TW201605459A - Anti-viral composition, method for producing the composition, and virus inactivation method - Google Patents

Abstract

To provide an anti-viral composition, an anti-viral agent, and a photocatalyst, which exhibit excellent anti-viral property under light and in the dark; a method for producing the anti-viral composition; and a virus inactivation method. The anti-viral composition of the present invention contains BiVO4 and a divalent copper compound. The anti-viral agent and photocatalyst of the present invention each contain the anti-viral composition of the present invention. The anti-viral composition production method includes a mixing step of mixing BiVO4, a divalent copper compound or a divalent copper compound raw material, water, and an alkaline substance, to thereby form a mixture; and a separation step of separating an anti-viral composition from the mixture. The virus inactivation method of the present invention inactivates a virus by use of the anti-viral composition of the present invention, the anti-viral agent of the present invention, or the photocatalyst of the present invention.

Description

Antiviral composition, method for producing the same, and virus inactivation method

The present invention relates to an antiviral composition for inactivating a virus, an antiviral agent containing the antiviral composition, a photocatalyst, a method for producing the antiviral composition, and a virus inactivation method.

In recent years, new viruses that have a negative impact on human health have been found to have strong doubts about the expansion of their infection. Photocatalysts have attracted attention as materials for preventing the spread of infections of such viruses (for example, Patent Documents 1 and 2 are incorporated by reference).

Patent Document 1 describes a bacteriophage ‧ virus deactivator composed of copper anatase-type titanium oxide in a range of CuO/TiO ₂ (% by mass) = 1.0 to 3.5. It was found that the bacteriophage ‧ virus was inactivated by the copper-containing titanium oxide, and the deactivating agent of the invention described in Patent Document 1 was completed. Patent Document 2 describes that platinum-supported tungsten oxide particles exhibit antiviral activity under visible light irradiation.

Barium vanadate (hereinafter referred to as BiVO ₄ ) is widely known as an excellent visible light-reactive water-splitting photocatalyst (for example, Non-Patent Documents 1 to 3). The band gap is about 2.3 eV, which is smaller than the band gap of titanium oxide of 3.0 to 3.2 eV. That is, the photocatalyst can effectively utilize light of a longer wavelength side (visible light) than titanium oxide which is widely known as a photocatalyst material. Further, in BiVO ₄ , there is also a report example of decomposition of a photocatalyst as an organic substance. For example, Patent Document 3 describes BiVO ₄ powder carrying silver fine particles or copper oxide fine particles, and exhibits high activity as a photocatalyst for photolysis of endocrine disrupting substances.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-232729

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

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-330047

[Non-patent literature]

[Non-Patent Document 1] J. Phys. Chem. B2006, 110, pp 11352-11360

[Non-Patent Document 2] J. Am. Chem. Soc. 1999, 121, pp 11459-11467

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

In Patent Document 1, the samples of CuO/TiO ₂ were subjected to ultraviolet irradiation (Examples 1 to 4, Comparative Examples 3 to 4), visible light irradiation (Comparative Example 2), and dark (Comparative Example 1). Viral assessment. On the other hand, under visible light irradiation (Comparative Example 2) and in the dark (Comparative Example 1), there was no phage/virus deactivation effect at all. However, the light of the white LED fluorescent lamp that has been rapidly popularized in recent years does not contain ultraviolet light. The inactivated agent of the bacteriophage ‧ virus described in Patent Document 1 has no antiviral activity at all under the dark and under visible light, and therefore it is assumed that there is no antiviral activity at all under the white LED fluorescent lamp. Therefore, the deactivating agent of the bacteriophage ‧ virus described in Patent Document 1 is extremely limited in its application to the interior material. The platinum-supporting tungsten oxide particles described in Patent Document 2 exhibit antiviral properties under visible light irradiation. However, since platinum is extremely rare and expensive, it is difficult to industrially utilize platinum-supporting tungsten oxide particles. Further, the bacteriophage ‧ virus deactivating agent described in Patent Document 1 and the platinum-supporting tungsten oxide particles described in Patent Document 2 are used to inactivate the virus for 1 to 6 hours, which is difficult to use. People are exposed to frequent components.

Patent Document 3 describes an excellent effect of BiVO ₄ powder carrying silver fine particles or copper oxide fine particles as a photocatalyst for photolysis of endocrine disrupting substances. However, in Patent Document 3, there is no description about antiviral activity. Further, the photocatalyst material having excellent organic substance decomposition activity is not necessarily excellent in antiviral activity (for example, Non-Patent Document 3). That is, the performance mechanisms of the two effects are fundamentally different, so that the organic matter decomposition activity is excellent and the antiviral activity is excellent. Therefore, the manufacturer cannot think of using BiVO ₄ powder carrying silver fine particles or copper oxide fine particles as an antiviral agent.

In order to solve the above problems, the present invention provides an antiviral composition, an antiviral agent, a photocatalyst, a method for producing the antiviral composition, and a virus loss which are excellent in antiviral properties which are excellent in both bright and dark places. The method of living is for the purpose.

The present inventors have found that a composition containing BiVO ₄ and a divalent copper compound exhibits excellent antiviral activity under visible light irradiation and in a dark place, and has completed the present invention. That is, the present invention provides the inventions of the following [1] to [19].

[1] An antiviral composition comprising BiVO ₄ and a divalent copper compound.

[2] The antiviral composition according to the above [1], wherein the mass of the copper element in the divalent copper compound is 0.01 to 20 parts by mass based on 100 parts by mass of the BiVO ₄ .

[3] The antiviral composition according to the above [1] or [2] wherein the divalent copper compound is (a) the following general formula (1): Cu ₂ (OH) ₃ X (1)

(where X is an anion)

The hydroxyl group-containing divalent copper compound, (b) divalent copper halide, (c) divalent copper mineral acid salt, (d) divalent copper organic acid salt, (e) copper oxide, (f) Selected from the group consisting of copper sulfide, (g) copper azide (II) and (h) copper ruthenate It is composed of one type or two or more types.

[4] The antiviral composition according to the above [3], wherein X of the general formula (1) is selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of a mineral acid, and OH. Either.

[5] The antiviral composition according to the above [3], wherein (b) the halogen of the divalent copper is one or two selected from the group consisting of copper chloride, copper fluoride and copper bromide. The above composition.

[6] The antiviral composition according to [3] above, wherein (c) the inorganic acid salt of divalent copper is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, tetraboric acid. One or two or more selected from the group consisting of copper, ammonium sulphate copper, guanamine sulphate copper sulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate.

[7] The antiviral composition according to [3] above, wherein (d) the organic acid salt of divalent copper is a divalent copper carboxylate.

[8] The antiviral composition according to the above [3] or [4] wherein the divalent copper compound is a hydroxyl group-containing divalent copper compound represented by the general formula (1).

[9] The antiviral composition according to any one of [1] to [8] wherein X is selected from the group consisting of Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 . One species.

[10] The antiviral composition according to any one of the above [1] to [9], which is irradiated with visible light of 800 lux for 3 minutes, and has a virus inactivating ability of 99.9% or more.

[11] An antiviral agent, which comprises the antiviral composition according to any one of the above [1] to [10].

[12] A photocatalyst comprising the antiviral composition according to any one of the above [1] to [10].

[13] A method for producing an antiviral composition, comprising the steps of: mixing a BiVO ₄ with a divalent copper compound or a divalent copper compound raw material with water and a basic substance, preparing a mixture, and reacting with the mixture; The separation step of separation of the viral composition.

[14] The method for producing an antiviral composition according to the above [13], which further comprises a heat treatment step of heat-treating the antiviral composition separated by the separation step.

[15] The method for producing an antiviral composition according to the above [13] or [14] wherein, in the mixing step, the pH of the mixture is adjusted to be in the range of 8 to 12.

[16] The method for producing an antiviral composition according to any one of the above [13], wherein the divalent copper compound raw material contains the general formula (2): CuX ₂ (2)

(where X is an anion)

At least one type of divalent copper compound represented.

The method for producing an antiviral composition according to any one of the above [13], wherein, in the mixing step, BiVO ₄ and a divalent copper compound or a divalent copper compound raw material and water are In the total mass of the alkaline materials, the mass ratio of BiVO ₄ is 3 to 25% by mass.

[18] The method for producing an antiviral composition according to any one of the above [13], wherein, in the mixing step, BiVO ₄ and a divalent copper compound or a divalent copper compound are used in water. After mixing and stirring, an alkaline substance is added.

[19] A virus inactivating method, which comprises the antiviral composition according to any one of [1] to [10], the antiviral agent according to [11], or the photocatalyst according to [12]. Inactivated.

According to the present invention, it is possible to provide an antiviral composition, an antiviral agent, a photocatalyst, a method for producing the antiviral composition, and a method for deactivating a virus which are excellent in antiviral properties which are excellent in light and dark.

[Best Mode for Carrying Out the Invention]

As a result of reviewing the results, the present inventors have found that a composition containing BiVO ₄ and a divalent copper compound can be used to obtain an antiviral composition and an antiviral agent which exhibit excellent antiviral properties in bright and dark places without ultraviolet light. The present invention is obtained by a photocatalyst, a method for producing the antiviral composition, and a virus inactivation method. Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments. In the present specification, "bright place" means that although there is visible light having a wavelength of 400 nm or more, ultraviolet light is not present, and "dark place" means ultraviolet light and no light is present.

[antiviral composition]

The antiviral composition of the present invention is a composition containing BiVO ₄ and a divalent copper compound. By combining BiVO ₄ and a divalent copper compound, an antiviral composition excellent in antiviral properties in the bright and dark places can be obtained.

<BiVO ₄ >

The BiVO _{4 of the} present invention exhibits high photocatalytic activity in the visible light field. In the case of BiVO ₄ , those manufactured by the solid phase method and the liquid phase method can be used, and any of the antiviral compositions of the present invention can be used. In BiVO _4, BiVO e.g. Japanese Laid-Open Patent Publication No. 2001-2419 describes a method of producing the maker ₄ and JP-A-2004-24936 Publication BiVO ₄ describes the method of manufacturing the manufacturer and the like.

The specific surface area of BiVO _4, preferably 1 ~ 200m ² / g, more preferably 3 ~ 100m ² / g, more preferably 4 ~ 70m ² / g, and especially preferably 8 ~ 50m ² / g. When the specific surface area of BiVO ₄ is 1 m ² /g or more, the frequency of contact with the virus against the surface of the viral composition is increased, and the antiviral properties in the bright and dark portions of the antiviral composition are more excellent. When the specific surface area of BiVO ₄ is 200 m ² /g or less, the operation of the antiviral composition becomes easier. Here, the specific surface area means a specific surface area measured by a BET method of nitrogen adsorption.

<2-valent copper compound>

The divalent copper compound of the present invention is a copper compound having a valence of 2 in copper. The divalent copper compound alone does not exhibit antiviral properties in the bright and dark places. However, it is surprising that by combining with BiVO ₄ , the divalent copper compound exhibits antiviral properties in the bright and dark places. The copper compound having a valence of 2 is a copper compound having a valence of 2, and is not particularly limited. For example, a divalent copper compound is represented by (a) the following general formula (1): Cu ₂ (OH) ₃ X (1)

(where X is an anion)

The hydroxyl group-containing divalent copper compound, (b) divalent copper halide, (c) divalent copper mineral acid salt, (d) divalent copper organic acid salt, (e) copper oxide, (f) And one or more selected from the group consisting of copper sulfide, (g) copper azide (II), and (h) copper ruthenate.

Preferred X of the general formula (1) is a conjugate base of a halogen such as Cl, Br or I, a carboxylic acid such as CH ₃ COO, a conjugate base of an inorganic acid such as NO _{3 or} (SO ₄ ) _1/2 , and Any one selected from the group of OH. The more preferable X of the general formula (1) is one or more selected from the group consisting of Cl, CH ₃ COO, NO ₃ , (SO ₄ ) _1/2 and OH, and the general formula (1) Preferably, X is one selected from the group consisting of Cl, CH ₃ COO, NO ₃ , (SO ₄ ) _1/2 and OH.

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.

Preferably, the inorganic acid salt of (c) divalent copper is 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 selected from the group consisting of copper pyrophosphate and copper carbonate.

Preferably, the organic acid salt of (d) divalent copper is a divalent copper carboxylate. Preferred examples of the carboxylate of the divalent copper include copper formate, copper acetate, copper propionate, copper butyrate, copper pentanoate, copper citrate, copper heptate, copper octoate, copper ruthenate, copper citrate, and meat. Copper myristate, copper palmitate, copper heptadecate, hard ester Acid copper, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper behenate, oxalic acid Copper, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetonitrile, ethyl b Copper beryllate, copper isovalerate, copper beta-tellinate, copper diethyl acetate, copper methyl sulfonate, copper salicylate, copper bis(2-ethylhexane), azelaic acid One or more selected from the group consisting of copper and copper naphthenate.

Other preferred divalent copper compounds include, for example, Oxine-copper, copper acetonate, copper ethyl acetoacetate, copper trifluoromethane sulfonate, copper phthalocyanine, copper epoxide, copper. One or two or more selected from the group consisting of isopropoxide, copper methoxide, and copper dimethyldithiocarbamate.

The divalent copper compound of the present invention is preferably a hydroxyl group-containing divalent copper compound represented by the above general formula (1), a divalent copper halide, a divalent copper inorganic acid salt, and a divalent copper organic acid salt. One or two or more selected from the group. In addition, the divalent copper compound of the present invention is more preferably a hydroxyl group-containing divalent copper compound represented by the above general formula (1). Further, the hydroxyl group-containing divalent copper compound represented by the above general formula (1) may be an anhydride or a hydrate.

The mass of the copper element (mass of Cu) in the divalent copper compound contained in the antiviral composition of the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the BiVO ₄ . Further, it is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass. When the mass of the copper element in the copper compound is 0.01 parts by mass or more based on 100 parts by mass of BiVO ₄ , the antiviral properties and antibacterial properties in the bright and dark places are good. Moreover, the quality of divalent copper in the copper compound relative to 100 parts by mass of BiVO ₄ to 20 parts by mass or less, to prevent the surface of BiVO ₄ are coated with a divalent copper compound, can increase the antiviral activity of the photocatalyst composition, At the same time, it is economical to inactivate the virus with a small amount of antiviral composition.

Here, the relative parts by mass of copper mass of divalent copper compound in the 100 BiVO _4, BiVO may feedstock with a divalent copper compound is added in an amount of raw material ₄ is calculated. Further, the content of each component of the antiviral composition can be measured by ICP (inductively coupled plasma) luminescence spectrometry described later with respect to the mass of the copper element in 100 parts by mass of the bivalent copper compound of BiVO ₄ . specific.

In the antiviral composition, the divalent copper compound can be carried on BiVO ₄ . In addition, the antiviral composition, the divalent copper compound may not be supported in BiVO _4, dispersed in BiVO _4.

As described above, the antiviral composition of the present invention contains BiVO ₄ and a divalent copper compound as essential components, but may contain other optional components within the range not inhibiting the object of the present invention. However, the total content of the BiVO ₄ and the divalent copper compound in the antiviral composition is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99, from the viewpoint of improvement of the antiviral property. More than or equal to 100% by mass.

[Method for Producing Antiviral Composition]

The antiviral composition of the present invention can be produced by the method for producing an antiviral composition of the present invention. In the method for producing an antiviral composition of the present invention, for example, a method for producing an antiviral composition according to the first to third embodiments described below.

[Method for Producing Antiviral Composition of First Embodiment of the Present Invention]

In the method for producing an antiviral composition according to the first embodiment of the present invention, a method of mixing a BiVO ₄ with a divalent copper compound or a divalent copper compound with water and a basic substance to prepare a mixture, and separating the mixture by the mixture The separation step of the viral composition. Hereinafter, a method for producing an antiviral composition according to the first embodiment of the present invention will be described in detail.

<mixing step>

(BiVO ₄ )

BiVO ₄ is the same as BiVO ₄ described in the above antiviral composition. The ratio of BiVO ₄ in the mixture, the mass of the mixture, that is, the total mass of the BiVO ₄ and the divalent copper compound raw material or the divalent copper compound raw material and the water and the alkaline substance, is preferably 3 to 25% by mass, more preferably It is preferably 5 to 22.5 mass%, more preferably 7 to 20 mass%. When the ratio of the BiVO ₄ is 3% by mass or more, the productivity of the antiviral composition becomes high and economical, and when the ratio of BiVO ₄ is 25% by mass or less, the viscosity of the mixture becomes high, and the operation of the mixture can be suppressed. difficult.

(2-valent copper compound or divalent copper compound raw material)

The divalent copper compound is the same as the divalent copper compound described in the above antiviral composition. In addition, the raw material of the divalent copper compound is, for example, one or two or more kinds of divalent copper compound raw materials represented by the following general formula (2).

CuX ₂ (2)

In the general formula (2), X is the same as X of the above general formula (1). That is, X is an anion, preferably a halogen such as Cl, Br or I, a conjugate base of a carboxylic acid such as CH ₃ COO, a conjugate base of a mineral acid such as NO _{3 or} (SO ₄ ) _1/2 , Or OH. More preferably X is Cl, or more CH ₃ COO, NO ₃ and (SO _{4) 1/2} is selected from one kind or two or more, more preferably Cl, CH ₃ COO, NO ₃ and (SO _{4) 1/2} One selected.

The divalent copper compound raw material is hydrolyzed to a divalent copper compound by a reaction represented by the following chemical formula, and is supported on the surface of BiVO ₄ to form an antiviral composition. Further, HX of the following chemical formula is removed by an antiviral composition by washing with water, drying, or the like.

2CuX ₂ +BiVO ₄ +3H ₂ O→Cu ₂ (OH) ₃ X/BiVO ₄ +3HX

Here, "Cu ₂ (OH) ₃ X/BiVO ₄ " means that Cu ₂ (OH) ₃ X is supported on BiVO ₄ .

The divalent copper compound raw material represented by the general formula (2) may be one type of divalent copper compound raw material (that is, X is a monomer of a specific one of the divalent copper compound raw materials), and may be, for example, Cu (NO). _{) 2} with a mixture of Cu (OH) ₂ as the copper compound X starting material mixture of differing valence of 2 or more thereof. Further, the divalent copper compound raw material represented by the general formula (2) may be CuX ¹ X ² (however, X ¹ and X ² are different anions from each other). Further, the divalent copper compound raw material represented by the general formula (2) may be an anhydride or a hydrate.

The copper element mass of the raw material of the divalent copper compound is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.3 to 10 parts by mass, per 100 parts by mass of the BiVO ₄ . When the mass of the copper element of the raw material of the bismuth copper compound is 0.01 parts by mass or more, an antiviral composition excellent in antiviral properties in the bright and dark places can be produced. In addition, when the copper element mass of the divalent copper compound raw material is 20 parts by mass or less, the surface of the BiVO ₄ is prevented from being coated with the divalent copper compound raw material, and an antiviral composition exhibiting good photocatalytic activity can be produced. Moreover, the antiviral composition produced can be inactivated in a small amount, so it is economical. Further, the copper element mass of the divalent copper compound is the same as the copper element mass of the divalent copper compound described in the above antiviral composition.

(water)

Water is the solvent used in making the mixture. The water may further contain a polar solvent other than water. The divalent copper compound or the divalent copper compound raw material and the basic substance are soluble in water, and the polar solvent contained in the water is not particularly limited. Polar solvents such as alcohols, ketones and mixtures thereof. More specifically, a polar solvent, for example, selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, dimethylformamide, and tetrahydrofuran, and one or two of these may be used alone or in combination. The above is mixed.

(alkaline substance)

Preferred basic substances such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, alkaline surfactant (for example BYK) ‧JAPAN (shares) system, BYK-9077, etc.). A particularly good alkaline substance is sodium hydroxide. The alkaline substance is preferably added as a solution. The concentration of the basic substance in the alkali solution to be added is preferably from 0.1 to 5 mol/L, more preferably from 0.3 to 4 mol/L, still more preferably from 0.5 to 3 mol/L. When the concentration of the basic substance in the alkali solution is 5 mol/L or less, when the alkali solution is added, precipitation of the divalent copper compound can be suppressed from becoming uneven.

(mixing)

The order in which the BiVO ₄ and the divalent copper compound or the divalent copper compound raw material and the water and the basic substance are mixed is not particularly limited. However, it is preferred to first mix the BiVO ₄ in water and stir as necessary, and then mix the divalent copper compound or the divalent copper compound raw material and stir them. Further, the divalent copper compound or the divalent copper compound raw material may be initially mixed in water and stirred as necessary, and then BiVO _{4 is} mixed and stirred. Further, a divalent copper compound or a divalent copper compound raw material may be mixed with BiVO ₄ in water to carry out stirring.

The timing of adding the alkaline substance, so that there BiVO ₄ and / or divalent copper compound, or a divalent copper compound to the feedstock prior to the timing of the mixing water, so BiVO ₄ and / or divalent copper compound or divalent copper compound starting material mixed in water The timing on the way and the timing of mixing the BiVO ₄ and/or divalent copper compound or the divalent copper compound raw material in water. It is sufficient to add a basic substance to at least one of the three timings. However, it is preferred to mix BiVO ₄ with a divalent copper compound or a divalent copper compound raw material in water, and to sufficiently stir the alkali material.

The stirring time of the BiVO ₄ and the divalent copper compound or the divalent copper compound raw material and the water and the alkaline substance is such that the BiVO ₄ and the divalent copper compound or the divalent copper compound raw material are uniformly mixed with the water and the alkaline substance, Specially limited. For example, the stirring time is preferably from about 5 to about 120 minutes, more preferably from about 10 to about 60 minutes, still more preferably from about 15 to about 45 minutes. Further, the temperature of the mixture at the time of stirring is not particularly limited, and is, for example, room temperature to about 70 °C.

The pH of the mixture of the BiVO ₄ and the divalent copper compound or the divalent copper compound starting material and the water and the basic substance may also be adjusted. The pH of the mixture can be adjusted, for example, by adjusting the amount of alkaline material in the mixture. The pH of the mixture of BiVO ₄ and a divalent copper compound or a divalent copper compound and water and a basic substance is preferably 8 to 12, more preferably 9 to 11.5, still more preferably 9.5 to 11. When the pH of the mixture is from 8 to 12, the raw material of the divalent copper compound is favorably hydrolyzed and supported on the surface of BiVO ₄ , and the amount of the basic substance used is lowered, and the waste liquid treatment is facilitated. Further, the pH of the mixture was a value measured using a pH meter (D-51, manufactured by Horiba, Ltd.). When the mixture is heated, the pH of the mixture at a temperature of 25 ° C is measured using the above pH meter, and then the mixture is heated.

<Separation step>

By the separation step, the antiviral composition can be isolated, for example, in a solid form, from the mixture obtained as described above. The separation method of the separation step is not particularly limited, and for example, the antiviral composition can be separated from the mixture by filtration, sedimentation separation, centrifugation, evaporation drying, or the like. Preferably, the antiviral composition is separated from the mixture by filtration of the mixture. The separated antiviral composition is washed, dried, pulverized, and classified as necessary.

<heat treatment step>

The antiviral composition separated from the mixture by the separation step can be further subjected to heat treatment. By this heat treatment, the divalent copper compound is more strongly supported on BiVO ₄ .

The heat treatment temperature in the heat treatment step is preferably 150 to 600 ° C, more preferably 200 to 500 ° C, still more preferably 250 to 450 ° C. When the heat treatment temperature is 150 ° C or more, the divalent copper compound is more strongly bonded to BiVO ₄ . When the heat treatment temperature is 600 ° C or lower, the growth of the particles by sintering and the reduction of the specific surface area are suppressed, and the antiviral properties of the obtained antiviral composition in the bright and dark places are further improved.

The heat treatment time in the heat treatment step is preferably from 1 to 10 hours, more preferably from 2 to 8 hours, still more preferably from 3 to 5 hours. When the heat treatment time is 1 hour or longer, the divalent copper compound is more strongly bonded to BiVO ₄ . When the heat treatment time is 10 hours or less, the growth of the particles by sintering and the reduction of the specific surface area are suppressed, and the antiviral properties in the visible and dark places of the obtained antiviral composition are further improved. Further, the heat treatment environment is preferably an environment in which oxygen is present in the air.

[Method for Producing Antiviral Composition of Second Embodiment of the Present Invention]

A method for producing an antiviral composition according to a second embodiment of the present invention includes a mixing step of mixing BiVO ₄ and a divalent copper compound. The mixing in the mixing step may be dry mixing or wet mixing, and may be carried out by a conventional mixing method. Further, the BiVO ₄ and the divalent copper compound are the same as the BiVO ₄ and the divalent copper compound described in the above antiviral composition.

When the BiVO ₄ and the divalent copper compound are mixed by wet mixing, the solvent used in the wet mixing may be one in which the BiVO ₄ and the divalent copper compound are not dissolved, and is not particularly limited. A solvent used in wet mixing, such as water, alcohols, ketones, and mixtures thereof. Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and mixtures thereof. Ketones such as acetone, acetamidine, methyl ethyl ketone and mixtures thereof.

In the antiviral composition produced by the production method of the second embodiment of the present invention, only the BiVO ₄ and the divalent copper compound are mixed, and the divalent copper compound is not well supported in BiVO ₄ . However, the antiviral composition produced by the production method also exhibits excellent antiviral properties in the bright and dark places.

The antiviral composition prepared by mixing the BiVO ₄ and the divalent copper compound can be further subjected to heat treatment. The method of heat treatment is, for example, the same as the heat treatment of the heat treatment step described above.

[Method for Producing Antiviral Composition According to Third Embodiment of the Present Invention]

A method for producing an antiviral composition according to a third embodiment of the present invention includes a step of mixing a mixture of BiVO ₄ and a solution of a divalent copper compound, a step of preparing a mixture, a heating step of heating the mixture, and separating the antiviral composition from the heated mixture. The separation step. The aqueous solution of the divalent copper compound is an aqueous solution of a divalent copper compound having a copper component concentration of about several tens of g/100 mL. Further, the separation method of the separation step is not particularly limited, and for example, the antiviral composition can be separated from the mixture by filtration, sedimentation separation, centrifugation, evaporation drying, or the like. Further BiVO ₄ and divalent copper compound with the BiVO ₄ and 2 by the same monovalent copper compound in the above description of the antiviral composition.

The production method in the third embodiment of the present invention is specifically carried out, for example, as follows. The amount of copper in the aqueous solution of the divalent copper compound is placed in a specific container in an amount of 0.01 to 20 parts by mass based on the mass of the BiVO ₄ to be added. Next, added into the container in BiVO _4, BiVO ₄ mixed with an aqueous solution of a divalent copper compound, so BiVO ₄ was suspended in an aqueous solution of copper compound to prepare a mixture. After heating the mixture at a temperature of about 50 to 90 ° C, the mixture was filtered to obtain an antiviral composition. Further, the concentration of the copper component in the aqueous solution of the divalent copper compound and the heating temperature of the mixture are not limited by the concentration of the copper component and the heating temperature. The antiviral composition obtained by filtration is washed, dried, pulverized, classified, and the like as necessary.

The antiviral composition separated from the mixture by the separation step may be further subjected to heat treatment. a method of heat treatment, for example, the above The same method as the heat treatment of the heat treatment step in the method of the embodiment.

[Antiviral agents and photocatalysts]

The antiviral agent and photocatalyst of the present invention comprise the antiviral composition of the present invention. Thereby, the antiviral agent and photocatalyst of the present invention have excellent antiviral properties in the bright and dark places.

[Formation of antiviral composition, antiviral agent and photocatalyst]

The form of use of the antiviral composition, the antiviral agent, and the photocatalyst of the present invention (hereinafter referred to as "the antiviral composition 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 specific container. Alternatively, the antiviral composition of the present invention or the like may be used in the form of use of the antiviral composition of the present invention or the like on the surface and/or inside of a specific substrate. Generally, the use form of the latter is better. Further, the base material, for example, a single base material composed of a general member such as fiber, metal, ceramic, or glass, and a composite base material composed of two or more members of the above member. However, the substrate is not limited to this.

The coating agent such as a floor wax which can be peeled off by a suitable means may contain the antiviral composition of the present invention or the like. Further, the antiviral composition of the present invention or the like can be fixed to a specific film, and the antiviral composition of the present invention can be made equal to the surface of the continuous film. Alternatively, the anti-viral property of the present invention can be used in the form of a film-like body produced by sputtering a thin film of BiVO ₄ formed on glass to form a film of the antiviral composition of the present invention by sputtering. Composition, etc. In addition, the antiviral composition of the present invention or the like may be used in the form of a coating prepared by dispersing a solvent such as the antiviral composition of the present invention.

The antiviral composition of the present invention is equal to the material to which the surface of the substrate is immobilized, and the antiviral composition of the present invention is equal to the material to which the surface of the substrate is fixed, for example, by a general immobilization means such as a binder. Any of an organic binder and an inorganic binder can be used as a binder for immobilizing the antiviral composition of the present invention. However, in order to avoid decomposition of the binder due to the photocatalyst, an inorganic binder is used. good. The kind of the binder is not particularly limited. The inorganic binder is, for example, an inorganic binder such as a cerium oxide system which is usually used to immobilize a photocatalyst substance on the surface of a substrate. The organic binder is, for example, a polymer binder which can be polymerized and volatilized to form a film.

A material containing the antiviral composition of the present invention or the like in the inside of the substrate, for example, a material obtained by dispersing the antiviral composition of the present invention or the like in a resin to prepare a dispersion and curing the dispersion. Any of a natural resin and a synthetic resin can be used as the resin in which the antiviral composition of the present invention is dispersed. Synthetic resin such as acrylic resin, phenol resin, polyurethane resin, acrylonitrile/styrene copolymer resin, acrylonitrile/butadiene/styrene copolymerization (ABS) resin, polyester resin and epoxy resin Etc., but not limited to such resins.

The site where the antiviral composition or the like of the present invention is used is not particularly limited. For example, in the presence of any light, the hair can also be used in the dark. An antiviral composition, etc. Further, the antiviral composition of the present invention or the like has a presence in the presence of water (for example, in water and sea water), in a dry state (for example, in a state of low-humidity such as winter), in a state of high humidity, or in the presence of an organic substance. Excellent virus inactivation characteristics that continuously inactivate the virus. For example, the antiviral composition of the present invention or the like can be disposed on a wall, a floor, a patio, or the like. In addition, in buildings, work machines, measuring devices, and internal parts and components of hospitals and factories (such as refrigerators, washing machines, food washers, etc., filters for air cleaners, etc.) The antiviral composition or the like of the present invention can be applied. In a dark place, for example, a mechanical interior, a storage compartment of a refrigerator, and a hospital facility (a waiting room, an operating room, etc.) that becomes a dark place at night or when not in use, but is not limited thereto.

In the past, as one of the measures against influenza, it has been proposed to apply BiVO ₄ to a ceramic filter or a non-woven filter, and to combine an air cleaner that irradiates the filter with a light source for ultraviolet rays. However, when the antiviral composition of the present invention is used in the same manner as the filter of the air cleaner, the 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 a virus inactivating method for inactivating a virus 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, the virus can be inactivated using the antiviral composition of the present invention. Further, since the antiviral agent and photocatalyst of the present invention contain the antiviral composition of the present invention, the virus can be inactivated using the antiviral agent or photocatalyst of the present invention. The antiviral composition, the antiviral agent and the photocatalyst of the present invention have a virus deactivation ability of preferably 99.0% or more, more preferably 99.9% or more, under irradiation with visible light of 800 lux for 3 minutes. Here, the virus inactivating ability can be calculated by the formula of LOG (N/N ₀ ). In the formula, N ₀ is the phage concentration before visible light irradiation, and N is the phage concentration after visible light irradiation. The virus inactivation ability is described in detail in the examples described later.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples described below.

In the following Examples 1 to 4 and Comparative Examples 1 to 6, the following BiVO ₄ raw materials were used.

<BiVO ₄ raw materials>

An aqueous solution of NH ₂ VO ₃ (99.0%) and Bi(NO ₃ ) ₃ ‧5H ₂ O (Kanto Chemical Co., 99.9%) 0.12 mol/L was prepared by dissolving 2 mol/L of nitric acid. After mixing these aqueous solutions (100 mL), 3 g of urea was dissolved, and the mixture was heated to 90 ° C on a heating stirrer for 24 hours. The obtained suspension was filtered and dried to obtain a BiVO ₄ powder. The crystal structure of the dried BiVO ₄ raw material was measured using a powder X-ray diffractometer (manufactured by PANalytical Co., Ltd., X'pertPRO). The Cu-K α 1 line using a copper target was measured, and X-ray diffraction was performed under the measurement conditions of a tube voltage of 45 kV, a tube current of 40 mA, a measurement range of 2 θ=20 to 100 deg, a sampling width of 0.0167 deg, and a scanning speed of 3.3 deg/min. Determination. As a result of the measurement, it was found that the BiVO ₄ raw material was a single phase of BiVO ₄ .

Next, the production methods of Examples 1 to 4 and Comparative Examples 1 to 7 will be described.

<Example 1>

6 g of BiVO _{4 was} suspended in 100 mL of distilled water to prepare a suspension, and 0.0805 g (100 parts by mass of BiVO ₄ and 0.5 parts by mass of copper) of CuCl ₂ ‧2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) was added thereto. The suspension was stirred for 10 minutes. An aqueous solution of 1 mol/L sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH of the suspension to 10, followed by stirring and mixing for 30 minutes. The suspension was filtered, and the obtained powder was washed with pure water, dried at 80 ° C, and pulverized by a kneader to obtain the antiviral composition of Example 1.

<Example 2>

In addition to the addition of 0.0805 g of CuCl ₂ ‧2H ₂ O in suspension, 0.1179 g (relative to 100 parts by mass of BiVO ₄ and 0.5 parts by mass of copper) of CuSO ₄ ‧5H ₂ O (Kanto Chemical Co., Ltd.) was added. The antiviral composition of Example 2 was prepared in the same manner as in Example 1 except that the suspension was prepared.

<Example 3>

The same method as in Example 1 except that the amount of the suspension of CuCl ₂ ‧2H ₂ O was changed from 0.0805 g to 0.1610 g (relative to 100 parts by mass of BiVO ₄ and 1 part by mass in terms of copper) The antiviral composition of Example 3 was prepared.

<Example 4>

The same procedure as in Example 1 was carried out except that the amount of the CuCl ₂ ‧2H ₂ O suspension was changed from 0.0805 g to 0.4829 g (relative to 100 parts by mass of BiVO ₄ and 3 parts by mass in terms of copper). The antiviral composition of Example 4 was prepared.

<Comparative Example 1>

Comparative Example 1 is a BiVO ₄ raw material.

<Comparative Example 2>

5 g (100 parts by mass) of BiVO ₄ raw material and 0.025 g (0.5 parts by mass) of copper (manufactured by Kanto Chemical Co., Ltd., powder, 45 μm or less, 325 mesh) were placed in an agate mortar, and pulverized and mixed for 30 minutes. The composition of Comparative Example 2.

<Comparative Example 3>

In addition to the addition of 0.0805 g of CuCl ₂ ‧2H ₂ O in suspension, 0.0625 g (relative to 100 parts by mass of BiVO ₄ and 0.5 parts by mass of zinc) of ZnCl ₂ (manufactured by Kanto Chemical Co., Ltd.) was suspended. A composition of Comparative Example 3 was produced in the same manner as in Example 1 except for the turbid liquid.

<Comparative Example 4>

In addition to the addition of 0.0805 g of CuCl ₂ ‧2H ₂ O in suspension, 0.1452 g (relative to 100 parts by mass of BiVO ₄ , 0.5 parts by mass of iron) of FeCl ₃ ‧6H ₂ O (Kanto Chemical Co., Ltd.) was added. The composition of Comparative Example 4 was prepared in the same manner as in Example 1 except for the suspension.

<Comparative Example 5>

In addition to the addition of 0.0805 g of CuCl ₂ ‧2H ₂ O in suspension, 0.1215 g (relative to 100 parts by mass of BiVO ₄ , 0.5 parts by mass of nickel) of NiCl ₂ ‧6H ₂ O (Kanto Chemical Co., Ltd.) was added. The composition of Comparative Example 5 was prepared in the same manner as in Example 1 except for the suspension.

<Comparative Example 6>

BiVO ₄ except that the rutile titanium oxide was changed to F1-R (Showa Titanium Co., Ltd. , Ltd.). In the same manner as in Example 1 of the embodiment, making the composition of Comparative Example 6.

<Comparative Example 7>

3 g of CuCl ₂ ‧2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) was suspended in 100 mL of distilled water, and stirred for 10 minutes. Then, an aqueous solution of 1 mol/L sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH to 10, and the mixture was stirred and mixed for 30 minutes to prepare a mixture. The mixture was filtered, and the obtained powder was washed with pure water, dried at 80 ° C, and pulverized by a kneader to prepare a composition of Example 7 of a Cu ₂ (OH) ₃ Cl single phase composition.

<Measurement>

The following measurements were carried out on Examples 1 to 4 and Comparative Examples 1 to 7 produced as above.

(ICP emission spectroscopic analysis)

Copper ions and the like in the compositions of Examples 1 to 4 and Comparative Examples 3 to 5 were quantified by ICP emission spectroscopic analysis. Specifically, Examples 1 to 4 and Comparative Examples 3 to 5 were heated in a fluoric acid solution to be completely dissolved to prepare a solution. Further, an ICP emission spectrometer (manufactured by Shimadzu Corporation, model ICPS-7500) was used to analyze the extract liquid extracted from the solution, and to quantify the copper ions in the composition.

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

The antiviral properties of the compositions of Examples 1 to 4 and Comparative Examples 1 to 7 were confirmed by the following methods by a model experiment using phage. Further, a method of using a phage inactivating ability as a model of antiviral properties is described, for example, in Appl. Microbiol Biotechnol., 79, pp. 127-133 (2008), and it is known that this method can be used to obtain reliability. result. This measurement is based on JISR1706.

Spread the filter paper in a deep Petri dish and add a small amount of sterile water. A glass plate having a thickness of about 5 mm was placed on the filter paper, and a glass plate (50 mm × 50 mm × 1 mm) coated with 0.25 mg of the sample of the examples and the comparative examples was placed thereon. Using 1/500 NB, 100 μL of Q phage (NBRC20012) suspension having a phage infection price of about 6.7×10 ⁶ to about 2.6×10 ⁷ pfu/mL was prepared, and the sample was coated with phage to coat the PET. Film made of (polyethylene terephthalate). The glass plate was capped in the deep culture dish as a measurement kit. Prepare several identical measurement kits.

In addition, as a light source, a 15W white fluorescent lamp (made by Panasonic), an all-white fluorescent lamp, and FL15N is equipped with an ultraviolet blocking filter (Nippon Resin Industrial Co., Ltd., N-113). A plurality of measurement kits were allowed to stand at a position where the illuminance was 800 lux (illuminance meter: TOPCON system, measured by IM-5). The phage concentration of the sample on the glass plate was measured after 3 minutes, 10 minutes, and 60 minutes from the start of light irradiation. Moreover, the illuminance of the room at the time of measurement was 200 lux or less. Further, the elapsed time from the start of the light irradiation was measured using a commercially available code table.

The measurement of the phage concentration was carried out 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 shaker. This phage recovery solution was appropriately diluted with physiological saline added to peptone. The mixed solution of 5.0×10 ⁸ to 2.0×10 ⁹ /mL of Escherichia coli (NBRC106373) and the LB soft cold day medium supplemented with calcium were added, and 1 mL of the previously diluted solution was added and mixed, and the solution was dispersed. The LB cold medium supplemented with calcium was cultured at 37 ° C for 15 hours, and the number of plaques of the phage was visually measured. The phage concentration N was determined by multiplying the number of plaques obtained by the dilution ratio of the phage recovery solution.

The relative concentration of phage (LOG(N/N ₀ )) was determined from the initial phage concentration N ₀ and the phage concentration N after a certain time. Further, the smaller the value of LOG (N/N ₀ ) (the larger the negative value), the better the antiviral property of the sample.

(Evaluation of antiviral properties in the dark: determination of LOG (N/N ₀ ))

The measurement kit was placed in a dark place, and the same measurement was carried out as above (the measurement of the antiviral property in the bright spot: LOG (N/N ₀ )), except that the light was not irradiated from the light source. Further, the smaller the value of LOG (N/N ₀ ) (the larger the negative value), the better the antiviral property of the sample.

<Result>

(ICP emission spectroscopic analysis)

Ratio Example of copper ions in a relatively ₄ of 100 parts by mass of BiVO 0.5 parts by mass, the proportion of Example 2 in copper ions embodiment, relatively ₄ of 100 parts by mass of BiVO 0.5 parts by mass, for example, copper ions 3 embodiment the ratio , relative to 100 parts by mass of BiVO ₄ to 1 parts by mass, the proportion of copper ion in Example 4, 100 parts by mass relative to the BiVO ₄ to 3 parts by mass. From this, it can be seen that in Examples 1 to 4, the total amount of copper ions (from CuCl ₂ ‧2H ₂ O) added was supported on the surface of BiVO ₄ .

The proportion of zinc ions in Comparative Example 3 was 0.5 parts by mass based on 100 parts by mass of BiVO ₄ . From this, it is understood that the total amount of the added zinc ions is supported on the surface of the BiVO ₄ . Further, the proportion of the iron ions in Comparative Example 4 was 0.5 parts by mass based on 100 parts by mass of the BiVO ₄ . From this, it can be seen that the total amount of the added iron ions is supported on the surface of the BiVO ₄ . The proportion of nickel ions in Comparative Example 5 was 0.5 parts by mass relative to 100 parts by mass of BiVO ₄ . From this, it is understood that the total amount of the added nickel ions is supported on the surface of the BiVO ₄ .

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

The results are shown in Table 1 below.

(Evaluation of antiviral properties in the dark: determination of LOG (N/N ₀ ))

The results are shown in Table 2 below.

From the comparison of Examples 1 to 4 with Comparative Examples 1 to 7, it is understood that Examples 1 to 4 have excellent antiviral properties in the bright and dark places. In particular, even in Examples 1 to 4, light irradiation conditions of extremely short 3 minutes were observed, and it was confirmed that 99.9% of phage was inactivated, and it was excellent in immediate effect as compared with the conventional photocatalyst. In particular, it is understood that Examples 2 to 4 have a virus deactivation ability of 99.9% or more after being irradiated with visible light of 800 lux for 3 minutes.

Claims (19)

Toxic antiviral composition, characterized in comprising BiVO ₄ lines and divalent copper compound. The antiviral composition according to claim 1, wherein the mass of the copper element in the divalent copper compound is 0.01 to 20 parts by mass based on 100 parts by mass of the BiVO ₄ . The antiviral composition according to claim 1, wherein the divalent copper compound is (a) the following general formula (1): Cu ₂ (OH) ₃ X (1) (wherein X is an anion) The hydroxyl group-containing divalent copper compound, (b) divalent copper halide, (c) divalent copper mineral acid salt, (d) divalent copper organic acid salt, (e) copper oxide, (f) And one or more selected from the group consisting of copper sulfide, (g) copper azide (II), and (h) copper ruthenate. The antiviral composition according to claim 3, wherein X of the general formula (1) is any one selected from the group consisting of a halogen, a conjugate base of a carboxylic acid, a conjugate base of a mineral acid, and OH. The antiviral composition according to claim 3, wherein the halogen of the divalent copper (b) is one or more selected from the group consisting of copper chloride, copper fluoride and copper bromide. Composition. The antiviral composition according to claim 3, wherein the inorganic acid salt of the (c) divalent copper is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, sulfuric acid. One or more selected from the group consisting of ammonium copper, copper amide sulfate, copper ammonium chloride, copper pyrophosphate and copper carbonate Composition. The antiviral composition according to claim 3, wherein the organic acid salt of the divalent copper (d) is a divalent copper carboxylate. The antiviral composition according to claim 3, wherein the divalent copper compound is a hydroxyl group-containing divalent copper compound represented by the above general formula (1). The antiviral composition according to claim 3, wherein the X is one selected from the group consisting of Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 . The antiviral composition according to any one of claims 1 to 9, which is irradiated with visible light of 800 lux for 3 minutes, and has a virus inactivating ability of 99.9% or more. An antiviral agent comprising the antiviral composition according to any one of claims 1 to 10. A photocatalyst comprising the antiviral composition according to any one of claims 1 to 10. A method for producing an antiviral composition, comprising the steps of: mixing a BiVO ₄ with a divalent copper compound or a divalent copper compound raw material with water and a basic substance, preparing a mixture, and antiviral by the mixture; The separation step of composition separation. The method for producing an antiviral composition according to claim 13, further comprising a heat treatment step of subjecting the antiviral composition separated by the separation step to heat treatment. The manufacturer of the antiviral composition as recited in claim 13 In the above mixing step, the pH of the aforementioned mixture is adjusted to be in the range of 8 to 12. The method for producing an antiviral composition according to claim 13, wherein the divalent copper compound raw material contains at least one of the general formula (2): CuX ₂ (2) (wherein X is an anion) Valence copper compound. The method for producing an antiviral composition according to claim 13, wherein in the mixing step, the total quality of the BiVO ₄ and the divalent copper compound or the divalent copper compound raw material and the water and the basic substance are The mass ratio of the aforementioned BiVO ₄ is 3 to 25% by mass. 13 after the method of manufacturing the antiviral composition according to the requested item, wherein, in the mixing step, the BiVO ₄ is mixed with the divalent copper compound or the monovalent copper compound material 2 in water, stirred, adding a basic substance. A virus inactivation method characterized in that the virus is deactivated by using the antiviral composition according to any one of claims 1 to 10, the antiviral agent described in claim 11, or the photocatalyst described in claim 12.