solution into the suspension. Thereafter, 10.000 g of urea (manufactured by Kanto Chemical Co., Ltd.) was placed in the suspension, heated at a temperature of 80 ° C on a heating stirrer, and maintained at a temperature of 80 ° C for 8 hours. After the obtained suspension was filtered and dried, BiVO ₄ / cerium oxide-coated titanium oxide A (5 parts by mass of BiVO ₄ supported on 100 parts by mass of titanium oxide coated with cerium oxide) was obtained. ).

A suspension was prepared by suspending 6.000 g of BiVO ₄ / cerium oxide-coated titanium oxide A powder in 100 mL of distilled water, and 0.081 g (for BiVO ₄ / cerium oxide-coated titanium oxide A powder 100 parts by mass) CuCl ₂ ‧2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) containing 0.5 part by mass of copper was placed in the suspension and stirred for 10 minutes. The pH of the suspension was changed to 10, and an aqueous solution of 1.0 mol/L of sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added thereto, 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 dispersed by a stirrer to prepare the same sample as in Example 1. And, CuCl ₂ ‧2H ₂ O after hydrolysis of ₃ Cl Cu ₂ (OH). The pH measuring device was carried out using D-51 manufactured by Horiba.

<Example 4>

A sample of Example 4 was produced in the same manner as in Example 3 except that the titanium oxide A coated with cerium oxide was replaced by the cerium oxide-coated titanium oxide B.

<Comparative Example 1>

A sample of Comparative Example 1 was produced in the same manner as in Example 1 except that the titanium oxide A coated with cerium oxide was replaced by titanium oxide A (manufactured by Showa Denko Ceramics Co., Ltd., model F-4).

<Comparative Example 2>

A sample of Comparative Example 2 was produced in the same manner as in Example 3 except that titanium oxide A coated with cerium oxide was replaced by titanium oxide A.

<Comparative Example 3>

10.000 g of cerium oxide-coated titanium oxide B was suspended in 300 mL of distilled water to prepare a suspension, and the pH of the suspension was adjusted to 1.3 with a 5.0 mol/L HNO ₃ aqueous solution. Next, 3.052 mL of each of 0.752 g of Bi(NO ₃ ) ₃ ‧5H ₂ O (manufactured by Kanto Chemical Co., Ltd.) and 0.182 g of NH ₄ VO ₃ (manufactured by Kanto Chemical Co., Ltd.) and 5.0 mol of 4.0 mL were prepared. The /L HNO ₃ solution was applied to the suspension in the order of a solution of Bi(NO ₃ ) ₃ ‧5H ₂ O HNO _{3 and a} solution of NH ₄ VO ₃ dissolved in HNO ₃ . Thereafter, 10.000 g of urea (manufactured by Kanto Chemical Co., Ltd.) was placed in a suspension, heated at a temperature of 80 ° C on a heating stirrer, and maintained at a temperature of 80 ° C for 8 hours. The obtained suspension was filtered and dried to obtain BiVO ₄ / cerium oxide-coated titanium oxide A (5 parts by mass of BiVO _{4 was} carried for 100 parts by mass of titanium oxide coated with cerium oxide) ). Further, in Comparative Example 3, the sample of Comparative Example 3 was produced without the step of adding CuCl ₂ /2H ₂ O in Example 3.

<Comparative Example 4>

After suspending 6.00 g of cerium oxide-coated titanium oxide B powder in 100 mL of distilled water, 0.081 g (0.5 part by mass of 100 parts by mass of copper of titanium oxide A powder coated with cerium oxide) was prepared. CuCl ₂ ‧2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) was added to the suspension and stirred for 10 minutes. In order to make the pH of the suspension 10, a 1 mol/L sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) aqueous solution was added, and the mixture was stirred and mixed for 30 minutes to obtain a slurry. After the slurry was filtered, the obtained powder was washed with pure water, dried at 80 ° C, and dispersed in a stirrer to prepare a sample of Comparative Example 4. Further, for Comparative Example 4, it was not included in Example 3, which prepared 0.752 g of each of Bi(NO ₃ ) ₃ ‧5H ₂ O (manufactured by Kanto Chemical Co., Ltd.) and 0.182 g of NH ₄ VO ₃ (Kanto Chemical Co., Ltd.). ) Ltd.) and 3.0mL 4.0mL of 5mol / L of HNO ₃ solution, to dissolve the _{Bi (NO 3) 3 ‧5H 2} O of the HNO ₃ solution, NH ₄ VO ₃ was dissolved sequence of HNO ₃ solution was administered in suspension In the preparation step in the liquid, a sample of Comparative Example 4 was produced in the same manner as in Example 3 except that the titanium oxide B powder coated with cerium oxide without BiVO ₄ was used.

The amounts of Bi and V which were coated with cerium oxide and the amounts of Bi and V adsorbed on the titanium oxide of Examples 1, 2 and Comparative Example 1 are shown in Table 2. And adsorption The mass parts of Bi and V are values of 100 parts by mass of the input amount of Bi or V. The method for measuring the adsorption amount of Bi and V will be described later.

The results of the evaluation of 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. In addition, the mass part of the Cu ₂ (OH) ₃ Cl is a part by mass in terms of Cu in terms of 100 parts by mass of titanium oxide, titanium oxide, and BiVO ₄ coated with cerium oxide. The details of the measurement method will be described later.

<Evaluation method>

Further, the compositions or evaluations of the samples of Examples 1 to 4 and Comparative Examples 1 to 4 described in Tables 1 to 3 were measured by the following methods.

(High frequency inductively coupled plasma luminescence spectroscopic analysis)

The high-frequency inductively coupled plasma luminescence spectroscopic analysis was used to quantify the Bi and V in the input Bi and V of Examples 1, 2 and Comparative Example 1, and the Bi and V adsorbed on the titanium oxide coated with cerium oxide. % by mass. Specifically, each sample is heated in a hydrofluoric acid solution, and after completely dissolved, a solution is prepared. The extract extracted from the solution was analyzed using an ICP emission spectrometer (manufactured by Shimadzu Corporation, model ICPS-7500) to quantify Bi and V in the composition. The results are shown in Table 2.

(X-ray diffraction measurement)

The samples of Examples 3 and 4 and the samples of Comparative Examples 2 and 3 were subjected to X-ray diffraction measurement, and the combination of Bi and V present in the sample was carried out. Identification of objects. The measurement apparatus was an "X'pertPRO" manufactured by PANalytical Co., Ltd., and a copper target was used, and a Cu-K α 1 line was used, and the tube voltage was 45 kV, the tube current was 40 mA, the measurement range was 2 θ = 20 to 100 deg, and the sampling width was 0.0167 deg. X-ray diffraction measurement was performed under the conditions of 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 the titanium oxide A coated with cerium oxide, the titanium oxide B coated with cerium oxide, and the titanium oxide A is a fully automatic BET specific surface area measuring device manufactured by Mountech "Macsorb, HM model- 1208", measured by nitrogen using the BET3 point method. The results are shown in Table 1.

(Evaluation of antiviral properties under visible light (bright spot): determination 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 using a model experiment using phage. Further, a method of utilizing the inert energy of a phage as a model of antiviral properties, for example, as described in Appl. Microbiol Biotechnol., 79, pp. 127-133 (2008), is known to be faithful by the method. The result. Further, the 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 coated on a glass plate (50 mm × 50 mm × 1 mm) to prepare a sample for evaluation. The samples of Examples 3 and 4 and the samples of Comparative Examples 2 to 4 were applied to 2.5 mg of the above glass plate to prepare an evaluation sample having a coating amount per unit area of 1.0 g/m ² .

Apply filter paper to the deep dish and add a small amount of sterilized water. The sample for evaluation described above was placed on the filter paper. The phage infection price was about 6.7×10 ⁶ to about 2.6×10 ⁷ pfu/ml, and 100 μL of the suspension of Q β phage (NBRC20012) was added thereto, and the surface of the sample was contacted with the phage to coat the PET. A film made of (polyethylene terephthalate). The deep type dish is covered with a glass plate as a measuring device. Prepare a plurality of devices for the same measurement.

In addition, as a light source, a 15W white fluorescent lamp (made by Panasonic Co., Ltd., Full white fluorescent lamp, FL15N) is attached with a blocking ultraviolet filter (Nippon Resin Industrial Co., Ltd., N-113). A plurality of measuring devices were allowed to stand at a position where the illuminance was 800 lux (illuminance meter: measured by IM-5 manufactured by Topcon). The phage concentration of the sample on the glass plate was measured after 60 minutes from the start of the light irradiation. Moreover, the room illuminance at the time of measurement was 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 soaked in 9.9 ml of phage recovery solution (SCDLP medium), and shaken for 10 minutes with a vibrating machine.

The phage recovery solution was appropriately diluted using physiological saline containing peptone. To separately mix the cultured 5.0×10 ⁸ to 2.0×10 ⁹ /ml coliform (NBRC106373) culture solution and the calcium-added LB soft cold day medium, add 1 ml of the diluted liquid, and then add the liquid. The phage plaque number was visually counted by culturing in LB cold medium supplemented with calcium and culturing at 37 ° C for 15 hours. The phage concentration N was determined by multiplying the number of plaques obtained by the dilution ratio 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 the predetermined time. The smaller the value of LOG(N/N ₀ ), in other words, the larger the absolute value, the better the antiviral properties of the sample. The results are shown in Table 3.

<Result>

The results obtained by the above examples and comparative examples will be explained.

(High-frequency Inductive coupling plasma luminescence spectrometry)

As a result of Table 2 of high-frequency inductively coupled plasma luminescence spectroscopic analysis, titanium oxide coated with cerium oxide was compared with titanium oxide, and it was found that cerium ions and vanadate ions were not easily adsorbed.

(X-ray diffraction measurement)

As a result of the results shown in Table 3 by XRD diffraction, it was found that the compounds of Bi and V present in the samples of Examples 3 and 4 and Comparative Example 3 were BiVO ₄ .

The sample of Comparative Example 2 had a weak absorption peak intensity and could not be identified.

(Evaluation of antiviral properties in visible light irradiation: determination of LOG (N/N ₀ ))

The evaluation results of the antiviral properties in the visible light irradiation are shown in Table 3. It is found that Examples 3 and 4 of the combination of titanium oxide, BiVO ₄ and divalent copper compounds coated with cerium oxide have a higher performance. Antiviral activity.

It can be seen from the comparison of Examples 1 and 2 of Table 1 and Comparative Example 1 that the titanium oxide coated with cerium oxide is difficult to adsorb cerium ions and vanadic acid ions, and the larger the amount of cerium oxide coating, the higher the effect. . It was found that the samples of Examples 3 and 4 had a virus inertness of 99.0% or more at 60 minutes of visible light irradiation of 800 lux. From the comparison of Examples 3 and 4 of Table 3 and Comparative Example 2, it was found that the larger the amount of cerium oxide coating, the easier it is to carry BiVO ₄ , and as a result, it was confirmed that the antiviral activity was improved. Further, from the comparison between Example 4 and Comparative Examples 3 and 4, it was confirmed that a combination of titanium oxide coated with cerium oxide, BiVO ₄ , and a divalent copper compound is important for exhibiting antiviral activity.

Claims (18)

An antiviral composition comprising titanium dioxide coated with cerium oxide carrying BiVO ₄ and a divalent copper compound. The antiviral composition of claim 1, wherein the titanium oxide coated with cerium 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 titanium oxide coated with cerium oxide is produced by a gas phase method. The antiviral composition according to claim 1 or 2, wherein the proportion of cerium oxide is 1 to 30% by mass based on 100 parts by mass of the titanium oxide coated with cerium oxide. The antiviral composition according to claim 1 or 2, wherein the ratio of the aforementioned BiVO ₄ is 1 to 20 parts by mass based on 100 parts by mass of the titanium oxide coated with cerium oxide. The antiviral composition of claim 1 or 2, wherein the mass of the copper element in the divalent copper compound is 0.01 to 20 by mass based on 100 parts by mass of the total of the above-mentioned ceria-coated titanium oxide and BiVO ₄ Share. The antiviral composition according to claim 1 or 2, wherein the aforementioned divalent copper compound is selected from the group consisting of (a) general formula (1): Cu ₂ (OH) ₃ X (1) (wherein X represents an anion) A divalent copper compound containing a hydroxyl group, (b) a halogen of a divalent copper, (c) a mineral acid salt of divalent copper, (d) an organic acid salt of divalent copper, (e) copper oxide, (f) One or more of copper sulfide, (g) copper azide (II), and (h) copper ruthenate. The antiviral composition of claim 7, wherein X of the general formula (1) is one or more selected from the group consisting of a conjugate base of a halogen, a carboxylic acid, a conjugate base of an inorganic acid, and an OH group. By. The antiviral composition of claim 7, wherein X in the above 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 of claim 7, wherein (b) the halogen of the divalent copper is one or more selected from the group consisting of copper chloride, copper fluoride, and copper bromide. The antiviral composition of claim 7, wherein (c) the inorganic acid salt of divalent copper is selected from the group consisting of copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium copper sulfate. And one or more of a group of copper amide sulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate. The antiviral composition of claim 7, wherein (d) the organic acid salt of divalent copper is a carboxylate of divalent copper. The antiviral composition according to claim 7, wherein the divalent copper compound is a divalent copper compound having a hydroxyl group represented by the general formula (1). The antiviral composition according to claim 1 or 2, which is a person having a virus inertness of 99.0% or more after being irradiated with visible light of 800 lux for 60 minutes. The antiviral composition requested item 1 or 2, which is supported comprising BiVO ₄ in the silicon dioxide-coated titanium oxide and the divalent copper compound, to the supporting silicon dioxide coated BiVO ₄ The titanium oxide is obtained by heating an acidic suspension of titanium oxide, cerium ions, vanadic acid ions, urea, and water coated with cerium oxide under atmospheric pressure. An antiviral agent comprising the antiviral composition according to any one of claims 1 to 15. A photocatalyst comprising the antiviral composition according to any one of claims 1 to 15. A virus inertization method characterized by using the antiviral composition according to any one of claims 1 to 15, an antiviral agent such as claim 16, or a photocatalyst according to claim 17 to inactivate the virus.