WO2024043320A1 - Viral infection inhibitor, viral infection inhibition product, and method for manufacturing viral infection inhibition product - Google Patents

Abstract

The present invention provides a viral infection inhibitor with excellent ethanol resistance, demonstrating an excellent viral infection inhibition effect (antiviral property) even after contact with an ethanol solution for disinfection. This viral infection inhibitor is characterized by containing a compound having a salt of a sulfo group, an organic acid, and water, wherein a portion of the organic acid is present in an undissolved state in the water at 25˚C. Preferably, the inhibitor is characterized in that the organic acid has a solubility of 20 g/L or less in water at 25˚C.

Description

Virus infection inhibitor, virus infection prevention product, and method for producing virus infection prevention product

The present invention relates to a virus infection inhibiting agent, a virus infection inhibiting product, and a method for producing a virus infection inhibiting product.

In recent years, in addition to the seasonal influenza virus epidemic, the new coronavirus (COVID-19) has been spreading worldwide.

In addition, the highly pathogenic avian influenza virus has mutated and has been confirmed to infect humans, and there is also concern about the Sars virus, which has an extremely high mortality rate, and anxiety about the virus is only increasing.

To address these problems, Patent Document 1 discloses an RNA virus infection-inhibiting compound containing an RNA virus infection inhibiting compound having at least one substituent of a structural formula represented by a predetermined general formula on the side chain of a linear polymer. Viral infection inhibitors have been proposed.

WO2010/147165 publication

On the other hand, even with antiviral products such as articles whose surfaces have been treated with RNA virus infection inhibitors or antiviral films containing RNA virus infection inhibitors, in order to remove viruses and prevent viral infections, It is common practice to disinfect the surface of antiviral products with a disinfectant ethanol solution.

However, when an antiviral product treated with the above RNA virus infection inhibitor is disinfected with a disinfecting ethanol solution, there is a problem in that the antiviral properties of the RNA virus infection inhibitor decrease.

The present invention provides a virus infection prevention device that has excellent ethanol resistance and has an excellent virus infection prevention effect (antiviral property) even after contact with a disinfectant ethanol solution (ethanol: 80% by mass, water: 20% by mass). The present invention provides a virus infection inhibiting agent, a virus infection inhibiting product using the virus infection inhibiting agent, and a method for producing the same.

The virus infection inhibitor of the present invention is characterized in that it contains a compound having a salt of a sulfo group, an organic acid, and water, and a part of the organic acid exists in an insoluble state in the water at 25°C. shall be.

The water-based paint of the present invention is characterized by containing the above virus infection inhibitor.

The virus infection prevention product of the present invention is
It is characterized in that it contains a base material and a dried product of the virus infection inhibitor contained on the surface of the base material.

The method for manufacturing the virus infection inhibiting product of the present invention includes a step of attaching the virus infection inhibitor to the surface of a base material, and a step of drying the virus infection inhibitor attached to the surface of the base material to produce a dried product. It is characterized by including.

Since the virus infection inhibitor of the present invention contains a compound having a salt of a sulfo group and an organic acid, it has an excellent effect of inhibiting virus infection against both enveloped and non-enveloped viruses. It has the effect of inhibiting viral infection against various types of viruses.

The virus infection inhibitor of the present invention has excellent ethanol resistance and has an excellent virus infection prevention effect (antiviral property) even after contact with a disinfectant ethanol solution, and is effective against various types of viruses. Maintains the inhibitory effect for a long period of time.

The virus infection inhibitor of the present invention contains a compound having a salt of a sulfo group, an organic acid, and water, and a part of the organic acid is present in an insoluble state in water.

[Compound having sulfo group salt]
A compound having a salt of a sulfo group has a salt of a sulfo group (-SO ₃ H) in the molecule. A compound having a salt of a sulfo group exhibits a virus infection inhibiting effect due to its molecular structure containing a salt of a sulfo group (-SO ₃ X:X is a metal element or NH ₄ ⁺ ). Compounds having a salt of a sulfo group have particularly excellent virus infection inhibiting effects against enveloped viruses. In addition, compounds having a salt of a sulfo group include a carboxy group (-COOH), a phosphonic acid group [-P(=O)(OH) ₂ ], a phosphoric acid group [-OPO(OH) ₂ ], a thiol group (- SH) and a hydroxy group (-OH).

The salt of the sulfo group is not particularly limited, and includes, for example, sodium salt (-SO ₃ Na), calcium salt [(-SO ₃ ^- ) ₂ Ca ²⁺ ], ammonium salt (-SO ₃ ^- NH ₄ ⁺ ), Examples include magnesium salt [(-SO ₃ ^- ) ₂ Mg ²⁺ ], barium salt [(-SO ₃ ^- ) ₂ Ba ²⁺ ], and sodium salt (-SO ₃ Na) is preferred.

The compound having a salt of a sulfo group is preferably an organic compound. In the present invention, an organic compound refers to a compound containing at least one (preferably two or more) carbon atoms and carbon-hydrogen bonds (C--H bonds) in the molecule.

When the compound having a salt of a sulfo group is an organic compound, the affinity with the organic acid described later improves, and the compound having a salt of a sulfo group and the organic acid become close to each other, and the compound having a salt of a sulfo group and the organic acid This improves the effect of inhibiting virus infection against both non-enveloped viruses (non-enveloped viruses) and enveloped viruses (enveloped viruses).

The compound having a salt of a sulfo group preferably has an aromatic ring. When a compound having a salt of a sulfo group has an aromatic ring, its affinity with an organic acid improves, and the compound having a salt of a sulfo group and the organic acid become close to each other. The interaction with acids is improved, and the effect of inhibiting virus infection against both enveloped viruses and non-enveloped viruses is improved.

The aromatic ring may be a monocyclic aromatic ring or a complex of monocyclic aromatic rings condensed (fused aromatic ring). The aromatic ring is not particularly limited, and includes, for example, a benzene ring, a naphthalene ring, an anthracene ring, biphenyl, phenoxyphenyl, and the like, with benzene rings and naphthalene rings being preferred. The aromatic ring has one or more hydrogen atoms removed from the aromatic ring and the fused aromatic ring, and is bonded to other atoms through covalent bonds.

In the compound having a sulfo group salt, the sulfo group salt is preferably bonded directly or indirectly to the aromatic ring, and more preferably directly bonded to the aromatic ring. Due to the affinity between the aromatic ring of the compound having a sulfo group salt and the organic acid, the compound having the sulfo group salt and the organic acid become close to each other, and the sulfo group salt of the compound having the sulfo group salt and the organic acid become close to each other. The synergistic effect can be improved, and the effect of inhibiting virus infection against both enveloped viruses and non-enveloped viruses can be improved.

In a compound having a sulfo group salt, when the sulfo group salt is indirectly bonded to an aromatic ring, the sulfo group salt is an alkylene group having 1 to 4 carbon atoms (preferably a methylene group or an ethylene group). ) is preferably bonded to the aromatic ring. While maintaining the affinity between the aromatic ring in the compound having a sulfo group salt and the organic acid, the sulfo group salt is appropriately spaced from the aromatic ring due to the alkylene group, making the sulfo group salt more The virus infection inhibitor can be oriented in an exposed state and has an excellent effect of inhibiting virus infection.

In the present invention, an alkylene group is a divalent atomic group produced by removing (withdrawing) hydrogen atoms bonded to two different carbon atoms in an aliphatic saturated hydrocarbon, and is Contains both branched atomic groups.

Examples of alkylene groups include methylene group (-CH ₂ -), ethylene group (-CH ₂ -CH ₂ -), propylene group [-CH(CH ₃ )-CH ₂ -], trimethylene group [-CH ₂ - CH ₂ --CH ₂ --], butylene group, amylene group [-(CH ₂ ) ₅ --], hexylene group, and the like.

Compounds having a salt of a sulfo group are not particularly limited as long as they have one or more salts of a sulfo group in the molecule, and examples include linear alkylbenzene sulfonates, α-olefin sulfonates, alkyl Examples include diphenyl ether sulfonate, polyoxyalkylene alkyl ether sulfate, and linear polymer having a sulfo group salt in the side chain.

Examples of linear alkylbenzenesulfonates include sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, magnesium dodecylbenzenesulfonate, barium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, and tridecylbenzenesulfonate. Examples include ammonium benzenesulfonate, sodium tetradecylbenzenesulfonate, ammonium tetradecylbenzenesulfonate, and sodium dodecylbenzenesulfonate is preferred.

In the present invention, an alkyl group is a monovalent atomic group remaining after one hydrogen atom is removed from an aliphatic saturated hydrocarbon.

The number of carbon atoms in the alkyl group of the linear alkylbenzene sulfonate is preferably 10 or more, more preferably 11 or more, and even more preferably 12 or more. The number of carbon atoms in the alkyl group of the linear alkylbenzenesulfonic acid is preferably 25 or less, more preferably 20 or less, and even more preferably 18 or less. When the number of carbon atoms in the alkyl group is within the above range, the compound having a sulfo group salt and the organic acid become close to each other due to the affinity between the hydrophobic moiety derived from the alkyl group and the organic acid, and the compound having a sulfo group salt becomes close to the organic acid. The synergistic effect between the sulfo group salt and the organic acid can be improved, and the effect of inhibiting virus infection against both enveloped viruses and non-enveloped viruses can be improved.

Examples of the α-olefin sulfonate include C12 to C18 sodium olefin sulfonate, C12 to C18 calcium olefin sulfonate, ammonium C12 to C18 olefin sulfonate, C12 to C18 magnesium olefin sulfonate, and C12 to C18 olefin sulfonate. Examples include barium olefin sulfonate, and C14 sodium tetradecene sulfonate is preferred.

The number of carbon atoms in the α-olefin of the α-olefin sulfonate is preferably 12 or more, and preferably 14 or more. The number of carbon atoms in the α-olefin of the α-olefin sulfonate is preferably 22 or less, more preferably 18 or less. When the number of carbon atoms in the α-olefin is within the above range, the hydrophobic moiety derived from the α-olefin chain of the compound having a sulfo group salt has an affinity with the organic acid, so that the compound having the sulfo group salt and the organic acid The synergistic effect between the sulfo group salt of the compound having a sulfo group salt and the organic acid can be improved, and the virus infection inhibiting effect against both enveloped viruses and non-enveloped viruses can be improved.

Examples of the alkyldiphenyl ether sulfonate include sodium salts, calcium salts, ammonium salts, magnesium salts, and barium salts of alkyldiphenyl ether sulfonic acid having an alkyl group of C6 to C18, and sodium dodecyl diphenyl ether sulfonate having a C12 group is preferred. .

The number of carbon atoms in the alkyl group of the alkyl diphenyl ether sulfonate is preferably 8 or more, more preferably 10 or more. The number of carbon atoms in the alkyl group of the alkyldiphenyl ether sulfonate is preferably 24 or less, more preferably 18 or less. When the number of carbon atoms in the alkyl group is within the above range, the compound having a sulfo group salt and the organic acid become close to each other due to the affinity between the hydrophobic moiety derived from the alkyl group of the compound having a sulfo group salt and the organic acid. , the synergistic effect between the sulfo group salt of a compound having a sulfo group salt and an organic acid can be improved, and the virus infection inhibiting effect against both enveloped viruses and non-enveloped viruses can be improved.

In the polymer having a salt of a sulfo group in the side chain of the linear polymer, the linear polymer is not particularly limited, and for example, vinyl polymer, polyester, and polyurethane are preferable, and vinyl polymer is preferable.

The linear polymer having a salt of a sulfo group in the side chain is not particularly limited, and includes, for example, a polymer containing a styrene sulfonate component, a styrene sulfonate homopolymer, and styrene-styrene sulfonic acid. Examples include salt copolymers, sulfonate salts of compounds obtained by sulfonating the benzene ring of polystyrene, and sulfonate salts of compounds obtained by sulfonating the benzene ring of a polymer containing a styrene component.

Furthermore, the linear polymer having a sulfo group salt in its side chain is preferably a homopolymer or copolymer of a monomer having a sulfo group salt. Examples of monomers having a salt of a sulfo group include sodium p-styrenesulfonate, sodium m-styrenesulfonate, sodium o-styrenesulfonate, calcium p-styrenesulfonate, calcium m-styrenesulfonate, - Calcium styrene sulfonate, ammonium p-styrene sulfonate, ammonium m-styrene sulfonate, ammonium o-styrene sulfonate, sodium naphthalene sulfonate, calcium naphthalene sulfonate, etc., with sodium styrene sulfonate being preferred; Sodium p-styrenesulfonate is more preferred because it has less steric hindrance in terms of reactivity.

Note that the monomer having a salt of a sulfo group may form a copolymer with other monomers. Examples of copolymerizable monomers include alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene, and acrylonitrile. , acrylic acid, sodium acrylate, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, acrylamide, methacrylamide, diacetone acrylamide, vinyltoluene, xylene sulfonic acid, vinylpyridine, vinyl sulfonic acid, vinyl alcohol, methyl methacrylate , sodium methacrylate, hydroxyethyl methacrylate, etc., but styrene is preferred.

A polymer having a sulfo group salt in the side chain of a linear polymer can be produced by a general-purpose method. For example, a method of radical polymerizing a monomer having a sulfo group salt, A method of radical polymerizing a monomer having a sulfo group and a monomer copolymerizable with this monomer, a method in which the sulfo group of a polymer containing a monomer component having a sulfo group is removed by an alkali (e.g., sodium hydroxide, hydroxide Examples include a method of neutralizing using calcium, potassium hydroxide, ammonium hydroxide, etc.).

In a virus infection inhibitor, the content of a compound having a sulfo group salt is the total amount of the compound having a sulfo group salt, organic acid (organic acid dissolved in water and organic acid insoluble in water), and water. It is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and even more preferably 3 parts by mass or more based on 100 parts by mass. When the content of the sulfo group salt is 0.1 parts by mass or more, the effect of inhibiting virus infection against enveloped viruses and non-enveloped viruses can be further improved due to the synergistic effect with the organic acid. The upper limit of the content of the compound having a salt of a sulfo group is not particularly limited, but from the viewpoint of manufacturing cost of the virus infection inhibitor, the content of the compound having a salt of a sulfo group, organic acids (organic acids dissolved in water and The amount is preferably 50 parts by mass or less per 100 parts by mass of the total amount of organic acid (organic acid insoluble in water) and water.

[Organic acid]
Viral infection inhibitors contain organic acids. Since the virus infection inhibitor contains an organic acid, it promotes the release of the sulfo group salt in a compound having a sulfo group salt and improves the virus infection inhibitory effect against non-enveloped viruses. The effect of inhibiting virus infection against enveloped viruses and non-enveloped viruses can be improved.

Furthermore, a compound having a sulfo group weakens the capsid (protein shell) of non-enveloped viruses, and can improve the effect of organic acids on inhibiting virus infection against non-enveloped viruses.

As described above, the virus infection inhibitor improves the virus infection inhibiting effect against enveloped viruses and non-enveloped viruses by containing a compound having a sulfo group salt and an organic acid.

The organic acid may be any organic compound as long as it can promote release of some or all of the sulfo group salts in a compound having a sulfo group salt, and may be a polymer. Organic acids have a carboxy group (-COOH), a sulfo group (-SO ₃ H), a phosphonic acid group [-P(=O)(OH) ₂ ], or a phosphoric acid group [-OPO(OH) ₂ ] in the molecule. ], and may have only one type of these functional groups, or may have multiple types of functional groups. Organic acids can more effectively maintain or promote the release of some or all of the sulfo group salts in compounds that have sulfo group salts, thereby further improving the effect of inhibiting virus infection against enveloped viruses and non-enveloped viruses. Therefore, it is preferable to have a carboxy group.

Organic acids have a carboxy group (-COOH), a sulfo group (-SO ₃ H), a phosphonic acid group [-P(=O)(OH) ₂ ], and a phosphoric acid group [-OPO(OH) ₂ ] in the molecule. It is preferable to have a plurality of functional groups selected from the group consisting of the following, it is more preferable that a carboxyl group is included in the plurality of functional groups, and it is more preferable to have a plurality of carboxyl groups. When the organic acid has a plurality of the above-mentioned functional groups, the release of some or all of the sulfo group salts in the compound having the sulfo group salts can be maintained or promoted more reliably, and enveloped viruses and non-enveloped viruses can be The effect of inhibiting virus infection against enveloped viruses can be further improved. Note that the organic acid preferably does not contain a sulfo group salt in its molecule.

The organic acid has a carboxy group (-COOH), a sulfo group (-SO ₃ H), a phosphonic acid group [-P(=O)(OH) ₂ ], or a phosphoric acid group [-OPO(OH)] in the molecule. ₂ ], there are no particular limitations, such as adipic acid (solubility: 14 g/L), benzoic acid (solubility: 3.4 g/L), lauric acid (solubility: 0 g/L), azelaic acid. (Solubility: 2.4g/L), Sebacic acid (Solubility: 0.25g/L), Dodecanedioic acid (Solubility: 0g/L), Fumaric acid (Solubility: 6.3g/L), Phthalic acid (Solubility: 7.2g/L), isophthalic acid (solubility: 0.13g/L), terephthalic acid (solubility: 0.017g/L), methylenedisalicylic acid (solubility: 0g/L), cis-Δ4-tetrahydrophthalic acid ( Solubility: 0g/L), Caproic acid (Solubility: 11g/L), Enanthic acid (Solubility: 2.4g/L), Caprylic acid (Solubility: 0.68g/L), Pelargonic acid (Solubility: 0.28g/L) L), capric acid (solubility: 0.15g/L), lauric acid (solubility: 0.0048g/L), myristic acid (solubility: 0g/L), palmitic acid (solubility: 0g/L), stearic acid ( Solubility: 0g/L), Myristoleic acid (Solubility: 0g/L), Oleic acid (Solubility: 0g/L), Ricinoleic acid (Solubility: 0g/L), Salicylic acid (Solubility: 2.0g/L), Gallic acid Acid hydrate (solubility: 11g/L), benzylic acid (solubility: 1.4g/L), 4-aminobenzoic acid (solubility: 6g/L), triglycolamic acid (solubility: 1.3g/L) , polyacrylic acid (solubility: 250 g/L or more), 1,3-propanediaminetetraacetic acid (solubility: 9 g/L), diethylenetriaminepentaacetic acid (solubility: 4 g/L), etc., adipic acid, fumaric acid, Preferred are phthalic acid, isophthalic acid, terephthalic acid, triglycolamic acid, 1,3-propanediaminetetraacetic acid, and diethylenetriaminepentaacetic acid. The solubility shown in parentheses is the solubility of the organic acid in water at 25°C. Note that the organic acids may be used alone or in combination of two or more kinds.

When the organic acid is a polymer, for example, the side chain of the linear polymer has a carboxy group (-COOH), a sulfo group (-SO ₃ H), a phosphonic acid group [-P(=O )(OH) ₂ ] or a polymer having a phosphoric acid group [-OPO(OH) ₂ ].

Carboxy group (-COOH), sulfo group (-SO ₃ H), phosphonic acid group [-P(=O)(OH) ₂ ] or phosphoric acid group [-OPO(OH)] in the side chain of the linear polymer. ₂ ], the linear polymer is not particularly limited, and for example, vinyl polymers, polyesters, and polyurethanes are preferred, and vinyl polymers are more preferred.

Carboxy group (-COOH), sulfo group (-SO ₃ H), phosphonic acid group [-P(=O)(OH) ₂ ] or phosphoric acid group [-OPO(OH)] in the side chain of the linear polymer. The polymer having [ _-P Examples thereof include a polymer containing a monomer component having a phosphoric acid group [-OPO(OH) ₂ ], and a polymer containing a monomer component having a phosphoric acid group [-OPO(OH) ₂ ].

Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, and mono(meth)acryloyloxysuccinate. Examples include ethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, carboxybetaine type monomers, and acrylic acid and methacrylic acid are preferred. In addition, the monomer having a carboxy group may be used alone or in combination of two or more types.

Examples of monomers having a sulfo group include p-styrenesulfonic acid, m-styrenesulfonic acid, o-styrenesulfonic acid, acrylamide t-butylsulfonic acid, vinylsulfonic acid, and 2-(methacryloyloxy)ethanesulfonic acid. , 3-(methacryloyloxy)propanesulfonic acid, 4-[(3-methacrylamidopropyl)dimethylammonio]butane-1-sulfonic acid, and the like. In addition, the monomer having a sulfo group may be used alone or in combination of two or more kinds.

Examples of the monomer having a phosphonic acid group include vinylphosphonic acid and alkyl vinylphosphonate. In addition, the monomer having a phosphonic acid group may be used alone or in combination of two or more types.

Examples of the monomer having a phosphoric acid group include phosphoric acid monoacrylate, phosphoric acid diacrylate, phosphoric acid monomethacrylate, phosphoric acid dimethacrylate, phosphoric acid methacrylic acid 2-hydroxyethyl ester, and the like. In addition, the monomer having a phosphoric acid group may be used alone or in combination of two or more kinds.

When the organic acid is a polymer, the polymer contains a carboxy group (-COOH), a sulfo group (-SO ₃ H), a phosphonic acid group [-P(=O)(OH) ₂ ], or a phosphoric acid group [ -OPO(OH) ₂ ] is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, It is more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass.

Carboxy group (-COOH), sulfo group (-SO ₃ H), phosphonic acid group [-P(=O)(OH) ₂ ] or phosphoric acid group [-OPO(OH)] in the side chain of the linear polymer. ₂ ] has a carboxy group (-COOH), a sulfo group (-SO ₃ H), a phosphonic acid group [-P(=O)(OH) ₂ ], or a phosphoric acid group [-OPO(OH) ₂ ] may contain a monomer component copolymerizable with the monomer having the following.

Examples of the copolymerizable monomer include alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene, Examples include acrylonitrile, sodium acrylate, acrylamide, methacrylamide, diacetone acrylamide, vinyltoluene, vinylpyridine, methyl methacrylate, sodium methacrylate, and hydroxyethyl methacrylate.

Carboxy group (-COOH), sulfo group (-SO ₃ H), phosphonic acid group [-P(=O)(OH) ₂ ] or phosphoric acid group [-OPO(OH)] in the side chain of the linear polymer. ₂ ] can be produced by a general-purpose radical polymerization method.

In the virus infection inhibitor, at 25°C, a part of the organic acid does not dissolve in water and exists in an insoluble state. That is, at 25° C., a portion of the organic acid in the virus infection inhibitor is dissolved in water, while a portion of the organic acid is not dissolved in water and is present in the water in an insoluble state. At 25°C, some of the organic acid is precipitated in the water.

A virus infection inhibitor exhibits an excellent virus infection inhibiting effect due to the interaction between a compound having a salt of a sulfo group and an organic acid. When the virus infection inhibitor is used, it is used in the form of a dried product produced by drying and removing water. If all the organic acids in the virus infection inhibitor are dissolved, the compound having a sulfo group salt and the organic acid will tend to precipitate separately during the drying process to dry and remove water, and as a result, the sulfo group salt-containing compound and the organic acid will easily separate. The interaction between a compound having a salt of the group and an organic acid may be weakened.

Therefore, in the virus infection inhibitor, a part of the organic acid is present in an insoluble state (precipitated state) in water, and a compound having a sulfo group salt that precipitates during the drying process of the water in the virus infection inhibitor is prepared. It makes it easier for organic acids to adhere to the surface in an insoluble state (precipitated state), and allows the interaction between compounds with sulfo group salts and organic acids to occur more effectively, and is excellent even after contact with ethanol solutions for disinfection. It is designed to have the effect of preventing virus infection.

Organic acids that are insoluble in water (organic acids precipitated in water) are foreign substances in the virus infection inhibitor that contains water, so they are gradually generated during the drying process of the virus infection inhibitor. It is extruded onto the surface of the dried product, and as a result, the virus infection inhibitor is more likely to exist on the surface of the dried product produced by drying. As a result, compounds with sulfo group salts and organic acids, which are in a state where they can interact more effectively, are concentrated on the surface of the dried material, and the dried material is removed after contact with the ethanol solution for disinfection. It also has an excellent effect on preventing viral infection.

Additionally, in the virus infection inhibitor, part of the organic acid is dissolved in water. In this way, a part of the organic acid is dissolved in water, and during the drying process of the virus infection inhibitor, the organic acid is applied with excellent adhesion to the substrate to which the dried virus infection inhibitor is attached. It can be precipitated from water. Therefore, the dried product produced by drying the virus infection inhibitor exhibits excellent adhesion to the substrate and is firmly integrated with the surface of the substrate, making it unlikely to come into contact with the disinfectant ethanol solution. However, it is possible to stably impart an excellent virus infection inhibiting effect to the base material over a long period of time.

In the virus infection inhibitor, a part of the organic acid is present in an insoluble state in water, so the virus infection inhibitor usually becomes cloudy.

The solubility of the organic acid in water at 25°C (solubility in water at 25°C) is preferably 20 g/L or less, more preferably 18 g/L or less. When the solubility of an organic acid in water at 25°C is 20 g/L or less, the affinity between the compound having a salt of a sulfo group and the organic acid increases, and the compound having a salt of a sulfo group and the organic acid improve. As a result, the synergistic effect between the sulfo group salt of a compound having a sulfo group salt and an organic acid can be improved, and the effect of inhibiting virus infection against both enveloped viruses and non-enveloped viruses can be improved. Note that the solubility of an organic acid in water at 25° C. refers to the mass of the organic acid that dissolves in 1 L of water. That is, the solubility of an organic acid in water at 25°C refers to the mass of the organic acid in a saturated solution (25°C) containing 1 L of water.

The solubility of the organic acid in water at 25°C is preferably 0.1 g/L or more, more preferably 1 g/L or more. If the solubility of an organic acid in water at 25°C is 0.1 g/L or more, the sulfo group salt of a compound having a sulfo group salt will be dissolved when a protein aqueous solution containing a virus, such as saliva or sputum, comes into contact with the organic acid. It promotes release and improves the effectiveness of preventing virus infection against non-enveloped viruses.

The solubility of organic acids in water at 25°C is determined by OECD Chemical Test Guidelines No. 105 (water solubility), measured at 25°C.

The pKa1 of the organic acid at 25° C. is more preferably 4.6 or less, more preferably 3.8 or less. When the pKa1 at 25°C of the organic acid is 4.6 or less, the effect of inhibiting virus infection against enveloped viruses is improved due to the synergistic effect of the sulfo group salt and the organic acid, and when it is 3.8 or less, the sulfo group By promoting the release of the salt, protein denaturation by protons is caused, and the effect of inhibiting virus infection not only against enveloped viruses but also against non-enveloped viruses is improved.

Here, in the present invention, when the electrolyte HA is ionized into A ^- and H ⁺ and takes the ionization equilibrium equation (1), the acid dissociation constant Ka is defined by the equation (2), and pKa is the acid dissociation constant Ka. It is defined by the common logarithm (3) of the reciprocal of the constant Ka.

When the organic acid is a polyvalent acid, ionization of the polyvalent acid proceeds in multiple stages, and pKa1 refers to pKa calculated based on the ionization constant of the first stage.

The pKa1 of an organic acid at 25°C is a value measured by titration. Specifically, titration is performed at 25°C using an organic acid and sodium hydroxide, and the pH at 25°C is measured at the half-equivalence point (the point at which half of the amount that completes neutralization is dropped). Then, pKa1 can be determined.

When the organic acid is a polymer, it is preferable that the organic acid includes a crosslinked polymer. A part of the organic acid can be present in a water-insoluble state in the virus infection inhibitor, and the dried product produced from the virus infection inhibitor has an excellent ability to inhibit virus infection even after contact with an ethanol solution for disinfection. The effect can be maintained.

The method for crosslinking the polymer is not particularly limited, and may be carried out in a commonly used manner. As a method for crosslinking a polymer, for example, (1) after polymerizing monomers to obtain a polymer, crosslinking the polymer by supplying a crosslinking aid and a peroxide to the polymer and heating it; and (2) a method in which monomers are polymerized to obtain a polymer, and then a crosslinking agent is supplied to the polymer and heated to crosslink the polymer.

The crosslinking aid is not particularly limited, and examples thereof include divinylbenzene, trimethylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, trimellitic acid triallyl ester, and triallylisocyanate. Nurate, ethylvinylbenzene, neopentyl glycol dimethacrylate, 1,2,4-benzene tristriallyl ester, 1,6-hexanediol dimethacrylate, lauryl methacrylate, stearyl methacrylate, diallyl phthalate, diallyl terephthalate, isophthalic acid Examples include diallyl. Note that the crosslinking aids may be used alone or in combination of two or more.

The peroxide is not particularly limited, and examples thereof include 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl perbenzoate, cumyl hydroperoxide, t-butyl hydroperoxide, and 1,1-dichlorobenzoyl peroxide. (t-butylperoxy)-3,3,5-trimethylhexane, n-butyl-4,4-di(t-butylperoxy)valerate, α,α'-bis(t-butylperoxyisopropyl)benzene , 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and t-butylperoxycumene. Note that peroxides may be used alone or in combination of two or more types.

The crosslinking agent is not particularly limited, and general-purpose crosslinking agents can be used, such as epoxy crosslinking agents, isocyanate crosslinking agents, imine crosslinking agents, and the like. Note that the crosslinking agents may be used alone or in combination of two or more.

Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and trimethylolpropane-modified tolylene diisocyanate.

Examples of the epoxy crosslinking agent include N,N'-(cyclohexane-1,3-diylbismethylene)bis(diglycidylamine), N,N,N',N'-tetraglycidyl-1,3-benzenedi (Methanamine) and the like are preferred.

When the organic acid contains a crosslinked polymer, the gel fraction of the organic acid is preferably 65% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more. The gel fraction of the organic acid is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 96% by mass or less. When the gel fraction of the organic acid is 65% by mass or more, a part of the organic acid can be more reliably present in an insoluble state in water, and even after contact with a disinfectant ethanol solution, the virus infection inhibitor The dried product can maintain an excellent virus infection inhibiting effect. Moreover, since the polymer has a crosslinked structure, the crosslinked part of the polymer is insoluble in the ethanol solution, while the non-crosslinked part of the polymer can move freely, allowing it to efficiently adsorb viruses. By doing so, it is possible to exhibit an excellent virus infection prevention effect even after contact with a disinfectant ethanol solution. When the gel fraction of the organic acid is 99% by mass or less, by dissolving a part of the organic acid in water, it is possible to improve the adhesion of the virus infection inhibitor to the base material of the dried product, and it can be used for disinfection. The excellent virus infection inhibiting effect imparted to the substrate can be stably maintained even after contact with the ethanol solution.

The gel fraction of an organic acid refers to a value measured in the following manner. Ag organic acid was weighed, immersed in purified water at 60°C for 24 hours, insoluble matter was filtered through a 200-mesh wire mesh, and the residue on the wire mesh was vacuum-dried at 80°C for 16 hours to obtain a dry residue. The weight of (Bg) is measured, and the gel fraction of the organic acid is calculated using the following formula.
Gel fraction of organic acid (mass%) = (B/A) x 100

When the organic acid is a polymer, the weight average molecular weight of the organic acid is preferably 3,000 or more, preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more. When the weight average molecular weight of the organic acid is 3000 or more, the number of adsorption points with the virus per molecule of the organic acid increases, the interaction between the organic acid and the virus becomes stronger, and the virus infection inhibiting effect of the virus infection inhibitor is reduced. can be improved.

The weight average molecular weight of the organic acid is preferably 1,000,000 or less, more preferably 900,000 or less, more preferably 800,000 or less, and more preferably 500,000 or less. When the weight average molecular weight of the organic acid is 1,000,000 or less, the aggregation of insoluble components of the organic acid is reduced, resulting in a form in which the organic acid and the virus are likely to interact, and the virus infection inhibitory agent is used to inhibit viral infection. The blocking effect is improved.

In the present invention, the weight average molecular weight of the polymer is a value measured by GPC (gel permeation chromatography) in terms of polystyrene. In addition, when a polymer is crosslinked, the weight average molecular weight of a polymer refers to the weight average molecular weight of a polymer before crosslinking.

For example, the measurement can be performed using the following measuring device and measurement conditions.
Gel permeation chromatograph: Manufactured by Waters, product name “2690 Separations Model”
Column: Manufactured by Showa Denko, product name “GPC KF-806L”
Detector: Differential refractometer Sample flow rate: 1mL/min
Column temperature: 40℃
Eluent: THF

The organic acid is preferably solid at 1 atm (1013.25 hPa) and 25°C. When the organic acid is solid at 1 atm and 25° C., it is more likely to appear on the surface of a processed coating film or other virus infection prevention product, making it more likely to come into contact with viruses, thereby improving the virus infection prevention effect.

In the virus infection inhibitor, the content of organic acid is based on 100 parts by mass of the compound having a salt of a sulfo group, the organic acid (organic acid dissolved in water and organic acid in a water-insoluble state), and water. The amount is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. When the content of the organic acid is 5 parts by mass or more, a part of the organic acid tends to exist in an insoluble state, and the effect of inhibiting virus infection against enveloped viruses and non-enveloped viruses can be further improved.

The upper limit of the content of organic acids in virus infection inhibitors is not particularly limited, but from the viewpoint of manufacturing cost of virus infection inhibitors, compounds having sulfo group salts, organic acids (organic acids dissolved in water), etc. and a water-insoluble organic acid) and water, preferably 70 parts by mass or less, based on the total amount of 100 parts by mass.

In a virus infection inhibitor, the mass ratio between the content of a compound having a sulfo group salt and the content of an organic acid (organic acid dissolved in water and organic acid in a water-insoluble state) The ratio (content of the compound/content of the organic acid) is preferably 0.01 or more, more preferably 0.02 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. In a virus infection inhibitor, the mass ratio between the content of a compound having a sulfo group salt and the content of an organic acid (organic acid dissolved in water and organic acid in a water-insoluble state) The ratio (content of compounds contained/content of organic acids) is preferably 1.7 or less, more preferably 1.6 or less, and even more preferably 1.55 or less. When the mass ratio of the content of the compound having a salt of a sulfo group to the content of an organic acid (content of a compound having a salt of a sulfo group/content of an organic acid) is 0.01 or more, Virus adsorption by the sulfo group generated by liberating the salt of the sulfo group in a compound having a salt is promoted, and an excellent effect of inhibiting virus infection is exhibited. If the mass ratio between the content of the compound having a sulfo group salt and the content of the organic acid (content of the compound having a sulfo group salt/content of organic acid) is 1.7 or less, it will dissolve in water. Due to the action of the compound having a sulfo group salt and the organic acid dissolved in water, the adhesion between the water-insoluble organic acid and the substrate is improved, and the dry product of the virus infection inhibitor is It becomes difficult to peel off from the base material, and the excellent virus infection inhibiting effect imparted to the base material can be stably maintained even after contact with a disinfecting ethanol solution.

In the virus infection inhibitor, the water content is based on 100 parts by mass of the compound having a sulfo group salt, organic acid (organic acid dissolved in water and organic acid insoluble in water), and water. , is preferably 95 parts by weight or less, more preferably 90 parts by weight or less, and even more preferably 80 parts by weight or less. When the water content is 95 parts by mass or less, a part of the organic acid tends to exist in an insoluble state, and the effect of inhibiting virus infection against enveloped viruses and non-enveloped viruses can be further improved. The lower limit of the water content is not particularly limited, but from the viewpoint of manufacturing cost of virus infection inhibitors, compounds with sulfo group salts, organic acids (organic acids dissolved in water and organic acids insoluble in water) It is preferably 30 parts by weight or more based on 100 parts by weight of the total amount of acid) and water.

[Other ingredients]
The virus infection inhibitor may contain additives such as a dispersant, a thickener, an antioxidant, and an ultraviolet absorber within a range that does not impair its physical properties.

Examples of dispersants include anionic surfactants (excluding compounds having a sulfo group salt in the molecule), cationic surfactants, nonionic surfactants, amphoteric surfactants (however, , excluding compounds having a sulfo group salt in the molecule). As the dispersant, anionic surfactants (excluding compounds having a salt of a sulfo group in the molecule) are preferred since they improve the dispersibility of organic acids that are insoluble in water.

Examples of the anionic surfactant (excluding compounds having a sulfo group salt in the molecule) include alkyl sulfate ester salts, alkyl ethoxy sulfate ester salts, phosphate ester salts, and the like.

Examples of the cationic surfactant include fatty amine salts, quaternary ammonium salts, alkylpyridinium salts, and the like.

Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester (for example, polyethylene glycol distearate, etc.), and polyoxyethylene distyrene. phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, poly Oxyethylene fatty acid amides, fatty acid alkanolamides (e.g., coconut fatty acid alkanolamides such as coconut fatty acid dimethanolamide, coconut fatty acid diethanolamide, coconut fatty acid dipropanolamide, etc.), fatty acid alkylolamides, alkyl alkanolamides, acetylene glycol, acetylene glycol oxyethylene adducts, polyethylene glycol polypropylene glycol block copolymers, and the like.

Examples of the amphoteric surfactant (excluding compounds having a sulfo group salt in the molecule) include tertiary amine oxide, betaine, alkyl betaine, and the like.

The thickener may be a natural polymer compound or a synthetic polymer compound. Examples of natural polymer compounds include pectin, gelatin, carrageenan, xanthan gum, gum arabic, glucomannan, gellan gum, and alginic acid. Examples of the synthetic polymer compound include polyethylene glycol and polyvinyl alcohol.

[Viral infection inhibitor]
The virus infection inhibitor contains water-insoluble components (precipitated components). In the virus infection inhibitor, almost all of the insoluble portion is composed of organic acids that are present in an insoluble state in water. A part of the water-insoluble components (precipitated components) may include components other than organic acids.

At 25°C, the content of insoluble matter in the virus infection inhibitor is the total amount of compounds having sulfo group salts, organic acids (organic acids dissolved in water and organic acids in a water-insoluble state), and water. It is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, based on 100 parts by mass. When the content of insoluble matter is 1 part by mass or more, by improving the interaction between the compound having a sulfo group salt and the organic acid, the virus infection inhibitor can be used even after contact with a disinfectant ethanol solution. The excellent virus infection inhibiting effect of the dried product can be maintained. At 25°C, the upper limit of the content of insoluble matter in the virus infection inhibitor is not particularly limited, but from the viewpoint of coating properties, compounds having sulfo group salts, organic acids (organic acids dissolved in water), etc. It is preferably 70 parts by mass or less based on 100 parts by mass of the total amount of the acid, water-insoluble organic acid) and water.

At 25°C, the content of organic acid in the insoluble matter of the virus infection inhibitor is more preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more. more preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, preferably 95% by mass or more, It is more preferably 98% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass. When the content of the organic acid is 10% by mass or more, the interaction between the compound having a sulfo group salt and the organic acid is improved, so that the virus infection inhibitor is effective even after contact with an ethanol solution for disinfection. The excellent virus infection inhibiting effect of the dried product can be maintained. At 25°C, the upper limit of the content of organic acid in the insoluble portion of the virus infection inhibitor is not particularly limited.

At 25°C, the content of insoluble matter in the virus infection inhibitor refers to the value measured in the following manner. First, the mass of only the type 5 C filter paper based on JIS P3801 is measured. Next, after suction-filtering 100 g of the virus infection inhibitor through the filter paper, the filter paper is dried at 120° C. for 2 hours, and the total dry mass of the undissolved matter remaining on the surface of the dry filter paper and the filter paper is measured. By subtracting the mass of only the filter paper from this total mass, the mass of the insoluble matter in the virus infection inhibitor is determined. Note that the filter paper after suction filtration contains compounds with sulfo group salts and organic acids dissolved in water, and these dissolved components precipitate as the filter paper dries, adding up to the above total. Although it will be included in the dry mass, the mass of the dissolved matter dissolved in water is extremely small compared to the mass of the undissolved matter in the virus infection inhibitor, so the undissolved mass in the virus infection inhibitor does not affect the content of

At 25°C, the D90 particle size of the insoluble matter contained in the virus infection inhibitor is preferably 1 μm or more, more preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. At 25°C, the D90 particle size of the insoluble matter contained in the virus infection inhibitor is preferably 25 μm or less, more preferably 22 μm or less, more preferably 20 μm or less, more preferably 18 μm or less, and even more preferably 16 μm or less. It is preferably 14 μm or less, more preferably 12 μm or less. When the D90 particle size is 1 μm or more, the surface area of the organic acid that accounts for most of the undissolved content becomes small, the aggregation of the undissolved organic acid is reduced, and the interaction between the virus infection inhibitor and the virus is reduced. The virus infection inhibiting effect of the virus infection inhibiting agent is improved. When the D90 particle size is 25 μm or less, the surface area can be increased to facilitate contact with viruses, and the virus infection inhibiting effect of the virus infection inhibitor can be improved. Furthermore, the dried product of the virus infection inhibitor can be more uniformly adhered to the surface of the base material, and the virus infection inhibiting effect can be imparted to the base material in a more uniform state.

At 25°C, the D90 particle size of the insoluble portion contained in the virus infection inhibitor is determined by the cumulative frequency of the volume-based particle size distribution determined by the laser scattering method (accumulated from particles with small particle size), as described below. ) is 90% (90% cumulative particle diameter). By adjusting the D90 particle size of the insoluble matter in the virus infection inhibitor to preferably 1 to 25 μm, the inclusion of coarse particles in the organic acid that accounts for most of the insoluble matter is reduced. Organic acids have functional groups [carboxy group (-COOH), sulfo group (-SO ₃ H), phosphonic acid group [-P(=O)(OH) ₂ ]] or phosphoric acid group [-OPO(OH)] in the molecule. ) ₂ ]], but by adjusting the D90 particle size of the insoluble portion, in which the organic acid occupies the majority, to the above range, the amount of the above functional groups present in the organic acid can be adjusted, and the virus It imparts an excellent virus infection inhibiting effect to the infection inhibitor.

At 25°C, the D50 particle size of the insoluble matter contained in the virus infection inhibitor is preferably 0.5 μm or more, more preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. preferable. At 25°C, the D50 particle size of the insoluble matter contained in the virus infection inhibitor is preferably 20 μm or less, more preferably 18 μm or less, more preferably 14 μm or less, more preferably 12 μm or less, and even more preferably 11 μm or less. preferable.

In the virus infection inhibitor, preferably, the D50 particle size of the insoluble portion is within the above range (preferably 0.5 to 20 μm) and the D90 particle size is 1 to 25 μm, so that most of the organic acid is It is possible to reduce the inclusion of coarse particles having a particle diameter far from the D50 particle diameter in the insoluble matter that occupies the D50 particle diameter, and to make the particle diameter of the insoluble matter more appropriate.

By adjusting the particle size of the insoluble fraction to a more appropriate range, the amount of the above-mentioned functional groups present on the surface of the organic acid, which accounts for the majority of the insoluble fraction, can be adjusted more appropriately, and this can be used as a virus infection inhibitor. Provides superior virus infection prevention effects more effectively.

The D90 particle size and D50 particle size of the insoluble matter are the particle size (90% Cumulative particle size and 50% cumulative particle size).

The virus infection inhibitor contains a compound having a sulfo group salt and an organic acid (excluding compounds having a sulfo group salt) as active ingredients, but the method for producing the virus infection inhibitor is not particularly limited. First, a virus infection inhibitor can be produced by supplying a compound having a sulfo group salt and an organic acid (excluding compounds having a sulfo group salt) to water and uniformly mixing them in a conventional manner. In the obtained virus infection inhibitor, almost all (preferably all) of the compound having a salt of a sulfo group is dissolved in water, while a part of the organic acid is dissolved in water. The remainder remains in an insoluble state without being dissolved in water. The dried product obtained by drying the virus infection inhibitor to remove water has an excellent virus infection prevention effect, and even after contact with a disinfectant ethanol solution, it has an excellent virus infection prevention effect ( It has antiviral properties) and excellent ethanol resistance.

Note that the effect of inhibiting virus infection refers to the effect of eliminating or reducing the infectivity of a virus to cells, or preventing it from proliferating in cells even if infected. Examples of methods for confirming the presence or absence of virus infectivity include ISO 18184 and JIS L1922 for textile products, and ISO 21702 for products with plastics and non-porous surfaces other than textile products. The Antibacterial Products Technology Association (SIAA) certifies antiviral processing marks to products that meet the safety and certain antiviral efficacy standards for antiviral finishing agents, and the standards for antiviral efficacy are based on ISO 21702 evaluations. The difference (antiviral activity value) between the common logarithm value of the viral infectivity value of the blank product (product without the addition of antiviral processing agent) and the common logarithm value of the viral infectivity value of the processed product (product with addition of antiviral processing agent) It is 2.0 or more. Viral infection inhibitors are used as antiviral processing agents. The virus infection inhibitor may be used by being added to a surface coating agent such as a paint, and evaluated by the above evaluation method.

In the present invention, for example, when evaluating the virus infection inhibiting effect under the following conditions, the difference in the common logarithm value of the virus infectivity titer (antiviral A product with an activity value of 2.0 or higher is defined as a virus infection inhibitor. At that time, regardless of the type of virus to be evaluated, for at least one type of virus, the difference in the common logarithm value of the virus infectivity value (antiviral activity value) between the blank product and the processed product is 2.0 or more. Treated as a virus infection inhibitor.

10 parts by weight of the virus infection inhibitor in terms of solid content (in terms of the total amount of the compound having a salt of a sulfo group and organic acid), and a water-based paint (for example, acrylic emulsion, solid content of binder component: 40% by mass, solvent: water). ) is uniformly mixed with 90 parts by weight in terms of binder component as a solid content to prepare a water-based paint. The water-based paint is selected so that a part of the organic acid is present in a water-insoluble state in the resulting water-based paint. After applying the obtained water-based paint onto a polyester film, it is dried at room temperature for 1 hour, and further dried at 120° C. for 1 hour to form a coating film with a thickness of 10 μm.

Soak 0.5 mL of a disinfecting ethanol solution (ethanol: 80% by mass, water: 20% by mass) into a square cotton cloth with a side of 6cm [attached white cloth for JIS L0803 compliant test cotton (Kanakin No. 3)]. Then, attach a cotton cloth to the friction element of a friction tester type I (for example, manufactured by Imoto Seisakusho Co., Ltd.). Next, the surface of the obtained coating film was rubbed back and forth 400 times at a pressure of 40 g/cm ² , and after drying at room temperature, it was used as a test coating film. In addition, the cotton cloth is replaced with a new cotton cloth impregnated with 0.5 mL of disinfectant ethanol solution every 100 times.

The antiviral test of the obtained test coating film was conducted in accordance with ISO21702. For the virus suspension after the reaction, the virus infectivity value (common logarithm value) of the test coating is calculated by the plaque method.

A blank coating film was prepared in the same manner as above except that no virus infection inhibitor was contained, and based on this blank coating, the virus infection titer (common logarithm value) (PFU/cm ² ) was determined in the same manner as above. Calculate.

Calculate the antiviral activity value by subtracting the virus infection titer of the test coating from the virus infection titer of the blank coating.

Other methods include the plaque method and the hemagglutination titer (HAU) measurement method described in "Medical and Pharmaceutical Virology" (first edition published in April 1990).

Viral infection inhibitors have the effect of inhibiting virus infection against various viruses due to the synergistic effect of a compound having a sulfo group salt and an organic acid (excluding compounds having a sulfo group salt), and are effective against enveloped viruses and non-enveloped viruses. It exhibits excellent virus infection prevention effects against both enveloped viruses. The virus infection inhibitor has a part of the organic acid present in an insoluble state (precipitated state) in water, so it has an excellent virus infection inhibiting effect (antiviral property) even after contact with a disinfectant ethanol solution. It has excellent ethanol resistance, and can also firmly adhere the dried product obtained by drying the virus infection inhibitor to the base material, stably imparting excellent virus infection inhibiting effects to the base material. be able to.

Examples of enveloped viruses include influenza viruses (e.g., type A, type B, etc.), rubella virus, Ebola virus, coronaviruses (e.g., SARS virus, new coronavirus (SARS-CoV-2)), measles virus, varicella virus, etc. Herpes zoster virus, herpes simplex virus, mumps virus, arbovirus, respiratory syncytial virus, hepatitis virus (e.g., hepatitis B virus, hepatitis C virus, etc.), yellow fever virus, AIDS virus, rabies virus, hantavirus, dengue virus, Nipah virus , lyssavirus, etc.

Examples of non-enveloped viruses include adenovirus, norovirus, rotavirus, human papillomavirus, poliovirus, enterovirus, coxsackievirus, human parvovirus, encephalomyocarditis virus, and rhinovirus.

The virus infection inhibitor is applied to the surface of the base material to which it is desired to impart a virus infection inhibiting effect, and then the water contained in the virus infection inhibitor is evaporated and removed to produce a dry product. Integrate into the surface of the material. The substrate on which the dried material is attached exhibits a virus infection inhibiting effect as a virus infection inhibiting product.

Substrates to which the dried virus infection inhibitor is attached include, for example, synthetic resin moldings, wallpaper, decorative sheets, flooring materials, textile products (woven fabrics, non-woven fabrics, knitted fabrics), and vehicles (for example, cars, airplanes, ships). Examples include daily necessities and interior materials (such as seats, child seats, and the foam materials that make up these), kitchen supplies, baby products, and architectural interior materials.

Architectural interior materials are not particularly limited, and include, for example, flooring materials, wallpaper, ceiling materials, paints, doorknobs, switches, switch covers, wax, and the like.

Vehicle interior supplies and vehicle interior materials are not particularly limited, and include, for example, seats, child seats, seat belts, car mats, seat covers, doors, ceiling materials, floor mats, door trims, instrument panels, consoles, glove boxes, hanging leather, handrails, etc. can be mentioned.

The virus infection inhibitor may be used by being supplied to a water-based paint. When a water-based paint is used by supplying a virus infection inhibitor, the water-based paint contains water as a solvent. Therefore, when a virus infection inhibitor is contained in a water-based paint, it is preferable to include it in a proportion such that a part of the organic acid does not dissolve in water and exists in an insoluble state in the water-based paint containing the virus infection inhibitor. . After applying a water-based paint containing a virus infection inhibitor to the base material, the water is evaporated and removed to produce a dried product of the virus infection inhibitor, and this dried product is integrated onto the surface of the base material. let The substrate on which the dried material is attached exhibits a virus infection inhibiting effect as a virus infection inhibiting product.

A water-based paint is a paint using an aqueous solvent containing water as a main component (in the solvent, preferably 50% by mass or more of water). Water-based paints contain a water-based solvent and a binder component. The water-based paint may contain additives such as pigments, curing agents, extenders, fillers, anti-aging agents, thickeners, etc. within the range that does not impair its physical properties. Note that, as a method for incorporating the virus infection inhibitor into the water-based paint, for example, a method of supplying the virus infection inhibitor and the water-based paint to a dispersion device and uniformly mixing them can be mentioned. Note that examples of the dispersion device include a high-speed mill, a ball mill, and a sand mill.

The present invention will be explained in more detail below using Examples, but the present invention is not limited thereto.

[Preparation of crosslinked polyacrylic acids 1 to 4]
An epoxy crosslinking agent (sorbitol polyglycidyl ether, Nagase ChemteX, product name "Denacol EX-614B") was added to an aqueous solution of polyacrylic acid (product name "Aqualic HL-415" manufactured by Nippon Shokubai Co., Ltd., weight average molecular weight: 10,000). ) was supplied and mixed uniformly to prepare a polyacrylic acid solution. Table 1 shows the contents of polyacrylic acid and epoxy crosslinking agent in the polyacrylic acid solution.

The polyacrylic acid solution was heated to 120° C. for 90 minutes to crosslink the polyacrylic acid and dry it to obtain crosslinked polyacrylic acid.

(Examples 1 to 19, Comparative Examples 1 to 3)
A compound having a sulfo group salt of the type shown in Table 2 and an organic acid were supplied to water and mixed uniformly to prepare a virus infection inhibitor. Table 2 shows the contents of the compound having a sulfo group, organic acid, and water in the virus infection inhibitor. In Table 2, "a compound having a salt of a sulfo group" was written as a "salt compound".

Regarding the organic acids used in the production of virus infection inhibitors, melting point under 1 atm (1013.25 hPa), solubility in water at 25°C (g/L), pKa1 at 25°C, molecular weight (in the case of polymers) , weight average molecular weight before crosslinking) and gel fraction (mass %) are shown in Table 2.

In Table 2, "solubility in water at 25°C" and "pKa1 at 25°C" are simply written as "solubility" and "pKa1", respectively.

Regarding the obtained virus infection inhibitor, the content (mass%) of insoluble matter present in an insoluble state (precipitated state) in water at 25°C, and the content (mass%) of insoluble matter present in an insoluble state in water. Table 2 shows the D50 particle size (μm) and D90 particle size (μm) for each sample.

Regarding the obtained virus infection inhibitor, Table 2 shows the content of organic acid in the insoluble matter existing in an insoluble state (precipitated state) in water at 25°C. In the virus infection inhibitors of Examples 1 to 19, the content of organic acid in the insoluble matter was all over 90% by mass.

In Table 2, the amount of insoluble matter present in an insoluble state in water is simply written as "insoluble matter." The D50 particle diameter and D90 particle diameter of the insoluble matter that exists in an insoluble state in water can be found in the "D50 particle diameter (μm)" and "D90 particle diameter (μm)" columns of "Insoluble matter details". Each is described. The content of organic acid in the insoluble matter existing in an insoluble state (precipitated state) in water is described in the column of "Content of organic acid (mass %)" in "Details of insoluble matter". In Table 2, "<Y" (Y is a number) means "less than Y". ">Y" (Y is a number) means "greater than Y".

The obtained virus infection inhibitor was subjected to an antiviral test using influenza virus (enveloped virus) and feline calicivirus (non-enveloped virus), and the results are shown in Table 1.

(Antiviral test)
10 parts by weight of a virus infection inhibitor in terms of solid content (in terms of the total amount of compounds having sulfo group salts and organic acids), a water-based paint (acrylic emulsion, manufactured by Showa Denko K.K., trade name "Polysol AM-200"), and a binder. Component solid content: 40% by mass, solvent: water) was uniformly mixed with 90 parts by weight in terms of binder component to prepare a water-based paint. In the obtained water-based paint, a part of the organic acid was present in a water-insoluble state. The resulting water-based paint was applied onto a polyester film, dried at room temperature for 1 hour, and further dried at 120° C. for 1 hour to form a coating film with a thickness of 10 μm.

Soak 0.5 mL of a disinfecting ethanol solution (ethanol: 80% by mass, water: 20% by mass) into a square cotton cloth with a side of 6cm [attached white cloth for JIS L0803 compliant test cotton (Kanakin No. 3)]. Then, a cotton cloth was attached to the friction element of a friction tester type I (manufactured by Imoto Seisakusho Co., Ltd.). Next, the surface of the obtained coating film was rubbed back and forth 400 times at a pressure of 40 g/cm ² , and after drying at room temperature, it was used as a test coating film. The cotton cloth was replaced with a new cotton cloth impregnated with 0.5 mL of disinfectant ethanol solution every 100 times.

The antiviral test of the obtained test coating film was conducted in accordance with ISO21702. Regarding the virus suspension after the reaction, the virus infectivity value (common logarithm value) of the test coating was calculated by the plaque method.

A blank coating film was prepared in the same manner as above except that no virus infection inhibitor was contained, and based on this blank coating, the virus infection titer (common logarithm value) (PFU/cm ² ) was determined in the same manner as above. was calculated. The virus infectivity titer (common logarithmic value) of the blank coating film was 6.5 PFU/cm ² .

The antiviral activity value was calculated by subtracting the virus infection titer of the test coating from the virus infection titer of the blank coating.

The virus infection inhibiting agent of the present invention can produce a virus infection inhibiting product that exhibits an excellent virus infection inhibiting effect. The virus infection prevention product has excellent ethanol resistance and has an excellent virus infection prevention effect (antiviral property) even after contact with disinfectant ethanol solution, and has a virus infection prevention effect against various types of viruses. Maintain over a long period of time.

(Cross reference to related applications)
This application claims priority based on Japanese Patent Application No. 2022-134596 filed on August 26, 2022, and the disclosure of this application is incorporated herein by reference in its entirety.

Claims (13)

1. A virus infection inhibitor comprising a compound having a salt of a sulfo group, an organic acid, and water, wherein a part of the organic acid exists in an insoluble state in the water at 25°C.
2. The virus infection inhibitor according to claim 1, wherein the organic acid has a solubility in water of 20 g/L or less at 25°C.
3. Claim 1 or claim 1, wherein the content of insoluble matter at 25°C is 1 part by mass or more based on 100 parts by mass of the compound having a salt of a sulfo group, the organic acid, and the water. Item 2. The virus infection inhibitor according to item 2.
4. The mass ratio of the content of the compound having the salt of the sulfo group to the content of the organic acid (content of the compound having the salt of the sulfo group/content of the organic acid) is 0.01 to 1.7. The virus infection inhibiting agent according to claim 1 or 2, characterized in that:
5. The virus infection inhibitor according to claim 1 or 2, wherein the organic acid has a carboxy group.
6. The virus infection inhibitor according to claim 1 or 2, wherein the organic acid has a pKa1 of 4.6 or less at 25°C.
7. The virus infection inhibitor according to claim 1 or 2, wherein the organic acid contains a crosslinked polymer.
8. The virus infection inhibitor according to claim 7, wherein the organic acid has a gel fraction of 65 to 99% by mass.
9. The virus infection inhibitor according to claim 1 or 2, wherein the D90 particle size of the insoluble portion at 25° C. is 1 to 25 μm.
10. The virus infection inhibitor according to claim 1 or 2, wherein the compound having a salt of a sulfo group has an aromatic ring.
11. A water-based paint characterized by containing the virus infection inhibitor according to claim 1 or 2.
12. base material and
    A virus infection inhibiting product comprising a dried product of the virus infection inhibiting agent according to claim 1 or 2, which is contained on the surface of the base material.
13. A step of attaching the virus infection inhibitor according to claim 1 or claim 2 to the surface of the base material,
    A method for producing a product for preventing virus infection, comprising the step of drying the virus infection inhibitor attached to the surface of the base material to produce a dried product.