JP2015134726A - Antiviral composition, production method thereof and virus inactivation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiviral composition, an antiviral agent and a photocatalyst, exhibiting excellent antiviral performance under visible light, and a production method of the antiviral composition and a virus inactivation method.SOLUTION: The antiviral composition contains iron oxide (III) (FeO) and bivalent copper compound. The antiviral agent and the photocatalyst contain the antiviral composition. The production method [1] of the antiviral composition comprises: a carrying step having a step of preparing fluid dispersion by mixing iron oxide (III) (FeO), water and one or more kind selected from a bivalent copper compound and a bivalent copper compound raw material represented by the general formula CuX, where X represents an anion; and a separation step of separating antiviral composition from the fluid dispersion, or the production method [2] of the antiviral composition comprises physically mixing iron oxide (III) (FeO) and the bivalent copper compound. The virus inactivation method inactivates virus by using the antiviral composition, the antiviral agent or the photocatalyst.

Description

The present invention relates to an antiviral composition containing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound that inactivates viruses, an antiviral agent and a photocatalyst including the antiviral composition, and an antiviral thereof The present invention relates to a method for producing a composition and a method for inactivating viruses.

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

Patent Document 1 describes a phage virus inactivating agent comprising anatase-type titanium oxide containing copper in a range of CuO / TiO ₂ (mass% ratio) = 1.0 to 3.5. By finding that titanium oxide containing copper inactivates phage virus, the inactivation agent of the invention described in Patent Document 1 has been completed. On the other hand, Patent Document 1 describes that anatase-type titanium oxide containing copper could not inactivate phages and viruses by irradiation with only visible light. That is, for the sample of CuO / TiO ₂ , antiviral evaluation was performed under ultraviolet irradiation (Examples 1 to 4, Comparative Examples 3 to 4), under visible light irradiation (Comparative Example 2), and in the dark (Comparative Example 1). Is going. And under visible light irradiation (Comparative Example 2) and in the dark (Comparative Example 1), there was no phage / virus inactivation effect. By the way, the light of white LED illumination which has been rapidly spreading in recent years does not include ultraviolet light. The phage / virus inactivating agent described in Patent Document 1 is expected to have no antiviral performance even under white LED illumination since it has no antiviral performance under dark and visible light irradiation. . For this reason, the application to the interior material of the phage virus inactivating agent described in Patent Document 1 is extremely limited.
Patent Document 2 describes that platinum-supported tungsten oxide particles exhibit antiviral activity under visible light irradiation. Although platinum-supported tungsten oxide particles exhibit antiviral properties under visible light irradiation, platinum is extremely rare and expensive, and thus it is difficult to industrially use platinum-supported tungsten oxide particles. In addition, the platinum-supported tungsten oxide particles described in Patent Document 2 have a very long light irradiation time of 2 to 6 hours for inactivating viruses, and are difficult to apply to members that are frequently touched by humans.

Further, in the combination of titanium oxide and copper or copper compound as described above, attention is paid to the valence of the copper compound, and a monovalent copper compound is also used as the copper compound.
That is, it is known that monovalent copper alone is excellent in inactivation performance of microorganisms and viruses, and that divalent copper does not have inactivation performance of microorganisms and viruses. Based on the known matter, a monovalent copper compound is used as a copper compound in a combination of titanium oxide and copper or a copper compound.
For example, Patent Document 3 describes a microorganism inactivating agent that contains a monovalent copper compound as an active ingredient and is used for inactivating microorganisms for a short time. Patent Document 3 describes a microorganism inactivating agent containing a photocatalytic substance together with a monovalent copper compound, and also describes that a titanium oxide catalyst can be used as the photocatalytic substance. Furthermore, Patent Document 3 describes that a monovalent copper compound has a much stronger inactivation effect on microorganisms than a divalent copper compound.
However, monovalent copper compounds are easily oxidized, and are particularly easily oxidized when they are microparticulated (200 nm or less) for transparency. When Cu ₂ O (red) is oxidized to change to CuO (black), color unevenness occurs, resulting in poor design. In addition, oxidation reduces the antiviral activity.

By the way, iron (III) oxide (Fe ₂ O ₃ ) has long been known as a photocatalyst, and its band gap is smaller than that of titanium oxide or tungsten oxide, and it can be used effectively for photons on longer wavelengths. It has been.
On the other hand, since the band gap is small, the conduction band level is located on the more positive side than that of titanium oxide or tungsten oxide. As a result, it is widely known that the photocatalytic activity is hardly exhibited even when irradiated with weak visible light having a low potential of excited electrons.
For example, Patent Document 4 describes that a complex in which iron (III) oxide (Fe ₂ O ₃ ) is baked and fixed on a silica nanostructure decomposes an organic substance under visible light irradiation. On the other hand, it is described that generally available iron (III) oxide (Fe ₂ O ₃ ) does not show any photocatalytic activity with respect to organic matter decomposition.
And the antiviral performance of the photocatalyst using iron (III) oxide (Fe ₂ O ₃ ) as a main raw material is not well known.

JP 2006-232729 A JP 2011-136984 A JP 2011-190192 A JP 2012-245481 A

  An object of the present invention is to provide an antiviral composition, an antiviral agent, a photocatalyst, a method for producing the antiviral composition, and a virus inactivating method that exhibit excellent antiviral performance under visible light. is there.

As a result of intensive studies, the present inventors have found that a composition containing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound exhibits excellent antiviral performance under visible light. The present invention has been completed to obtain an antiviral composition, an antiviral agent, a photocatalyst, a method for producing the antiviral composition, and a method for inactivating the virus.

That is, the present invention provides the following [1] to [19].
[1] An antiviral composition containing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound.
[2] The antiviral composition according to [1] above, wherein the iron (III) oxide (Fe ₂ O ₃ ) is α-iron (III) oxide (Fe ₂ O ₃ ).
[3] The above [1] or [2], wherein the mass of copper element in the divalent copper compound is 0.01 to 60 parts by mass with respect to 100 parts by mass of iron (III) oxide (Fe ₂ O ₃ ). An antiviral composition as described in 1. above.
[4] The divalent copper compound is (a) the following general formula (1):
Cu ₂ (OH) ₃ X (1)
(In the formula, X represents an anion)
(B) Divalent copper halide, (c) Divalent copper inorganic acid salt, (d) Divalent copper organic acid salt, (e) Cupric oxide , (F) copper sulfide, (g) copper (II) azide and (h) one or more selected from copper silicate, according to any one of [1] to [3] above Antiviral composition.
[5] (a) X in the general formula (1) representing a hydroxyl group-containing divalent copper compound is one or more selected from Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 The antiviral composition according to [4] above.
[6] The antiviral composition according to [4], wherein (b) the halide of divalent copper is one or more selected from copper chloride, copper fluoride, and copper bromide.
[7] (c) Divalent copper inorganic acid salt is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium sulfate copper, amide copper sulfate, ammonium chloride copper, The antiviral composition according to [4] above, which is one or more selected from copper pyrophosphate and copper carbonate.
[8] The antiviral composition according to [4], wherein (d) the organic acid salt of divalent copper is a divalent copper carboxylate.
[9] An antiviral agent containing the antiviral composition according to any one of [1] to [8].
[10] A photocatalyst containing the antiviral composition according to any one of [1] to [8].
[11] A dispersion obtained by mixing at least one selected from iron (III) oxide (Fe ₂ O ₃ ), water, a divalent copper compound, and a divalent copper compound raw material represented by the following general formula (2) The manufacturing method of an antiviral composition which has the carrying | support process which has the process of producing, and the isolation | separation process which isolate | separates an antiviral composition from the said dispersion liquid.
General formula (2):
CuX ₂ (2)
(In the formula, X represents an anion)
[12] The method for producing an antiviral composition according to [11] above, wherein in the supporting step, an alkaline substance is further mixed to prepare a dispersion.
[13] The method for producing an antiviral composition according to the above [11] or [12], wherein the obtained dispersion is heat-treated in the supporting step.
[14] A method for producing an antiviral composition, comprising physically mixing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound.
[15] The virus is inactivated using the antiviral composition according to any one of [1] to [8] above, the antiviral agent according to [9] above, or the photocatalyst according to [10] above. , Virus inactivation method.
[16] The method for producing an antiviral composition according to the above [12] or [13], wherein the pH of the dispersion is adjusted within the range of 8 to 12 in the supporting step.
[17] In the supporting step, iron (III) (Fe ₂ O ₃ ), water, and a divalent copper compound and at least one selected from divalent copper compound raw materials represented by the above general formula (2) ratio of the mass of iron oxide in the total mass _{(III) (Fe 2 O 3} ) is 3 to 25 mass%, the production method of the above-mentioned [11] to antiviral composition according to any one of [13].
[18] Physical mixing is performed at a ratio of the mass of iron (III) (Fe ₂ O ₃ ) in the total mass of iron (III) oxide (Fe ₂ O ₃ ) and the divalent copper compound is 3 to 25 mass%. The method for producing an antiviral composition according to the above [14].
[19] A method for producing an antiviral composition, further comprising a heat treatment step in the production method according to any one of [11] to [18].

  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 virus inactivating method that exhibit excellent antiviral performance under visible light. it can.

Shows an embodiment 1,5,8,11 and 12 and the sample of Comparative Example 1, 2, 3, 8, the phage concentration at 60 minutes after irradiation with visible light _{(LOG (N / N 0)} ) It is.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[Antiviral composition]
The antiviral composition of the present invention is a composition containing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound. By combining iron oxide (III) (Fe ₂ O ₃ ) and a divalent copper compound, an antiviral composition that exhibits excellent antiviral performance under visible light can be obtained.

<Iron oxide (III) (Fe ₂ O ₃ )>
The iron (III) oxide (Fe ₂ O ₃ ) used in the present invention alone does not exhibit antiviral performance under visible light. Surprisingly, however, antiviral performance under visible light is manifested in combination with a divalent copper compound that alone does not exhibit antiviral performance under visible light.
The iron (III) oxide (Fe ₂ O ₃ ) to be used is iron (III) oxide having any phase of α phase (for example, hematite), γ phase (for example, maghemite), β phase, ε phase or amorphous phase ( Fe ₂ O ₃ ) may be used, or may be used alone or as a mixture, but from the viewpoint of photocatalytic activity and cost, iron (III) oxide (Fe ₂ O ₃ ) is preferably an α phase (for example, hematite). ) -Iron (III) oxide (Fe ₂ O ₃ ) having) or γ-iron (III) oxide (Fe ₂ O ₃ ) having a γ phase (eg maghemite), more preferably an α phase (eg hematite). Α-iron oxide (III) (Fe ₂ O ₃ ).
As the iron (III) oxide (Fe ₂ O ₃ ), one produced by a known method can be used. For example, α-type (α-iron (III) oxide (Fe ₂ O ₃ )) can be obtained by heating α-type hydrate or hydroxide, or heating nitrate or oxalate. It also oxidizes iron (III) iron (II) (Fe ₃ O ₄ ) or slowly oxidizes iron compounds to produce iron (III) iron (II) (Fe ₃ O ₄ ) first. By doing so, the γ-type (γ-iron oxide (III) (Fe ₂ O ₃ )) can be obtained. In addition, it can be obtained by firing iron sulfide in the air, but industrially, it is produced by firing iron sulfate to about 650 to 700 ° C. The production method of iron (III) oxide (Fe ₂ O ₃ ) to be used is not limited to these.
Examples of commercially available iron oxide (III) (Fe ₂ O ₃ ) include iron oxide powder manufactured by Kanto Chemical Co., Ltd. (product name: iron oxide (III)).

The BET specific surface area of iron (III) oxide (Fe ₂ O ₃ ) is preferably 1 to 200 m ² / g, more preferably 3 to 150 m ² / g, and further preferably 4 to 125 m ² / g. Yes, and particularly preferably 8 to 100 m ² / g. When the BET specific surface area is 1 m ² / g or more, the frequency of contact of the virus with the surface of the antiviral composition increases, and the antiviral performance of the antiviral composition under visible light becomes more excellent. When the BET specific surface area of iron (III) oxide (Fe ₂ O ₃ ) is 200 m ² / g or less, handling of the antiviral composition becomes easier. Here, the BET specific surface area is defined by the BET multipoint method by nitrogen adsorption in accordance with JIS Z8830, and the relative pressure of nitrogen gas (adsorbate gas) is within a range of 0.05 to 0.30, It is a specific surface area determined by measuring three points.

The BET equivalent average primary particle size (nm) of iron (III) oxide (Fe ₂ O ₃ ) can be determined by measuring the BET specific surface area S (m ² / g) described above and using the following formula.
BET conversion average primary particle size (nm) = 6000 / (S × ρ)
Calculated from Here, ρ represents the density (g / cm ³ ) of the measurement substance.
For example, the density of iron oxide (III) (Fe ₂ O ₃ ) can be calculated using 5.2 g / cm ³ and the density of titanium oxide (TiO ₂ ) can be calculated using 4.0 g / cm ³ .
The average primary particle diameter in terms of BET when using iron (III) oxide (Fe ₂ O ₃ ) is preferably 5 nm to 1.1 μm, more preferably 7 nm to 385 nm, still more preferably 9 nm to 288 nm, particularly preferably. 11 nm to 144 nm. If the average primary particle diameter in terms of BET is 1.1 μm or less, antiviral performance is exhibited, and if it is 5 nm or more, handling is excellent.

<Divalent copper compound>
The divalent copper compound used in the present invention is a copper compound having a copper valence of 2. A divalent copper compound alone does not exhibit antiviral performance under visible light. Surprisingly, however, antiviral performance under visible light is manifested in combination with iron (III) oxide (Fe ₂ O ₃ ), which alone does not exhibit antiviral performance under visible light. The divalent copper compound is not particularly limited as long as it is a copper compound having a copper valence of 2. For example, the divalent copper compound is (a) the following general formula (1):
Cu ₂ (OH) ₃ X (1)
(In the formula, X represents an anion)
(B) Divalent copper halide, (c) Divalent copper inorganic acid salt, (d) Divalent copper organic acid salt, (e) Cupric oxide , (F) copper sulfide, (g) copper (II) azide, and (h) one or more selected from copper silicate.

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

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

  Preferred inorganic salt of (c) divalent copper is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium sulfate copper, amide copper sulfate, ammonium chloride copper, pyrophosphate It consists of 1 type, or 2 or more types selected from the group which consists of copper and copper carbonate.

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

  Other preferred divalent copper compounds are selected from the group consisting of oxine copper, acetylacetone copper, ethyl acetoacetate copper, trifluoromethane sulfonate copper, phthalocyanine copper, copper ethoxide, copper isopropoxide, copper methoxide and dimethyldithiocarbamate copper. 1 type or 2 types or more are mentioned.

  The divalent copper compound of the present invention is preferably (a) a hydroxyl group-containing divalent copper compound represented by the above general formula (1), (b) a divalent copper halide, and (c) an inorganic divalent copper. 1 type (s) or 2 or more types selected from the group which consists of an acid salt and the organic acid salt of (d) divalent copper. Moreover, since there are few impurities and cost does not start, the divalent copper compound of this invention is still more preferably a hydroxyl group-containing divalent copper compound represented by the above general formula (1). Note that (a) the hydroxyl group-containing divalent copper compound represented by the general formula (1) may be an anhydride or a hydrate.

Elemental copper mass in divalent copper compound contained in the antiviral composition of the present invention, with respect to 100 parts by weight of iron oxide _{(III) (Fe 2 O 3} ), preferably 0.01 to 60 mass Part, more preferably 0.1 to 20 parts by weight, still more preferably 0.1 to 15 parts by weight, and particularly preferably 0.3 to 10 parts by weight. When the copper element mass in the divalent copper compound is 0.01 parts by mass or more with respect to 100 parts by mass of iron (III) oxide (Fe ₂ O ₃ ), antiviral performance and antibacterial properties under visible light are obtained. Become good. Also, elemental copper mass in divalent copper compound, is not more than 60 parts by weight per 100 parts by weight of iron oxide _{(III) (Fe 2 O 3} ) , iron oxide _{(III) (Fe 2 O 3} ) Is prevented from being coated with a divalent copper compound, and the photocatalytic activity of the antiviral composition can be increased. In addition, when the mass of copper element in the divalent copper compound is 20 parts by mass or less with respect to 100 parts by mass of iron (III) oxide (Fe ₂ O ₃ ), a small amount of antiviral composition can be used. Since it can be inactivated, it becomes more economical.

Here, copper element mass in divalent copper compound with respect to 100 parts by mass of iron oxide _{(III) (Fe 2 O 3} ) is the raw material of the divalent copper compound and iron oxide _{(III) (Fe 2 O 3} ) material And can be calculated from the amount charged. In addition, the copper base mass in the divalent copper compound with respect to 100 parts by mass of iron oxide (III) (Fe ₂ O ₃ ) It can also be specified by measuring the content.

In the antiviral composition, the divalent copper compound may be supported on iron (III) oxide (Fe ₂ O ₃ ). In addition, in the antiviral composition, the divalent copper compound is not supported on iron (III) oxide (Fe ₂ O ₃ ), but the iron (III) oxide (Fe ₂ O ₃ ) and the divalent copper compound are simply It may be mixed.

As described above, the antiviral composition of the present invention contains iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound as essential components, but does not impair the object of the present invention. Other optional components may be contained. However, from the viewpoint of improving antiviral performance, the total content of iron (III) oxide (Fe ₂ O ₃ ) and divalent copper compound in the antiviral composition is preferably 90% by mass or more, and more Preferably it is 95 mass% or more, More preferably, it is 99 mass% or more, Most preferably, it is 100 mass%.

[Method for producing antiviral composition]
The antiviral composition of the present invention is one selected from iron (III) oxide (Fe ₂ O ₃ ), water, a divalent copper compound and a divalent copper compound raw material represented by the following general formula (2). It can be suitably manufactured by a supporting method having a step of preparing the dispersion by mixing the above and a manufacturing method having a separation step of separating the antiviral composition from the dispersion.
General formula (2):
CuX ₂ (2)
(In the formula, X represents an anion)
Further, the antiviral composition of the present invention, the manufacturing method of physical mixing iron oxide _{(III) (Fe 2 O 3} ) and a divalent copper compound, can be preferably produced.
As for the manufacturing method of the antiviral composition of this invention, the manufacturing method of the antiviral composition of the following 1st-3rd embodiment is mentioned, for example.

<The manufacturing method of the antiviral composition of the 1st Embodiment of this invention>
The manufacturing method of the antiviral composition in the 1st Embodiment of this invention is the hydroxyl-containing 2 represented by (a) general formula (1) among the bivalent copper compounds demonstrated by the said antiviral composition. In this method, a valence copper compound is supported on iron (III) oxide (Fe ₂ O ₃ ). Specifically, selected from iron (III) oxide (Fe ₂ O ₃ ) powder, water, an alkaline substance, and the divalent copper compound and the divalent copper compound raw material represented by the general formula (2). After obtaining a dispersion in which one or more of them are mixed, the divalent copper compound raw material is hydrolyzed, and (a) the hydroxyl group-containing divalent copper compound represented by the general formula (1) is converted into iron (III) (Fe ₂ A supporting step of depositing and supporting on O ₃ ), and a separation step of separating the antiviral composition from the obtained dispersion. Preferably, only the divalent copper compound material represented by the general formula (2) is used among the divalent copper compound and the divalent copper compound material represented by the general formula (2). Preferably, one or more selected from powders of iron (III) oxide (Fe ₂ O ₃ ), water, and the divalent copper compound and the divalent copper compound raw material represented by the general formula (2) Is obtained, and then an alkaline substance is mixed. Hereinafter, the manufacturing method of the antiviral composition in the 1st Embodiment of this invention is demonstrated in detail. In addition, in description of the manufacturing method of the antiviral composition in the following 1st Embodiment of this invention, a bivalent copper compound is (a) among the bivalent copper compounds demonstrated by the said antiviral composition. ) Represents a hydroxyl group-containing divalent copper compound represented by the general formula (1), and the divalent copper compound raw material represents a divalent copper compound raw material represented by the general formula (2).

(Supporting process)
[Iron oxide (III) (Fe ₂ O ₃ )]
Iron oxide _{(III) (Fe 2 O 3} ) is the same as the iron oxide described above antiviral composition _{(III) (Fe 2 O 3} ). Ratio of iron oxide _{(III) (Fe 2 O 3} ) , water, and one or more of the total weight for iron oxide selected from the divalent copper compound and a divalent copper compound precursor _{(III) (Fe 2 O 3} ) is Preferably it is 3-25 mass%, More preferably, it is 4-20 mass%, More preferably, it is 5-15 mass%. When the ratio of iron oxide (III) (Fe ₂ O ₃ ) is 3% by mass or more, the productivity of the antiviral composition becomes high and economical, and iron (III) (Fe ₂ O ₃ ) When the ratio is 25% by mass or less, it is possible to prevent the dispersion from becoming difficult to handle due to an increase in the viscosity of the dispersion.

[One or more selected from divalent copper compounds and divalent copper compound raw materials]
The divalent copper compound to be supported on iron (III) oxide (Fe ₂ O ₃ ) in the first embodiment refers to (a) the general formula (1) among the divalent copper compounds described in the antiviral composition. It is a hydroxyl group containing divalent copper compound represented by this. Moreover, (a) As a raw material of the bivalent copper compound represented by General formula (1), the 1 type, or 2 or more types of bivalent copper compound raw material represented by the said General formula (2) is mentioned, for example. .
In the general formula (2), X is the same as X in the general formula (1). That is, X is an anion, preferably a halogen such as Cl, Br and I, a conjugate base of a carboxylic acid such as CH ₃ COO, a conjugate base of an inorganic acid such as NO ₃ and (SO ₄ ) _1/2 , Or OH. X is more preferably one or more selected from Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 , and more preferably Cl, CH ₃ COO, NO ₃ and (SO _4). ) One type selected from _1/2 .

By the reaction shown in the following chemical formula, the divalent copper compound raw material represented by the general formula (2) is hydrolyzed to become a hydroxyl group-containing divalent copper compound represented by (a) the general formula (1), and iron oxide (III) Supported on the surface of (Fe ₂ O ₃ ). An antiviral composition is obtained as described above.
2CuX ₂ + Fe ₂ O ₃ + 3H ₂ O → Cu ₂ (OH) ₃ X / Fe ₂ O ₃ + 3HX
Here, “Cu ₂ (OH) ₃ X / Fe ₂ O ₃ ” indicates that Cu ₂ (OH) ₃ X is supported on iron (III) oxide (Fe ₂ O ₃ ).

The divalent copper compound raw material represented by the general formula (2) may be one divalent copper compound raw material (that is, a single divalent copper compound raw material in which X is a specific type), For example, it may be a mixture of two or more divalent copper compound raw materials having different Xs, such as a mixture of Cu (NO ₃ ) ₂ and Cu (OH) ₂ . Further, the divalent copper compound raw material represented by the general formula (2) may be CuX ¹ X ² (where X ¹ and X ² are different anions). Furthermore, the divalent copper compound raw material represented by the general formula (2) may be an anhydride or a hydrate.

  One or more total copper element masses selected from the divalent copper compound and the divalent copper compound raw material are the preferable copper element masses described in terms of the copper element mass in the divalent copper compound contained in the antiviral composition described above. Adjust so that

〔water〕
Water is a dispersion obtained by mixing iron oxide (III) (Fe ₂ O ₃ ), water, one or more selected from divalent copper compounds and divalent copper compound raw materials, and divalent copper compounds and divalent copper compounds. It is a solvent used when producing one or more aqueous solutions selected from raw materials. This water may further contain a polar solvent other than water. If 1 or more types chosen from an alkaline substance and a bivalent copper compound and a bivalent copper compound raw material melt | dissolve in water, the polar solvent contained in water will not be specifically limited. Examples of the polar solvent include alcohols, ketones, and a mixed solution thereof. More specifically, the polar solvent is selected from the group consisting of, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, dimethylformamide, and tetrahydrofuran, and these may be used alone or in combination. A mixture of seeds or more can be used.

[Alkaline substances]
Preferred alkaline substances include, for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, basic surfactant (for example, manufactured by Big Chemie Japan Co., Ltd., BYK-9077) and the like. A particularly preferred alkaline substance is sodium hydroxide. The alkaline substance is preferably added as a solution. The concentration of the alkaline substance in the alkaline solution to be added is preferably 0.1 to 5 mol / L, more preferably 0.3 to 4 mol / L, and still more preferably 0.5 to 3 mol / L. When the concentration of the alkaline substance in the alkaline solution is 5 mol / L or less, it is possible to suppress the precipitation of the divalent copper compound from becoming non-uniform when the alkaline solution is added.

〔mixture〕
The order in which one or more selected from iron (III) oxide (Fe ₂ O ₃ ), water, an alkaline substance, and a divalent copper compound and a divalent copper compound raw material are mixed is initially iron (III) (Fe ₂ It is preferable to mix O ₃ ) powder with water and stir as necessary, then mix one or more selected from divalent copper compounds and divalent copper compound raw materials, and stir these. First, one or more selected from divalent copper compounds and divalent copper compound raw materials are mixed with water and stirred as necessary, and then mixed with iron (III) oxide (Fe ₂ O ₃ ) powder. These may be stirred. In addition, one or more selected from iron (III) (Fe ₂ O ₃ ) powder, a divalent copper compound, and a divalent copper compound raw material may be simultaneously mixed and stirred in water.
The timing of adding the alkaline substance is the timing before mixing one or more selected from iron (III) (Fe ₂ O ₃ ) powder, divalent copper compound and divalent copper compound raw material with water, oxidation Iron (III) (Fe ₂ O ₃ ) powder, timing during mixing one or more selected from divalent copper compounds and divalent copper compound raw materials with water, and iron (III) oxide (Fe ₂ There is a timing after mixing O ₃ ) powder, one or more selected from a divalent copper compound and a divalent copper compound raw material with water. The alkaline substance may be added at at least one of these three timings. It should be noted that iron (III) (Fe ₂ O ₃ ) powder and at least one selected from a divalent copper compound and a divalent copper compound raw material are mixed in water and stirred sufficiently, and then an alkaline substance is added. Is preferred.

The stirring time for stirring at least one selected from iron (III) oxide (Fe ₂ O ₃ ), water, an alkaline substance, and a divalent copper compound and a divalent copper compound raw material is iron (III) (Fe ₂ O ₃ ) If it can mix uniformly 1 or more types chosen from water, an alkaline substance, a bivalent copper compound, and a bivalent copper compound raw material, it will not specifically limit. For example, the stirring time is preferably 5 to 120 minutes, more preferably 10 to 60 minutes, further preferably 15 to 45 minutes, and still more preferably 20 to 40 minutes. Further, the temperature of the dispersion during stirring is not particularly limited. For example, the temperature of the dispersion is preferably 3 to 95 ° C, more preferably 5 to 80 ° C, still more preferably 7 to 70 ° C, and still more preferably 10 to 60 ° C.

These iron oxide _{(III) (Fe 2 O 3} ), water, an alkaline material, as well as the pH of the mixed dispersion liquid at least one member selected from the divalent copper compound and a divalent copper compound precursor may be adjusted. For example, the pH of the dispersion can be adjusted by adjusting the amount of the alkaline substance in the dispersion. The pH of one or more dispersions selected from iron (III) oxide (Fe ₂ O ₃ ), water, an alkaline substance, and a divalent copper compound and a divalent copper compound raw material is preferably 8 to 12, more preferably. Is 9 to 11.5, more preferably 9.5 to 11. When the pH of the dispersion is 8 to 12, the divalent copper compound raw material is well hydrolyzed and supported on the surface of iron (III) oxide (Fe ₂ O ₃ ), and the amount of alkaline substance used is reduced. Therefore, waste liquid treatment becomes easy. The pH of the dispersion can be measured using a pH meter (for example, D-51, manufactured by Horiba, Ltd.). When heating the dispersion, the pH of the dispersion at a temperature of 25 ° C. is measured using a pH meter, and then the dispersion is heated.

(Separation process)
By the separation step, the antiviral composition can be separated from the dispersion liquid obtained as described above, for example, as a solid content. The separation method in this separation step is not particularly limited, and for example, the antiviral composition may be separated from the dispersion by filtration, sedimentation separation, centrifugation, evaporation to dryness, or the like. Preferably, the antiviral composition is separated from the dispersion by filtration of the dispersion. The separated antiviral composition is washed with water, dried, crushed, pulverized and classified as necessary.

(Heat treatment process)
You may heat-process the antiviral composition isolate | separated from the dispersion liquid by the isolation | separation process. By this heat treatment, the divalent copper compound is more firmly supported on iron (III) oxide (Fe ₂ O ₃ ).

The heat treatment temperature in the heat treatment step is preferably 150 to 600 ° C, more preferably 200 to 500 ° C, and further preferably 250 to 470 ° C. When the heat treatment temperature is 150 ° C. or higher, the divalent copper compound is strongly supported by iron (III) oxide (Fe ₂ O ₃ ). When the heat treatment temperature is 600 ° C. or lower, grain growth caused by sintering and reduction of the BET specific surface area are suppressed, and the antiviral performance under visible light in the resulting antiviral composition becomes better.

The heat treatment time in the heat treatment step is preferably 1 to 10 hours, more preferably 2 to 8 hours, and further preferably 3 to 5 hours. When the heat treatment time is 1 hour or longer, the divalent copper compound is more strongly supported on iron (III) oxide (Fe ₂ O ₃ ). When the heat treatment time is 10 hours or less, grain growth caused by sintering and reduction of the BET specific surface area are suppressed, and the antiviral performance under visible light in the resulting antiviral composition becomes better. The heat treatment atmosphere is preferably an atmosphere in which oxygen exists such as in the air.

<The manufacturing method of the antiviral composition of the 2nd Embodiment of this invention>
In the method for producing an antiviral composition according to the second embodiment of the present invention, a powder of iron (III) (Fe ₂ O ₃ ) is represented by the divalent copper compound and the general formula (2). It consists of a mixing step for preparing a dispersion by mixing with one or more aqueous solutions selected from divalent copper compound raw materials, a heating step for heating the dispersion, and a separation step for separating the antiviral composition from the heated dispersion. It is a manufacturing method. One or more aqueous solutions selected from the divalent copper compound and the divalent copper compound raw material represented by the general formula (2) have a copper component concentration of several to several tens of g / 100 mL. It is 1 or more types of aqueous solution chosen from a divalent copper compound raw material represented by a compound and the said General formula (2). The separation method in the separation step is not particularly limited, and the antiviral composition may be separated from the dispersion by, for example, filtration, sedimentation separation, centrifugation, evaporation to dryness, or the like.
Preferably, only the divalent copper compound is used among the divalent copper compound and the divalent copper compound raw material represented by the general formula (2).
Incidentally, in the explanation of the manufacturing method of the antiviral composition according to the second embodiment of the present invention, the iron oxide _{(III) (Fe 2 O 3} ), iron oxide (III described above antiviral composition ) (Fe ₂ O ₃ ). In addition, the divalent copper compound refers to (a) a hydroxyl group-containing divalent copper compound represented by the general formula (1) among the divalent copper compounds described in the antiviral composition, and (b) divalent copper. (C) inorganic salt of divalent copper, (d) organic salt of divalent copper, (e) cupric oxide, (f) copper sulfide, (g) copper (II) azide and (H) 1 type or 2 types or more selected from the group which consists of copper silicate is represented, and a bivalent copper compound raw material represents the bivalent copper compound raw material represented by the said General formula (2).

(Supporting process)
Specifically, the manufacturing method according to the second embodiment of the present invention is performed as follows, for example.
[Mixing process]
Preferred copper element described in terms of the copper element mass in the divalent copper compound contained in the antiviral composition is the mass of copper element in one or more aqueous solutions selected from divalent copper compounds and divalent copper compound raw materials It adjusts so that it may become mass, and puts 1 or more types of aqueous solution chosen from a bivalent copper compound and a bivalent copper compound raw material into a predetermined container. Specifically, 0.01 to 60 parts by mass with respect to 100 parts by mass of iron (III) oxide (Fe ₂ O ₃ ) added to one or more aqueous solutions selected from divalent copper compounds and divalent copper compound raw materials. One or more aqueous solutions selected from divalent copper compounds and divalent copper compound raw materials in such an amount are placed in a predetermined container.
Next, iron (III) (Fe ₂ O ₃ ) is put into the container, and iron (III) (Fe ₂ O ₃ ) is selected from divalent copper compounds and divalent copper compound raw materials. Mix with aqueous solution to make dispersion.
[Heating process]
The dispersion obtained in the mixing step is preferably heated to a temperature of 50 to 95 ° C.
The concentration of the copper component in one or more aqueous solutions selected from the divalent copper compound and the divalent copper compound raw material and the heating temperature of the dispersion are not limited to the above-described concentration and heating temperature of the copper component. .

(Separation process)
By the separation step, the antiviral composition can be separated from the dispersion liquid obtained as described above, for example, as a solid content. The separation method in this separation step is not particularly limited, and for example, the antiviral composition may be separated from the dispersion by filtration, sedimentation separation, centrifugation, evaporation to dryness, or the like. Preferably, the antiviral composition is separated from the dispersion by filtration of the dispersion. The separated antiviral composition is washed with water, dried, crushed, pulverized and classified as necessary.

(Heat treatment process)
You may heat-process the antiviral composition isolate | separated from the dispersion liquid by the isolation | separation process. The heat treatment method is, for example, the same method as the heat treatment in the heat treatment step in the method of the first embodiment described above.

<The manufacturing method of the antiviral composition of the 3rd Embodiment of this invention>
The manufacturing method of the antiviral composition in the third embodiment of the present invention is a manufacturing method in which iron (III) (Fe ₂ O ₃ ) and a divalent copper compound are physically mixed. The mixing in the embodiment may be dry mixing or wet mixing, and can be performed by a known mixing method.
Incidentally, in the explanation of the manufacturing method of the antiviral composition according to the third embodiment of the present invention, the iron oxide _{(III) (Fe 2 O 3} ), iron oxide (III described above antiviral composition ) (Fe ₂ O ₃ ). In addition, the divalent copper compound refers to (a) a hydroxyl group-containing divalent copper compound represented by the general formula (1) among the divalent copper compounds described in the antiviral composition, and (b) divalent copper. (C) inorganic salt of divalent copper, (d) organic salt of divalent copper, (e) cupric oxide, (f) copper sulfide, (g) copper (II) azide and (H) represents one or more selected from the group consisting of copper silicate.

When iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound are mixed by wet mixing, the solvent used in the wet mixing is iron (III) oxide (Fe ₂ O ₃ ), divalent copper compound and If it does not melt | dissolve, it will not specifically limit.

The antiviral composition produced by the production method of the third embodiment of the present invention is simply a mixture of iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound. However, the antiviral composition produced by this production method also exhibits excellent antiviral performance under visible light.

  You may heat-process the antiviral composition manufactured by the manufacturing method of the 3rd Embodiment of this invention further. The heat treatment method is, for example, the same method as the heat treatment in the heat treatment step in the method of the first embodiment described above.

[Antiviral agent and photocatalyst]
The antiviral agent and photocatalyst of the present invention include the antiviral composition of the present invention. Thereby, the antiviral agent and photocatalyst of the present invention have excellent antiviral performance under visible light.

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

The antiviral composition of the present invention may be contained in a coating agent such as floor polish that can be peeled off by an appropriate means. Further, the antiviral composition or the like of the present invention may be immobilized on a predetermined film, and the antiviral composition or the like of the present invention may be exposed on the surface of the continuous film. Alternatively, a film-like body prepared by further forming a thin film of the antiviral composition of the present invention by sputtering on the surface of a thin-film iron oxide (III) (Fe ₂ O ₃ ) formed on glass by sputtering In this form, the antiviral composition of the present invention may be used. In addition, the antiviral composition of the present invention may be used in the form of a paint prepared using a solvent in which the antiviral composition of the present invention is dispersed.

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

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

  The place where the antiviral composition of the present invention is used is not particularly limited. For example, the antiviral composition of the present invention and the like can be used in the presence of any light beam that exhibits the photocatalytic activity of the antiviral composition of the present invention. In addition, the antiviral composition of the present invention can be used in the presence of water (for example, in water and seawater), in a dry state (for example, in a low humidity state in winter, etc.), in a high humidity state, or in an organic matter. Even in the presence of coexistence, it has high virus inactivation properties and can inactivate viruses continuously. For example, the antiviral composition of the present invention can be placed on walls, floors, ceilings, and the like. In addition, any interior such as buildings such as hospitals and factories, machine tools, measuring devices, electrical appliances and parts (for example, interiors of refrigerators, washing machines and dishwashers, and filters of air cleaners, etc.) The antiviral composition of the present invention can be applied to an object. Further, in the presence of an arbitrary light beam that expresses the photocatalytic activity of the antiviral composition of the present invention, examples include the inside of the machine, a refrigerator storage room, and a hospital facility (waiting room, operating room, etc.). It is not limited to these.

  Conventionally, as a countermeasure against influenza, an air cleaning machine has been proposed in which a ceramic filter or a non-woven filter is coated with titanium oxide and a light source for irradiating the filter with ultraviolet light is incorporated. However, when the antiviral composition of the present invention is used for a filter of an air cleaner, if there is visible light, an ultraviolet light source is not necessary, thereby reducing the cost of the air cleaner, Safety can be increased.

[Virus inactivation method]
The present invention provides a virus inactivation 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 performance, viruses can be inactivated using the antiviral composition of the present invention. Moreover, since the antiviral agent and photocatalyst of this invention contain the antiviral composition of this invention, a virus can be inactivated using the antiviral agent or photocatalyst of this invention. The antiviral composition, antiviral agent and photocatalyst of the present invention have a virus inactivating ability of preferably 99.0% or more, more preferably 99.9% or more in 60 minutes of visible light irradiation with an illuminance of 800 lux. Have. Here, the virus inactivation ability can be calculated by the equation of LOG (N / N ₀ ). Wherein, N ₀ is the phage concentration before irradiation with visible light, N is the is the phage concentration after visible light irradiation. The ability to inactivate viruses will be described in detail in the examples below.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to the following Example.

In Examples 1 to 12 and Comparative Examples 1 to 8 described later, the following iron (III) (Fe ₂ O ₃ ) raw material was used.

<Α-Iron oxide (III) (Fe ₂ O ₃ )>
For α-iron oxide (III) (Fe ₂ O ₃ ) used in the production of Examples and Comparative Examples, powder of iron (III) oxide (Fe ₂ O ₃ ) manufactured by Kanto Chemical Co., Ltd. was used.
<Γ-iron oxide (III) (Fe ₂ O ₃ )>
As the γ-iron (III) oxide (Fe ₂ O ₃ ) used for the production of the examples and comparative examples, powder of γ-Fe ₂ O ₃ manufactured by IoLiTech Ionic Liquids Technologies GmbH was used.

(BET specific surface area)
BET of α-iron oxide (III) (Fe ₂ O ₃ ), γ-iron oxide (III) (Fe ₂ O ₃ ), nitrogen (N) -doped titanium oxide, and iron trioxide (Fe ₃ O ₄ ) As the specific surface area, a fully automatic BET specific surface area measuring device “Macsorb, HM model-1208” manufactured by Mountec Co., Ltd. was used.
In accordance with JIS Z8830, the gas adsorption amount was determined by measuring three points within a relative pressure of nitrogen gas (adsorbate gas) of 0.05 to 0.30 by the BET multipoint method by nitrogen adsorption.

(BET conversion average primary particle size)
The average primary particle size (nm) in terms of BET was determined by the BET multipoint method using α-iron oxide (III) (Fe ₂ O ₃ ), γ-iron oxide (III) (Fe ₂ O ₃ ), nitrogen (N) — The BET specific surface area S (m ² / g) of the doped titanium oxide and triiron tetroxide (Fe ₃ O ₄ ) was measured, and the following formula BET conversion average primary particle size = 6000 / (S × ρ)
Calculated from Here, ρ represents the density (g / cm ³ ) of the oxide.
Specifically, the density of α-iron oxide (III) (Fe ₂ O ₃ ), γ-iron oxide (III) (Fe ₂ O ₃ ), and iron trioxide (Fe ₃ O ₄ ) is 5.2 g. The density of nitrogen / N ³ -doped titanium oxide was calculated using 4.0 g / cm ³ .
Table 1 shows the measurement results of the oxides used in Examples and Comparative Examples.

<Production Example 1>
(Nitrogen (N) -doped titanium oxide)
63 g of titanium chloride (manufactured by Kanto Chemical Co., Inc.) was suspended in 1000 ml of distilled water cooled to 4 ° C., and 1000 g of 28% aqueous ammonia (manufactured by Kanto Chemical Co., Ltd.) was added dropwise. The precipitate was filtered, and the obtained powder was washed with pure water, dried at 80 ° C., and crushed with a mixer. The crushed material was heat-treated at 400 ° C. for 1 hour to produce nitrogen (N) -doped titanium oxide.

  Next, the manufacturing method of Examples 1-12 and Comparative Examples 1-8 is demonstrated.

<Example 1>
A suspension was prepared by suspending 6 g of α-iron (III) oxide (Fe ₂ O ₃ ) (manufactured by Kanto Chemical Co., Ltd.) in 100 ml of distilled water, and 0.0805 g (100 parts by mass of oxidation). CuCl ₂ .2H ₂ O (manufactured by Kanto Chemical Co., Inc.) of iron (III) (0.5 parts by mass with respect to Fe ₂ O ₃ ) was added to the suspension and stirred for 10 minutes. A dispersion was prepared. A 1 mol / L aqueous solution of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added so that the pH of this dispersion was 10, and the mixture was stirred and mixed at room temperature (20 ° C.) for 30 minutes. This dispersion was filtered, and the obtained powder was washed with pure water, dried at 80 ° C., and crushed with a mixer to obtain a sample.

<Example 2>
Instead of adding 0.0805 g CuCl ₂ · 2H ₂ O to the suspension, 0.1136 g (0.5 parts by mass copper with 100 parts by mass iron (III) oxide (Fe ₂ O ₃ )) A sample was obtained in the same manner as in Example 1 except that Cu (NO ₃ ) ₂ · 5H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added.

<Example 3>
A suspension was prepared by suspending 6 g of α-iron (III) oxide (Fe ₂ O ₃ ) (manufactured by Kanto Chemical Co., Ltd.) in 100 ml of distilled water, and 0.0805 g (100 parts by mass of oxidation). CuCl ₂ .2H ₂ O (manufactured by Kanto Chemical Co., Inc.) of iron (III) (0.5 parts by mass of copper with respect to Fe ₂ O ₃ ) was added to the suspension and stirred for 10 minutes. A dispersion was prepared. This dispersion was evaporated to dryness at 80 ° C., and the resulting powder was crushed with a mixer to obtain a sample.

<Example 4>
Instead of adding 0.0805 g of CuCl ₂ · 2H ₂ O to the suspension, 0.0952 g (100 parts by mass of α-iron (III) oxide (Fe ₂ O ₃ ) with 0.5 mass of copper) Part) Cu (CH ₃ COO) ₂ .H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added to the suspension to obtain a sample in the same manner as in Example 1.

<Example 5>
The antiviral composition obtained in Example 1 was heat-treated in air at 450 ° C. for 3 hours to obtain a sample.

<Examples 6 to 10>
The added amount of CuCl ₂ · 2H ₂ O is 0.05 parts by mass (Example 6) and 1 part by mass (Example 7) of copper with respect to 100 parts by mass of iron (III) oxide (Fe ₂ O ₃ ). Samples were obtained in the same manner as in Example 1 except that they were changed to 5 parts by mass (Example 8), 18 parts by mass (Example 9), and 50 parts by mass (Example 10).

<Example 11>
The powder of α-iron oxide (III) (Fe ₂ O ₃ ) (manufactured by Kanto Chemical Co., Ltd.) is changed to powder of γ-iron oxide (III) (Fe ₂ O ₃ ) (manufactured by IoLiTech Ionic Liquids Technologies GmbH) A sample was obtained in the same manner as in Example 1 except that.

<Example 12>
3 g of CuCl ₂ · 2H ₂ O (manufactured by Kanto Chemical Co., Inc.) was dissolved in 100 mL of distilled water and stirred for 10 minutes. A 1 mol / L aqueous solution of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added so that the pH was 10, and the mixture was stirred and mixed for 30 minutes. The precipitated Cu ₂ (OH) ₃ Cl slurry is filtered, and the resulting powder is washed with pure water, dried at 80 ° C., crushed with a mixer, and the Cu ₂ (OH) ₃ Cl single phase is removed. Obtained.
0.0504 g (0.5 parts by mass of copper with respect to 100 parts by mass of α-iron oxide (III) (Fe ₂ O ₃ )) of this Cu ₂ (OH) ₃ Cl single phase, α-iron oxide ( III) 6 g of the powder of (Fe ₂ O ₃ ) was physically mixed in an agate mortar for 30 minutes to obtain a sample.

<Comparative Example 1>
In Comparative Example 1, a powder of α-iron oxide (III) (Fe ₂ O ₃ ) (manufactured by Kanto Chemical Co., Inc.) was prepared and used as a sample.

<Comparative Example 2>
5 g (100 parts by mass) of powder of α-iron oxide (III) (Fe ₂ O ₃ ) and 0.025 g (0.5 parts by mass) of copper powder (manufactured by Kanto Chemical Co., Ltd.) are put in an agate mortar. A sample was obtained by grinding and mixing for 30 minutes.

<Comparative Example 3>
Instead of adding 0.0805 g of CuCl ₂ .2H ₂ O to the suspension, 0.0625 g (0.5 parts by mass of zinc with respect to 100 parts by mass of α-iron (III) oxide (Fe ₂ O ₃ )) Part) ZnCl ₂ (manufactured by Kanto Chemical Co., Inc.) was added to the suspension to obtain a sample in the same manner as in Example 1.

<Comparative Example 4>
Instead of adding 0.0805 g CuCl ₂ .2H ₂ O to the suspension, 0.545 g iron with 0.1452 g (100 parts by mass α-iron (III) oxide (Fe ₂ O ₃ )) Part) FeCl ₃ .6H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added to the suspension to obtain a sample in the same manner as in Example 1.

<Comparative Example 5>
Instead of adding 0.0805 g CuCl ₂ .2H ₂ O to the suspension, 0.1215 g (0.5 parts by mass of nickel per 100 parts by weight of α-iron (III) oxide (Fe ₂ O ₃ )) Part) NiCl ₂ .6H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added to the suspension to obtain a sample in the same manner as in Example 1.

<Comparative Example 6>
Instead of adding 0.0805 g of CuCl ₂ .2H ₂ O to the suspension, 0.1215 g (0.5 parts by mass of manganese with respect to 100 parts by mass of α-iron (III) oxide (Fe ₂ O ₃ )) Part) MnCl ₂ .4H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added to the suspension to obtain a sample in the same manner as in Example 1.

<Comparative Example 7>
A sample was obtained in the same manner as in Example 1 except that the powder of α-iron (III) oxide (Fe ₂ O ₃ ) was replaced with nitrogen (N) -doped titanium oxide prepared in Production Example 1. Got.

<Comparative Example 8>
The powder of α-iron oxide (III) (Fe ₂ O ₃ ) (manufactured by Kanto Chemical Co., Ltd.) was changed to powder of iron trioxide (Fe ₃ O ₄ ) (manufactured by Kanto Chemical Co., Ltd.). A sample was obtained in the same manner as in Example 1.

<Measurement>
The following measurements were performed for Examples 1 to 12 and Comparative Examples 1 to 8 produced as described above.

(ICP emission spectroscopy)
Copper ions and the like in the compositions of Examples 1 to 12 and Comparative Examples 2 to 8 were quantified by ICP emission spectroscopic analysis. Specifically, Examples 1-12 and Comparative Examples 2-8 were heated in a hydrofluoric acid solution and completely dissolved to prepare a solution. And the extract extracted from the solution was analyzed using an ICP emission spectrometer (model number ICPS-7500, manufactured by Shimadzu Corporation), and copper ions and the like in the composition were quantified.
(Identification of divalent copper compounds and other transition metal compounds)
About the obtained sample, "X'pertPRO" made by PANalytical is used as a measuring apparatus, a copper target is used, a Cu-Kα1 wire is used, a tube voltage is 45 kV, a tube current is 40 mA, a measurement range is 2θ = 20 to 100 deg, sampling X-ray diffraction measurement was performed under the conditions of a width of 0.0167 deg and a scanning speed of 3.3 deg / min, and the metal compound supported or mixed was identified.

(Evaluation of antiviral performance under visible light irradiation: measurement of LOG (N / N ₀ ))
The antiviral performance of the compositions of Examples 1 to 12 and Comparative Examples 1 to 8 was confirmed by the following method by model experiments using bacteriophages. A method of using the inactivation ability against bacteriophage as a model of antiviral performance is described in, for example, Appl. Microbiol Biotechnol. 79, pp. 127-133 (2008), and it is known that reliable results can be obtained by this method. This measurement is based on JIS R 1706.

A filter paper was laid in the deep petri dish, and a small amount of sterilized water was added. 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 example and the comparative example was placed thereon. On top of this, 1/500 NB was used to prepare a bacteriophage infectious titer of about 6.7 × 10 ⁶ to about 2.6 × 10 ⁷ pfu / ml, and 100 μL of QB phage (NBRC20012) suspension was dropped. In order to bring the sample surface into contact with the phage, an OHP film made of PET (polyethylene terephthalate) was covered. This deep petri dish covered with a glass plate was used as a measurement set. A plurality of similar measurement sets were prepared.

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

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

The relative phage concentration (LOG (N / N ₀ )) was determined from the initial phage concentration N ₀ and the phage concentration N after a predetermined time. The smaller the value of LOG (N / N ₀ ), the better the antiviral performance of the sample.

<Result>
(ICP emission spectroscopy)
Copper with respect to 100 parts by mass of iron (III) oxide (Fe ₂ O ₃ ), 100 parts by mass of nitrogen (N) -doped titanium oxide, or 100 parts by mass of iron trioxide (Fe ₃ O ₄ ) in each Example and Comparative Example The proportion of ions is 0.5 parts by mass in Examples 1 to 5, and Example 11, and Comparative Examples 2, 7 and 8, and Example 6 is 0.05 parts by mass. Example 7 was 1 part by mass, Example 8 was 5 parts by mass, Example 9 was 18 parts by mass, and Example 10 was 50 parts by mass. Thus, in Examples 1 to 11 and Comparative Examples 2, 7 and 8, the total amount of copper ions charged was iron (III) oxide (Fe ₂ O ₃ ) and nitrogen (N) -doped titanium oxide. Or supported on the surface of triiron tetroxide (Fe ₃ O ₄ ).
The amount of the Cu ₂ (OH) ₃ Cl single phase with respect to 100 parts by mass of iron (III) (Fe ₂ O ₃ ) in Example 12 is 0.5 parts by mass of copper ions, and the prepared Cu ₂ (OH) ₃ It was found that the entire amount of the Cl single phase was mixed with iron (III) oxide (Fe ₂ O ₃ ).

Ratio of zinc ions in Comparative Example 3 was 0.5 parts by mass with respect to the iron oxide _{(III) (Fe 2 O 3} ) 100 parts by weight. From this, it was found that the total amount of charged zinc ions was supported on the iron (III) oxide (Fe ₂ O ₃ ) surface. The ratio of iron ions of Comparative Example 4 was 0.5 parts by mass with respect to the iron oxide _{(III) (Fe 2 O 3} ) 100 parts by weight. From this, it was found that the total amount of charged iron ions was supported on the iron (III) oxide (Fe ₂ O ₃ ) surface. Furthermore, the proportion of nickel ions in Comparative Example 5 was 0.5 parts by mass with respect to the iron oxide _{(III) (Fe 2 O 3} ) 100 parts by weight. From this, it was found that the total amount of charged nickel ions was supported on the iron (III) oxide (Fe ₂ O ₃ ) surface. Furthermore, the proportion of manganese ions in Comparative Example 6 was 0.5 parts by mass with respect to the iron oxide _{(III) (Fe 2 O 3} ) 100 parts by weight. From this, it was found that the total amount of charged manganese ions was supported on the iron (III) oxide (Fe ₂ O ₃ ) surface.

(Identification of divalent copper compounds or other transition metal compounds)
Table 1 shows the results of the X-ray diffraction measurement.

(Evaluation of antiviral performance under visible light irradiation: measurement of LOG (N / N ₀ ))
The results are shown in Table 1 below.

From comparison between Examples 1-12 and Comparative Examples 1-8, it was found that the antiviral composition of the present invention has excellent antiviral performance under visible light. Under the light irradiation conditions for 60 minutes, about 99.9% of the phages were inactivated, and an excellent effect could be confirmed.
As shown in Table 1, only iron (III) oxide (Comparative Example 1), when iron metal (III) was loaded with metallic copper alone (Comparative Example 2), divalent copper on nitrogen (N) -doped titanium oxide When the compound was supported (Comparative Example 7), when the divalent copper compound was supported on triiron tetroxide (Fe ₃ O ₄ ) (Comparative Example 8), excellent antiviral performance was not expressed.
Furthermore, when other transition metals were supported (Comparative Examples 3 to 6), excellent antiviral performance was not obtained.
It was confirmed that extremely high antiviral performance was expressed by using the antiviral composition of the present invention containing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound.

Claims (15)

An antiviral composition containing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound. The antiviral composition according to claim 1, wherein the iron (III) oxide (Fe ₂ O ₃ ) is α-iron (III) oxide (Fe ₂ O ₃ ). Elemental copper by weight of the divalent copper compound is a 0.01 to 60 parts by mass with respect to the 100 parts by weight of iron oxide _{(III) (Fe 2 O 3} ), anti-according to claim 1 or 2 Viral composition. The divalent copper compound is (a) the following general formula (1):
Cu ₂ (OH) ₃ X (1)
(In the formula, X represents an anion)
(B) Divalent copper halide, (c) Divalent copper inorganic acid salt, (d) Divalent copper organic acid salt, (e) Cupric oxide (F) Copper sulfide, (g) Copper azide (II), and (h) One or more types selected from copper silicate. Viral composition. X in the general formula (1) representing the (a) hydroxyl group-containing divalent copper compound is one or more selected from Cl, CH ₃ COO, NO ₃ and (SO ₄ ) _1/2 . The antiviral composition according to claim 4.   The antiviral composition according to claim 4, wherein the (b) divalent copper halide is one or more selected from copper chloride, copper fluoride and copper bromide.   The inorganic salt of (c) divalent copper is copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper copper chloride, pyrophosphoric acid The antiviral composition of Claim 4 which is 1 type, or 2 or more types selected from copper and copper carbonate.   The antiviral composition according to claim 4, wherein the (d) divalent copper organic acid salt is a divalent copper carboxylate.   The antiviral agent containing the antiviral composition of any one of Claims 1-8.   The photocatalyst containing the antiviral composition of any one of Claims 1-8. One or more selected from iron (III) oxide (Fe ₂ O ₃ ), water, a divalent copper compound and a divalent copper compound raw material represented by the following general formula (2) are mixed to prepare a dispersion. The manufacturing method of an antiviral composition which has the carrying | support process which has a process, and the isolation | separation process which isolate | separates an antiviral composition from the said dispersion liquid.
General formula (2):
CuX ₂ (2)
(In the formula, X represents an anion)   The method for producing an antiviral composition according to claim 11, wherein in the supporting step, an alkaline substance is further mixed to prepare a dispersion.   The manufacturing method of the antiviral composition of Claim 11 or Claim 12 which heat-processes the obtained dispersion liquid at a carrying | support process. A method for producing an antiviral composition, comprising physically mixing iron (III) oxide (Fe ₂ O ₃ ) and a divalent copper compound.   The virus inactivation method which inactivates a virus using the antiviral composition of any one of Claims 1-8, the antiviral agent of Claim 9, or the photocatalyst of Claim 10.