JP6743798B2 - Antiviral agent - Google Patents

Description

The present invention relates to an antiviral agent containing metallic copper as an active ingredient.

Conventionally, silver ions and copper (II) ions have been used as active ingredients in materials having antibacterial and antiviral properties. These metal ions are supported on substances such as zeolite and silica gel, or in a solvent. There have been proposed various antiviral materials which are dispersed in.
However, the metal ion is capable of expressing antiviral properties against viruses having an envelope structure such as influenza virus, but expressing antiviral properties against viruses having no envelope structure such as Norovirus. I couldn't.

A monovalent copper compound is also known as a metal compound capable of expressing antiviral properties regardless of the presence or absence of an envelope structure. For example, in Patent Document 1 below, monovalent copper compound fine particles, a reducing agent, and a dispersion agent An antiviral composition containing a medium and having a pH of 6 or less is described. Patent Document 2 below contains monovalent copper compound fine particles and a dispersion medium, and the monovalent copper compound fine particles are chloride, acetic acid, sulfide, iodide, bromide, peroxide, oxide, water. A virus inactivating agent is described, characterized in that it is an oxide, cyanide, thiocyanate, or a mixture thereof. Patent Document 3 below describes a virus inactivating agent that includes a composition containing one or more visible light-responsive photocatalytic substances together with one or more monovalent copper compounds.

Japanese Patent No. 5194185 Japanese Patent No. 5452966 Japanese Patent No. 5570006

The virus inactivating agent having the monovalent copper compound as an active ingredient has an effect even on a norovirus that does not have an envelope structure, but fine particles of the monovalent copper compound easily aggregate, It is difficult to disperse uniformly, and when the dispersion is used as a virus inactivating agent, or when it is used as an antivirus molded product that is mixed with a coating material and coated, it can be used as an antiviral agent. It was difficult to efficiently express viral nature.
Further, the fine particles of the monovalent copper compound can be obtained by pulverizing, but it is easy to aggregate because there is no coating agent or stabilizer, and it is difficult to directly disperse the powder of the monovalent copper compound in the solvent. There is also a problem that oxidation of cuprous oxide to copper (II) oxide is likely to occur.

In order to solve such a problem, the present inventors propose fine particles of a monovalent copper compound capable of efficiently expressing antiviral properties, a dispersion liquid containing the same, and the like (Japanese Patent Application No. 2016-247641), As a result of continuing intensive studies on fine particles capable of more efficiently expressing high antiviral properties, it has been found that metallic copper can express higher antiviral properties than monovalent copper compounds.
Therefore, an object of the present invention is to provide an antiviral agent having a high antiviral property, which contains metallic copper as an active ingredient.

According to the present invention, an antiviral agent containing metal copper fine particles as an active ingredient, wherein the metal copper fine particles are a dispersion liquid dispersed in a solvent or a resin composition dispersed in a resin, or in a dry state. Ah is, the antiviral agent is provided, characterized in Oh Rukoto with metallic copper particles are coated with a fatty acid and / or ester compound.

In the above antiviral agent of the present invention,
1. The metal copper fine particles are metal copper fine particles having an average primary particle size of 500 nm or less,
2 . It antiviral activity of an antiviral agent containing the pre-Symbol metallic copper particles in an amount of 0.05 to 2.0% by weight is 3.0 or more,
3 . Generation of superoxide anion radicals, represented by the light emission quantity by chemiluminescence by reaction with MPEC antiviral agent comprising an amount of a metallic copper particles 0.05-2.0 wt% of gold Shokudo terms The amount is 5000 counts/mL or more,
4 . Protein reduction rate due BSA method antiviral agent comprising a gold Shokudo particles, is 10% or more,
Is preferred.

The antiviral agent of the present invention containing metallic copper as an active ingredient can exhibit excellent antiviral properties against viruses having no envelope structure such as norovirus. In addition, it is possible to exhibit antiviral properties superior to those of antiviral agents composed of monovalent copper compound fine particles having the same effect.
It is considered that the inactivation of the virus by metallic copper can inactivate the virus by denaturing the protein constituting the virus by the reactive oxygen species generated by metallic copper. Therefore, by using fine metal copper fine particles having an average primary particle size of 500 nm or less as an antiviral agent, the contact area with oxygen in the air is increased and a large amount of active oxygen species can be generated. It will often be possible to inactivate the virus.

Further, by coating the surface of the metal copper fine particles with a fatty acid and an ester compound, oxidation and agglomeration of the metal copper fine particles can be prevented and excellent antiviral properties can be expressed for a long period of time.
Further, by coating the surface of the metal copper fine particles with the fatty acid and the ester compound, it becomes possible to provide the antiviral agent in the form of a dispersion liquid. This dispersion, even when the high-concentration metal copper fine particles are contained in a non-aqueous solvent such as a low boiling point solvent, because the metal copper fine particles are dispersed uniformly without agglomeration, excellent antiviral properties are obtained. It can be efficiently expressed. Further, this dispersion can be suitably used as a diluting solvent for a coating composition, a resin composition and the like, which makes it possible to impart antiviral properties to a coating film and a resin molded product.
That is, by making the antiviral agent of the present invention in the form of a dispersion liquid in which the metal copper fine particles are dispersed, it is contained as a diluent of the resin composition constituting the fiber product or directly applied to the fiber product or the like. Alternatively, by impregnating or by applying a mixture of a binder resin and a dispersion liquid to a textile product or the like, it becomes possible to impart an antiviral property to the textile product or the like.
Further, a dispersed liquid antiviral agent in which fine metal copper particles are dispersed is mixed with a coating material and applied onto a film, a sheet, or a metal substrate to impart antiviral property to the surface or outer surface thereof. ..

Further, when the metal copper fine particles coated with a fatty acid and an ester compound are mixed in the resin composition, direct contact between the surface of the metal copper fine particles and the resin is reduced, which effectively suppresses the decomposition of the resin. Further, it is possible to reduce the decrease in the molecular weight of the resin, and it is also effectively prevented that the moldability and processability are impaired. Further, the metallic copper fine particles are uniformly and stably present on the surface of the molded body, and it becomes possible to impart excellent antiviral performance to the molded body for a long period of time.

The above-mentioned effects of the antiviral agent of the present invention are clear from the results of Examples described later. That is, in Comparative Examples 2, 5 and 6 in which a monovalent copper compound is used as an active ingredient, the case where the surface of the monovalent copper compound fine particles is coated with a fatty acid, an ester compound or the like (Comparative Example 5) or the monovalent copper compound When the fine particles are embedded in nylon 6 (Comparative Example 6), feline calicivirus which is an alternative virus to norovirus, even if it has an antiviral activity value of 3.0 or more against influenza virus. It does not have antiviral properties against. When the surface of the monovalent copper fine particles is not coated with fatty acid (Comparative Example 2), it does not have antiviral activity against not only feline calicivirus but also influenza virus due to oxidation and aggregation. Further, even if the metal copper fine particles are used, if the surface thereof is not coated with a fatty acid, the metal copper fine particles are oxidized and aggregated, and the excellent antiviral property of the metal copper cannot be sufficiently expressed ( Comparative Example 1).
On the other hand, the antiviral agent of the present invention has an antiviral activity value of 3.0 or more against not only influenza virus having an envelope structure but also feline calicivirus having no envelope structure. , And that it has excellent antiviral properties (Examples 1 to 9).

In the antiviral agent of the present invention, metallic copper, which is an active ingredient, can inactivate viruses and can exhibit excellent antiviral properties regardless of the presence or absence of an envelope structure.
That is, the excellent antiviral property of the antiviral agent of the present invention is that the oxidative power of active oxygen generated by metallic copper causes denaturation of viral proteins consisting of microproteins, and metallic copper functions as a thiol group of viral proteins. It is considered that the virus can be efficiently inactivated by denaturing the protein by the reaction. In particular, metallic copper has a larger amount of active oxygen that can be generated than monovalent copper, and is therefore considered to have superior antiviral properties to monovalent copper compound fine particles.
The antiviral agent of the present invention can adopt various forms as long as the active ingredient is metallic copper, but the metallic copper fine particles, the dispersion liquid in which the metallic copper fine particles are dispersed in the solvent, the metallic copper fine particles in the resin It is suitable that it is in the form of a dispersed resin composition.

The antiviral performance of the antiviral agent of the present invention can be evaluated by the following method.
That is, in the antiviral agent of the present invention in which the antiviral activity value, which is also measured in Examples described later, contains the copper metal fine particles in an amount of 0.05 to 2.0% by weight, an influenza virus having an envelope structure is obtained. Of course, it has an antiviral activity of 3.0 or more against feline calicivirus, which is a norovirus alternative virus having no envelope structure.
The amount of superoxide anion radicals generated from the antiviral agent is represented by the amount of luminescence measured by the chemiluminescence method by the reaction with MPEC (2-methyl-6-p-methoxyphenylethynylimidazopyrazinone). However, in the antiviral agent of the present invention containing the metal copper fine particles in an amount of 0.05 to 2.0% by weight in terms of metal copper, the amount of luminescence is 5000 counts/mL or more, and the above-mentioned active oxygen is used. It can efficiently generate large numbers of seeds and has excellent antiviral properties.
Furthermore, the antiviral agent of the present invention containing fine metal copper particles has a protein reduction rate of 10% or more measured by the BSA method (reaction with 0.2 ml of BSA solution (50 μg/mL)), Efficiently denatures the proteins that make up the virus to inactivate the virus and has excellent antiviral properties.

[Metallic copper particles]
The antiviral agent of the present invention is preferably in the form of metallic copper fine particles having an average primary particle size of 500 nm or less, particularly 10 to 200 nm.
When the metal copper fine particles are in the above range, the antiviral performance can be efficiently expressed. That is, since the metal copper fine particles having a small average primary particle diameter have a high contact rate with oxygen of the metal copper fine particles, active oxygen can be efficiently generated, and excellent antiviral performance can be expressed. Will be possible. In addition, the average primary particle diameter as referred to in the present specification means one in which there are no gaps between the metal copper fine particles and the metal copper fine particles, and the average thereof is taken.
It is particularly preferred that the metal copper fine particles are coated with a fatty acid and an ester compound on the surface of the metal fine particles, which prevents oxidation of the fine metal copper particles due to an increase in the surface activity of the metal copper fine particles. Therefore, it becomes possible to suppress the aggregation of fine particles, and it is possible to exhibit excellent antiviral properties for a long period of time.

Examples of the fatty acid coating the surface of the metallic copper fine particles include myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, p-toluic acid, succinic acid, malonic acid, tartaric acid, malic acid, glutaric acid, adipic acid, acetic acid, etc. And a combination of a plurality of these may be used, but higher fatty acids having 10 to 22 carbon atoms, especially stearic acid are particularly preferable.
The ester compound coating the surface of the metal copper fine particles may contain an ester compound derived from a fatty acid and a polyol as raw materials, in addition to the ester compound blended in a low boiling point solvent described later. These may be different ester compounds, but preferably, the ester compound blended in the low boiling point solvent is desirably the same as the ester compound derived from the raw materials.
Suitable ester compounds for coating the surface of the metal copper fine particles include ester compounds of the above-mentioned fatty acid ester compounds and polyols described later, for example, but not limited to, diethylene glycol distearate, ethylene glycol distearate, propylene glycol distearate. The rate etc. can be mentioned.

[Dispersion]
A preferred form of an antiviral agent is a dispersion obtained by dispersing the above-mentioned metal copper fine particles in a solvent, a dispersion in which the metal copper fine particles are dispersed in a low boiling point solvent, or a metal copper fine particle dispersed in a polyol. And a dispersion liquid obtained by redispersing powder in a paste state or a dry state obtained by removing a solvent from the dispersion liquid.
Such a dispersion liquid is a preferable form because it can be directly produced by the production method described later, is easy to handle, and can be impregnated into a fiber product or used as a diluent for a resin composition.
In such a dispersion liquid, it is sufficient that the amount of the metallic copper fine particles is contained in the dispersion liquid in an amount of 0.01 to 2% by weight, particularly 0.05 to 1% by weight. Viral performance can be obtained, and coatability and moldability can be secured.

Examples of the dispersion medium in the dispersion liquid include esters such as methyl acetate, ethyl acetate and butyl acetate, hydrocarbons such as hexane, heptane, toluene, xylene and cyclohexane, and ketones such as methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone. A boiling point solvent can be exemplified, but an ester solvent is preferable, and butyl acetate is particularly preferable. When the dispersion medium is a non-aqueous low boiling point solvent, the dispersion liquid can be effectively used as a diluent for a hydrophobic coating composition or resin composition.
In addition, the paste-like metal copper fine particles obtained by drying the dispersion liquid in which the metal copper fine particles are dispersed in the low boiling point solvent obtained by the production method described below is purified water, ion-exchanged water or the like water; It can also be redispersed in a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol; a general modified alcohol such as methanol modified, benzol modified, triol modified, methyl ethyl ketone modified, denatonium benzoate modified, and perfume modified.

The dispersion liquid preferably contains a dispersant in addition to the metallic copper fine particles. This makes it possible to obtain a dispersion liquid in which the metal copper fine particles are uniformly dispersed even when the metal copper fine particles are contained at a high concentration. Suitable dispersants will be described later.
Further, conventionally known additives such as an antioxidant, an ultraviolet absorber, an antistatic agent, a dye and the like can be added to the dispersion according to a conventionally known formulation.

[Resin composition]
As a resin composition obtained by dispersing the above-mentioned metal copper fine particles in a resin, which is a preferred form of an antiviral agent, a dispersion liquid containing the above-mentioned metal copper fine particles is used as a diluent solvent for a coating composition or a resin composition. The coating composition and resin composition used as above can be exemplified.
Thus, the coating composition or resin composition using the above-mentioned dispersion imparts antiviral performance without impairing the transparency of the coating film composed of such coating composition or the resin molded product composed of the resin composition. It becomes possible to do.
Examples of such a coating composition include thermosetting resins such as phenol resin, epoxy resin, urethane resin, melamine resin, urea resin, alkyd resin, unsaturated polyester resin, and silicone resin, or photocurable acrylic resin. Can be mentioned as a base resin.
Further, as the resin composition, in addition to the thermosetting resin, low-, medium-, high-density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, propylene. -Ethylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, olefin resin such as ethylene-propylene-butene-1 copolymer, polyethylene terephthalate, polybutylene terephthalate, Examples thereof include polyester resins such as polyethylene naphthalate, polyamide resins such as nylon 6, nylon 6,6 and nylon 6,10, and thermoplastic resins such as polycarbonate resins.

(Method for producing antiviral agent)
The antiviral agent of the present invention is not particularly limited in its production method as long as it contains metallic copper as an active ingredient, but the following production method is a particularly preferred embodiment, in which a metal ultrafine particle coated with a fatty acid and an ester compound is a solvent. The antiviral agent in the form of a dispersion liquid dispersed in can be efficiently prepared.

[First manufacturing method]
(1) First Step Fatty acid copper is added to a polyol, and this is heated to prepare a polyol dispersion liquid in which the metal copper fine particles whose surface is coated with the fatty acid are dispersed. At this time, it is more preferable that the surface of the metal copper fine particles is coated with a fatty acid and an ester compound of this fatty acid and a polyol.
The heating temperature is lower than the decomposition start temperature of the fatty acid copper used, and specifically, it is preferably in the range of 160 to 230°C. The heating and mixing time is preferably 60 to 360 minutes.

The amount of the fatty acid copper compounded is preferably in the range of 0.1 to 5 parts by weight per 100 parts by weight of the polyol. When the amount of the fatty acid copper is smaller than the above range, it may not be possible to impart sufficient antiviral property to the dispersion liquid as compared with the case where the amount is in the above range. On the other hand, when the amount of the fatty acid copper is larger than the above range, the economical efficiency is deteriorated and the coatability and moldability may be impaired as compared with the case where the amount is in the above range.
Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and glycerin, which are appropriately selected in combination with a low boiling point solvent described later.

(2) Second step Next, a fatty acid, preferably a polyol dispersion in which fine particles of metal copper coated with a fatty acid and an ester compound of the fatty acid are dispersed, and a low boiling point solvent in which a dispersant and an ester compound have been previously mixed are mixed. Then, a mixed solution is prepared.
The low boiling point solvent is preferably added to the polyol dispersion in an amount of 10 to 200 parts by weight based on 100 parts by weight of the polyol.
As the low boiling point solvent, the low boiling point solvents exemplified in the above-mentioned dispersion liquid can be used, and among them, butyl acetate, ethyl acetate, and methyl isobutyl ketone can be preferably used. It is important that the low boiling point solvent is incompatible with the polyol, and it is preferable to combine the low boiling point solvent so that the difference in solubility parameter (Sp value) between the polyol and the low boiling point solvent is 3 or more.
Preferably, when diethylene glycol (Sp value: 12.6) is used as the polyol, butyl acetate (Sp value: 8.4) is preferably used as the low boiling point solvent.

The amount of the dispersant compounded in the low boiling point solvent varies depending on the amount of the fatty acid, preferably the fatty acid and the metal copper fine particles coated with the ester compound of the fatty acid, in the polyol dispersion, but is 0 per 100 parts by weight of the low boiling point solvent. The amount is preferably 0.01 to 2 parts by weight.
The dispersant has at least one of an amine salt, a carboxylic acid or a carboxylic acid salt, and a hydroxyl group, which are neutralized with a primary, secondary, or tertiary amine or a counterion thereof in the adsorption group, and has a main chain and A polymeric dispersant having a fatty acid, polyether, polyester, polyurethane, or polyarylate in the side chain can be used.
These dispersants are adsorbed on the surface of the metal copper fine particles by having an adsorption group, improve the compatibility with the non-aqueous solvent by the main chain or side chains, repulsive force due to steric hindrance of the polymer chain, Aggregation of the metallic copper fine particles is suppressed, and the metallic copper fine particles are uniformly dispersed in the non-aqueous solvent, and the aggregation over time can be eliminated.
As the polymer dispersant, a type composed only of the main chain, a comb structure type having a side chain, or a type having a star structure can be used.

The amount of the ester compound blended in the low boiling point solvent varies depending on the amount of the fatty acid in the polyol dispersion, preferably the fatty acid and the metal copper fine particles coated with the ester compound of the fatty acid, but per 100 parts by weight of the low boiling point solvent. It is preferably in the amount of 0.1 to 2.0 parts by weight.
The ester compound blended in the low boiling point solvent is preferably an ester compound of a fatty acid and a polyol, and it is preferable that the fatty acid exemplified as the fatty acid coating the metal copper fine particles described above and the ester compound consisting of the above-mentioned polyol. is there.
The ester compound to be added to the low boiling point solvent is not necessarily the same as the fatty acid copper and the polyol used as the raw material, but it is preferable that the same type, for example, diethylene glycol as the raw material polyol, the raw material fatty acid. When copper stearate is used as the copper, it is preferable to add diethylene glycol distearate or ethylene glycol distearate as the ester compound.

(3) Third Step The polyol and the low boiling point solvent are phase-separated by allowing the mixed solution to stand at a temperature of 0 to 40° C. for 30 to 120 minutes. When the mixed solution is phase-separated, the metallic copper fine particles coated with the fatty acid and the ester compound of the fatty acid, which were present in the mixed solution, are extracted to the low boiling point solvent side. Since the dispersant is mixed in the low boiling point solvent, the adsorption groups of the dispersant are coordinated with the metal copper fine particles, whereby the metal copper fine particles are easily extracted into the low boiling point solvent.
Then, the polyol is removed from the phase-separated mixed liquid to obtain a dispersion liquid in which the metal copper fine particles coated with the fatty acid and the ester compound of the fatty acid are dispersed in the low boiling point solvent.
The removal of the polyol can be performed by a conventionally known method such as simple distillation, reduced pressure distillation, precision distillation, thin film distillation, extraction, and membrane separation.
As described above, when the metal copper fine particles are used in a dry state as an antiviral agent, and when the metal copper fine particles are redispersed in a solvent such as water, the obtained dispersion is filtered, centrifuged, By removing the low boiling point solvent by a conventionally known method such as volatilization, dry metal copper fine particles can be obtained.

[Second manufacturing method]
A preferred embodiment of the antiviral agent, a method for producing a dispersion in which copper metal fine particles coated with a fatty acid and an ester compound of a fatty acid are dispersed in a low boiling point solvent, in addition to the above-described production method, It can also be prepared by a method.
That is, in the first step in the above-mentioned first production method, in place of the fatty acid copper, by performing in the same manner as the first production method except that a combination of a fatty acid and a copper compound is added, a fatty acid and an ester compound are obtained. The antiviral agent in the form of a dispersion in which the coated copper metal fine particles are dispersed can be prepared.
Examples of the copper compound include oxides, acetic acid compounds, chlorides, bromides, hydroxides, cyanides, and the like, and any of copper acetate, copper chloride, and copper bromide can be preferably used.

[Third manufacturing method]
In the present invention, a dispersion liquid obtained by the first step in the above-mentioned first and second production method, which is obtained by dispersing the metal copper fine particles coated with the fatty acid and the ester compound of the fatty acid in the polyol, It can also be used as it is as an antiviral agent.
That is, a fatty acid copper or a fatty acid and a copper compound is added to a polyol, and the mixture is heated and mixed to prepare a polyol dispersion liquid in which fine metal copper particles are dispersed, and this is used as an antiviral agent. Can also

(Example 1)
2.5% by weight of copper stearate was added to diethylene glycol and heated with stirring. After heating at 190° C. for 2 hours, the diethylene glycol dispersion was cooled to 60° C. Then, 1.0% by weight of DISPERBYK-2090 (manufactured by BYK Chemie) as a dispersant and butyl acetate in which 1.0% by weight of diethylene glycol distearate were dissolved were added and stirred. After standing for about 1 hour, the butyl acetate layer was collected to prepare an antiviral agent composed of a metal copper fine particle dispersion liquid.

(Example 2)
An antiviral agent was prepared in the same manner as in Example 1 except that the heating temperature was changed to 210°C.

(Example 3)
An antiviral agent was prepared in the same manner as in Example 1 except that ethylene glycol distearate was added instead of diethylene glycol distearate.

(Example 4)
An antiviral agent was prepared in the same manner as in Example 1 except that copper laurate was added instead of copper stearate.

(Example 5)
An antiviral agent was prepared in the same manner as in Example 1 except that stearic acid and copper acetate were added instead of copper stearate.

(Example 6)
An antiviral agent was prepared in the same manner as in Example 1 except that ethylene glycol was used instead of diethylene glycol.

(Example 7)
2.5% by weight of copper stearate was added to diethylene glycol and heated with stirring. After heating for 2 hours from the time when the temperature reached 190° C., the diethylene glycol dispersion was cooled to room temperature to prepare an antiviral agent composed of a metal copper fine particle dispersion.

(Example 8)
An antiviral agent was prepared in the same manner as in Example 7 except that glycerin was used instead of diethylene glycol.

(Example 9)
The copper metal fine particles obtained by drying the solvent of the dispersion liquid of Example 1 to dryness were added to water and stirred to prepare an antiviral agent composed of the metal copper fine particle dispersion liquid.

(Comparative Example 1)
To butyl acetate, 0.05% by weight of a metallic copper fine particle reagent (manufactured by Sigma-Aldrich), 1.0% by weight of DISPERBYK-2090, and 1.0% by weight of diethylene glycol distearate were added, and dispersed by stirring with an ultrasonic vibration device. A liquid was obtained.

(Comparative example 2)
0.05% by weight of copper(I) oxide reagent, 1.0% by weight of DISPERBYK-2090, and 1.0% by weight of diethylene glycol distearate were added to butyl acetate, and the mixture was stirred by an ultrasonic vibration device to obtain a dispersion liquid.

(Comparative example 3)
0.05% by weight of copper(II) oxide reagent, 1.0% by weight of DISPERBYK-2090 and 1.0% by weight of diethylene glycol distearate were added to butyl acetate, and the mixture was stirred by an ultrasonic vibration device to obtain a dispersion liquid.

(Comparative example 4)
0.05 wt% of metallic silver reagent, 1.0 wt% of DISPERBYK-2090, and 1.0 wt% of diethylene glycol distearate were added to butyl acetate, and the mixture was stirred with an ultrasonic vibration device to obtain a dispersion liquid.

(Comparative example 5)
A dispersion was prepared in the same manner as in Example 1 except that 0.05% by weight of saccharin and 1.0% by weight of water were added to diethylene glycol.

(Comparative example 6)
Copper(I) oxide reagent powder was pulverized with a jet mill and nylon 6 particles having an average particle size of about 10 μm were mixed in a dry particle compounding device to expose copper(I) oxide on the surface of nylon 6 particles. Particles buried in the state were prepared. 0.05% by weight of the obtained particles was added to butyl acetate and stirred with an ultrasonic vibration device to obtain a dispersion liquid.

<Antiviral evaluation>
(Method of applying dispersion liquid to non-woven fabric)
90% by weight of antiviral agent (dispersion liquid) prepared so that the metal component concentration is 0.05% by weight with respect to the binder resin, and 9.9% by weight of a photocurable acrylic resin as a binder resin, and initiation of photopolymerization. 0.1% by weight of the agent was mixed to prepare a coating solution. An unprocessed nonwoven fabric was dipped in this coating solution, taken out, excess liquid was removed by a roller type squeezing machine, and then dried for 2 minutes by a dryer at 90°C. After that, UV irradiation was performed for 10 minutes to prepare a non-woven fabric having metal copper fine particles immobilized thereon.

(Method of evaluating anti-virus property of non-woven fabric)
1. A virus suspension is prepared by infecting host cells with a virus, culturing, and then removing the cell debris by centrifugation.
2. The virus suspension of 1 above was diluted 10 times with sterile distilled water to obtain a test virus suspension.
3. 0.4 g of the non-woven test piece is inoculated with 0.2 mL of the test virus suspension.
After standing at 4.25° C. for 2 hours, 20 mL of SCDLP medium is added and stirred with a vortex mixer to wash out the virus from the sample.
5. The virus infectivity is measured by the plaque measuring method, and the antiviral activity value is calculated.
6. If the antiviral activity value is 3.0 or more, it can be determined that the virus has sufficient antiviral properties.

Table 1 shows the results of the above antiviral evaluation using the influenza virus and feline calicivirus for the nonwoven fabrics using the antiviral agent (dispersion liquid) prepared in Examples 1 to 9 and Comparative Examples 1 to 6.

Since the antiviral agent of the present invention can take the form of ultrafine metal particles, the form of a dispersion liquid, the form of a resin composition using this dispersion liquid, etc., it is contained in a resin composition constituting a fiber product or the like. Or, by directly applying or impregnating it to textile products, masks, wet tissues, air conditioner filters, filters for air purifiers, clothes, work clothes, curtains, carpets, automobile parts, sheets, towels, wipers, etc. It is possible to impart antiviral properties to textile products such as.
In addition, it can be used for medical equipment, packaging film for medical equipment, waste containers, garbage bags, wall materials and flooring materials for nursing facilities or public facilities such as hospitals and schools, wax coating materials, and tools for treating vomiting. ..

Claims (5)

An anti-viral agent comprising as an active ingredient the metallic copper particles, the metallic copper particles, a resin composition dispersed in dispersion or resin dispersed in a solvent or dry state near is, fatty acids and / or antiviral agent characterized Oh Rukoto with metallic copper particles are coated with an ester compound. The antiviral agent according to claim 1, wherein the metal copper fine particles are metal copper fine particles having an average primary particle diameter of 500 nm or less. The antiviral agent according to claim 1 or 2 , wherein an antiviral activity value of the antiviral agent containing the copper metal fine particles in an amount of 0.05 to 2.0% by weight is 3.0 or more. Generation amount of superoxide anion radical represented by chemiluminescence emission amount by reaction of antiviral agent containing MPC in an amount of 0.05 to 2.0% by weight in terms of metallic copper with MPEC Is 5000 counts/mL or more, The antiviral agent of Claim 1 or 2 . The antiviral agent according to claim 1 or 2, wherein an antiviral agent containing copper metal fine particles has a protein reduction rate by the BSA method of 10% or more.