TW202348138A - Viral infection inhibitor, viral infection inhibiting member, and viral infection inhibiting paint - Google Patents

Abstract

The present invention provides a viral infection inhibitor capable of largely preventing whitening of a base material surface even when the viral infection inhibitor is contained in the base material and used. The viral infection inhibitor of the present invention is characterized by comprising a polymer compound that has at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, or a salt thereof and has a weight average molecular weight of 1000 or more, wherein the main chain of the polymer compound contains no nitrogen atoms. Therefore, the viral infection inhibitor can largely prevent whitening of a base material surface even when the viral infection inhibitor is contained in the base material and used, and a viral infection inhibiting member that has excellent viral infection inhibiting effects and is excellent in appearance can be configured.

Description

Viral infection inhibitor, virus infection inhibitory component and virus infection inhibitory paint

The present invention relates to a virus infection inhibitor, a virus infection inhibitory member and a virus infection inhibitory paint.

In recent years, in addition to the prevalence of seasonal influenza viruses, the novel coronavirus (COVID-19) has become a global pandemic.

In addition, the highly pathogenic avian influenza virus has mutated and been confirmed to be infected among humans. Furthermore, concerns have arisen about the SARS virus, which has a very high fatality rate, and human beings are increasingly worried about the virus.

In order to solve these problems, Patent Document 1 proposes an antiviral synthetic resin composition containing 0.5 parts by mass or more of a sulfonic acid-based surfactant with respect to 100 parts by mass of the synthetic resin. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2016-128395

[Problem to be solved by the invention]

However, the above-mentioned antiviral synthetic resin composition has a problem that when it is dispersed in a base material such as paint or synthetic resin and used, the surface of the base material becomes white.

The present invention provides a virus infection inhibitor that can substantially prevent whitening of the surface of the base material even when it is contained in a base material and used. [Technical means to solve the problem]

The viral infection inhibitor of the present invention is characterized by comprising a polymer compound having at least one amine group or a salt thereof selected from the group consisting of a primary amine group, a secondary amine group and a tertiary amine group, And the weight average molecular weight is more than 1000, and the main chain of the above-mentioned polymer compound does not contain nitrogen atoms.

The viral infection inhibitory member of the present invention is characterized by including a base material and the above-mentioned viral infection inhibitory agent contained in the base material. [Effects of the invention]

Since the virus infection inhibitor of the present invention has the above-mentioned structure, even when it is contained in a base material and used, whitening of the surface of the base material can be substantially prevented, and a virus having an excellent virus infection inhibitory effect and excellent appearance can be formed. Infection suppression components.

The viral infection inhibitor of the present invention includes a polymer compound having at least one amine functional group or a salt thereof selected from the group consisting of primary amine group, secondary amine group and tertiary amine group, and the weight average The molecular weight is above 1000, and the main chain of the above-mentioned polymer compound does not contain nitrogen atoms.

[Viral infection inhibitor] Viral infection inhibitors contain polymer compounds as active ingredients. In viral infection inhibitors, it has at least one amine functional group or its salt selected from the group consisting of primary amine group, secondary amine group and tertiary amine group, the weight average molecular weight is more than 1000 and the main chain does not contain nitrogen. The content of the atomic polymer compound in the active ingredient is preferably 50 mass% or more, more preferably 60 mass% or more, more preferably 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% Above, more preferably 95 mass% or more, more preferably 99 mass% or more, still more preferably 100 mass%.

In viral infection inhibitors, it has at least one amine functional group or its salt selected from the group consisting of primary amine group, secondary amine group and tertiary amine group, the weight average molecular weight is more than 1000 and the main chain does not contain nitrogen. The content of the atomic polymer compound is preferably 50 mass% or more, more preferably 60 mass% or more, more preferably 70 mass% or more, more preferably 80 mass% or more, more preferably 90 mass% or more, more preferably 95 mass% or more, more preferably 99 mass% or more, more preferably 100 mass%.

The polymer compound has at least one amine functional group or a salt of the amine functional group selected from the group consisting of primary amine group, secondary amine group and tertiary amine group. The polymer compound exhibits excellent virus infection inhibitory effect because it has at least one amine functional group or a salt of the amine functional group selected from the group consisting of primary amine group, secondary amine group and tertiary amine group, especially for those who do not have the virus. Envelope viruses have excellent virus infection inhibitory effects.

The amine functional group preferably contains a secondary amine group because the virus infection inhibitory effect of the virus infection inhibitor is improved, and even when the substrate is used containing the virus infection inhibitor, the surface of the substrate can be substantially prevented of whitening. Furthermore, in terms of having a virus infection inhibitory effect on both mantle viruses and non-mantle viruses, the amine functional group preferably contains a secondary amine group.

The amine functional group preferably forms a cyclic skeleton, and preferably forms an alicyclic cyclic skeleton. The reason is that the virus infection inhibitory effect of the virus infection inhibitor is improved, and it is easy to use the base material containing the virus infection inhibitor. In this case, the whitening of the surface of the substrate can also be largely prevented.

Furthermore, the primary amine group means a monovalent substituent represented by -NH ₂ . Secondary amine group means a divalent substituent (-NH-) produced by removing (taking away) a hydrogen atom from _-NH2 . The tertiary amine group means a trivalent substituent [≡N, formula (a)] produced by removing (taking away) two hydrogen atoms from _-NH2 . Among them, the amine functional group does not include the situation where the ketone group (>CO) is directly bonded to the nitrogen atom constituting the amine functional group.

The salt of the amine functional group is not particularly limited, but is preferably an acid addition salt. Examples of acids used as acid addition salts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, hydrobromic acid, maleic acid, malic acid, ascorbic acid, tartaric acid, lauric acid, stearic acid, and palmitic acid. Oleic acid, myristic acid, lauryl sulfate, linolenic acid, fumaric acid, preferably hydrochloride.

Furthermore, the virus infection inhibitory effect refers to the effect of losing or reducing the infectivity of the virus to cells or preventing the virus from proliferating in cells even if infected. As a method for confirming whether the virus is infective, for example, if it is a fiber product, ISO18184 or JIS L1922 can be cited, and if it is a plastic or non-porous surface product other than a fiber product, ISO21702 can be cited. Other examples include the plaque method and the erythrocyte agglutination titer (HAU) measurement method described in "Pharmaceutical Virology" (first edition published in April 1990).

The viral infection inhibitory effect of the viral infection inhibitor can be measured, for example, according to the following method. 3 parts by mass of a virus infection inhibitor and 97 parts by mass of an ultraviolet curable acrylic paint were mixed to prepare a virus infection inhibitor paint. Using a wire bar coater #8, apply the viral infection-inhibiting paint on the polyethylene film to a thickness of 18 μm to form a coating layer.

The coating layer is irradiated with ultraviolet light with a wavelength of 365 nm at 25°C until the cumulative light intensity reaches 500 mJ/cm ² to harden the ultraviolet curable acrylic paint to form a coating film with a thickness of 18 μm.

Cut out a flat square shape with a side of 5.0 cm from the coating film to prepare a test piece. The surface of the obtained test piece coating film was wiped with a flat square-shaped non-woven fabric with a side of 10 cm, and the non-woven fabric was moved back and forth 10 times to prepare a test coating film.

According to ISO21702, the antiviral test was conducted on the obtained test coating film. For the virus suspension after the reaction, calculate the virus infection titer (commonly used logarithmic value) (PFU/cm ² ) of the test coating through the plaque lysis method.

Except that it does not contain viral infection inhibitors, make a blank coating film according to the same method as above. Based on the blank coating film, calculate the virus infection titer (common logarithmic value) (PFU/cm ² ) according to the same method as above. .

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

Regarding the viral infection inhibitor, the antiviral activity value 10 minutes after the reaction in the antiviral test based on ISO21702 is preferably 0.6 or more, more preferably 1.0 or more, and more preferably 2.0 or more. Regarding the viral infection inhibitor, the antiviral activity value 24 hours after the reaction in the antiviral test based on ISO21702 is preferably 0.6 or more, more preferably 1.0 or more, and more preferably 2.0 or more. Regardless of the type of virus being evaluated, it is preferable that the antiviral activity value against at least one type of virus is 0.6 or more.

As a polymer compound having an amine functional group or a salt thereof, it has an amine functional group or a salt thereof in the side chain, and the main chain does not contain nitrogen atoms. The main chain of a polymer compound refers to the longest chain of the polymer compound. The length of the chain can be judged based on the number of atoms contained in the chain. The greater the number of atoms contained in the chain, the longer the chain is judged to be. The atoms contained in the main chain refer to the atoms that directly constitute the main chain. Therefore, for example, when an ethylene-based polymer constitutes the main chain, the main chain contains carbon atoms, but the hydrogen bonded to the carbon atoms is not included in the atoms directly constituting the main chain and is not included in the main chain.

Since the main chain of the polymer compound does not contain nitrogen atoms, it improves the interaction between the amine functional group of the polymer compound or its salt and the virus, improves the virus infection inhibitory effect of the virus infection inhibitor, and makes it easier for the substrate to contain viruses. When used as an infection inhibitor, whitening of the substrate surface can be largely prevented. The polymer compound only needs to contain no nitrogen atoms in the main chain. As long as the number of nitrogen atoms contained in the main chain of a polymer compound is 0. The atoms constituting the main chain only need to be atoms other than nitrogen atoms. Examples include carbon atoms, sulfur atoms, oxygen atoms, etc., preferably carbon atoms and sulfur atoms, preferably only carbon atoms, or carbon atoms and Sulfur atoms.

The polymer compound has an amine functional group or a salt thereof in the molecule. Examples of the polymer compound include polymers in which the side chain of a linear polymer contains an amine functional group or a salt thereof.

Among polymers in which the side chain of the linear polymer contains an amine functional group or a salt thereof, the linear polymer is not particularly limited. For example, vinyl polymers and polyesters are preferred, and vinyl polymers are more preferred.

Examples of polymers containing amine functional groups or salts thereof in the side chains of linear polymers include polymers containing "amine functional group-containing monomers containing amine functional groups or salts thereof as monomer units".

The amine functional group-containing monomer containing an amine functional group or a salt thereof is not particularly limited, and examples thereof include: 2-vinylpyridine, 4-vinylpyridine, vinylimidazole, (meth)acrylic acid dimethylamine Ethyl ester, diethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, N-(aminoalkyl)acrylamide, N-(aminoalkyl) Methacrylamide, monomer obtained by reacting glycidyl (meth)acrylate with ammonia or dimethylamine, etc., allylamine, diallylamine, methyldiallylamine, 1,2,2,6,6-Pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate or their amines Salts of functional groups, etc. Furthermore, the amine functional group-containing monomer containing an amine functional group or a salt thereof may be used alone or in combination of two or more types.

In addition, the polymer compound is preferably a polymer compound containing at least one repeating unit represented by the following formulas (1) to (6), because the virus infection inhibitor has an excellent virus infection inhibitory effect. Furthermore, in the present invention, n represents a repeating unit and is a natural number of 2 or more. n represents a repeating unit, and it goes without saying that n used in each general formula does not need to be the same.

The polymer containing an amine functional group-containing monomer as a monomer unit may be a homopolymer of an amine functional group-containing monomer, or a copolymer of an amine functional group-containing monomer and a monomer copolymerizable therewith.

The monomer copolymerizable with the amine functional group-containing monomer is not particularly limited, and examples thereof include: alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butyl Alkene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene, acrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, vinyltoluene, etc. Furthermore, the monomer copolymerizable with the amine functional group-containing monomer may be used alone or in combination of two or more.

The polymer compound preferably has a carboxyl group or a salt thereof in the molecule because the virus infection inhibitory effect of the virus infection inhibitor is improved.

The salt of the carboxyl group is not particularly limited, and examples thereof include potassium salt (-COOK), sodium salt (-COONa), calcium salt [(-COO ^- ) ₂ Ca ²⁺ ], and ammonium salt (-COO ^- NH ₄ ⁺ ), magnesium salt [(-COO ^- ) ₂ Mg ²⁺ ], barium salt [(-COO ^- ) ₂ Ba ²⁺ ], etc.

Examples of the polymer compound containing a carboxyl group include polymers in which the side chain of a linear polymer contains an amine functional group or a salt thereof, and a carboxyl group or a salt thereof.

Examples of polymers containing amine functional groups or salts thereof and carboxyl groups or salts thereof in the side chains of linear polymers include polymers containing the following monomers as monomer units: "containing amine functional groups or "Amine functional group-containing monomers of salts thereof", and "Carboxyl group-containing monomers containing carboxyl groups or salts thereof". In addition, the amine functional group-containing monomer containing an amine functional group or a salt thereof is the same as described above, so its description is omitted.

The carboxyl group-containing monomer containing a carboxyl group or a salt thereof is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, and amber. Acid mono(meth)acryloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, nicconic acid Acid, carboxybetaine type monomer or salt thereof, etc. are preferably oxalic acid. In addition, the carboxyl group-containing monomer may be used alone or in combination of two or more types.

Furthermore, the polymer compound containing an amine functional group or a salt thereof, and a carboxyl group preferably contains a repeating unit represented by the following formula (7), because the virus infection inhibitor has an excellent virus infection inhibitory effect.

Polymer compounds can be polymerized using general polymerization methods. For example, a monomer composition containing "an amine functional group-containing monomer containing an amine functional group or a salt thereof, and optionally a carboxyl group-containing monomer containing a carboxyl group or a salt thereof and other monomers" can be used. Polymerize in the presence of a general free radical polymerization initiator to obtain a polymer compound. In addition, it can also be polymerized by polymerizing a monomer composition including "an amine functional group-containing monomer containing an amine functional group or a salt thereof, and a hydroxyl group-containing monomer" in the presence of a general-purpose radical polymerization initiator. Obtain polymer compounds. Furthermore, examples of the radical polymerization initiator include: 1-hydroxycyclohexan-1-ylphenyl ketone, t-hexyl peroxypivalate, benzoyl peroxide, Thermal cracking free radical polymerization initiators such as azobisisobutyronitrile, etc. In addition, polymers with amine functional groups can also be synthesized through a condensation reaction or transesterification reaction between a polymer having a hydroxyl group and a monomer containing an amine functional group.

The nitrogen atom content rate of the polymer compound is preferably 0.1% or more, more preferably 0.5% or more. The nitrogen atom content of the polymer compound is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, more preferably 35% or less, still more preferably 30% or less. If the nitrogen atom content of the polymer compound is within the above range, whitening of the surface of the base material can be substantially prevented even when the base material is used containing a virus infection inhibitor.

The nitrogen atom content rate (%) of a polymer compound refers to the percentage of the nitrogen atomic weight relative to the total atomic weight of the repeating units constituting the polymer compound.

For example, in a polymer compound having a repeating unit represented by the following formula (8), the nitrogen atom content is calculated by the following formula. Among them, M ₁ and M ₂ mean monomer units. In the present invention, n, m and p represent repeating units, and are natural numbers of 2 or more.

Nitrogen atom content rate of polymer compounds (%) = 100 × {(Total nitrogen atomic weight contained in M ₁ ) × m + (Total nitrogen atomic weight contained in M ₂ ) × n} / { (Total atomic weight of M ₁ ) × m+(total atomic weight of M ₂ )×n}

In the present invention, the structural formula represented by formula (8) means a random copolymer, alternating copolymer or block copolymer of monomer unit M ₁ and monomer unit M ₂ . As the polymerization form of the polymer compound contained in the virus infection inhibitor, random copolymers are preferred because the charge states in the polymer chain are evenly distributed and the surface of the polymer compound becomes a suitable charge state, thereby preventing viral infection. The inhibitory effect on viral infection is improved.

The weight average molecular weight of the polymer compound is preferably 1,000 or more, more preferably 2,000 or more, and more preferably 3,000 or more. If the weight average molecular weight of the polymer compound is 1,000 or more, the polymer compound can interact with viruses at multiple points, thereby improving the virus infection inhibitory effect of the virus infection inhibitory component.

The weight average molecular weight of the polymer compound is preferably 1,000,000 or less, more preferably 900,000 or less, more preferably 800,000 or less, still more preferably 600,000 or less. If the weight average molecular weight of the polymer compound is 1,000,000 or less, the whitening of the surface of the base material containing the virus infection inhibitor can be reduced, the virus infection inhibitory effect can be more effectively expressed without damaging the appearance of the base material, and the agglutination of the virus infection inhibitory compound can be achieved As a result, the virus infection inhibitory compound and the virus easily interact with each other, and the virus infection inhibitory effect of the virus infection inhibitor is improved.

When the polymer compound is a mixture of a plurality of polymers, the weight average molecular weight of the polymer compound is the weight average molecular weight of the entire polymer compound.

Furthermore, in the present invention, the weight average molecular weight of the polymer compound is a polystyrene-converted value measured by GPC (gel permeation chromatography) method.

For example, the measurement can be performed with the following measurement device and measurement conditions. Gel permeation chromatography: Manufactured by Waters Co., Ltd. Trade name "2690 Separations Model" Pipe string: Manufactured by Showa Denko Co., Ltd. Trade name "GPC KF-806L" Detector: Differential Refractometer Sample flow: 1 mL/min Tube string temperature: 40℃ Eluent: THF

The pH of the 5% by mass aqueous solution of the polymer compound at 25°C is preferably 4 or less. The pH of the 5% by mass aqueous solution of the polymer compound at 25°C is preferably 9 or more. If the pH of a 5 mass% aqueous solution of a polymer compound is below 4 at 25°C, the surface of the polymer compound will reach an appropriate charge state, or the protons on the surface of the virus will increase, causing the electrostatic interaction with the virus infection inhibitor to change. Large, thereby improving the viral infection inhibitory effect of the viral infection inhibitor. If the pH of a 5% by mass aqueous solution of a polymer compound at 25°C is below 4 or above 10, the surface of the polymer compound reaches an appropriate charge state, or the surface of the virus is anionized, causing static electricity with the virus infection inhibitor. The interaction becomes larger, thereby increasing the infection inhibitory effect of the viral infection inhibitor. Furthermore, the pH of a 5 mass % aqueous solution of a polymer compound at 25°C refers to the pH value at 25°C of a mixed solution in which 5 g of the polymer compound is added to 95 g of purified water and uniformly mixed. Regarding the mixed liquid, all the polymer compounds may be dissolved in purified water or a part of the polymer compounds may be dissolved in purified water to form a saturated aqueous solution.

The pKa1 of the polymer compound at 25°C is preferably 8 or more, more preferably 8.5 or more. If the pKa1 of the polymer compound at 25°C is above 8, then under the interaction between the polymer compound and the virus, the surface of the polymer compound reaches an appropriate charge state, effectively capturing the virus, and the virus infection inhibitor has the virus infection inhibitory effect. Improvement, and even when the base material is used containing a virus infection inhibitor, whitening of the surface of the base material can be substantially prevented. The pKa1 of the polymer compound at 25°C is preferably 12 or less, more preferably 11 or less, still more preferably 10 or less. Here, when the electrolyte BH ⁺ is dissociated into B and H ⁺ and the dissociation equilibrium formula (b) is obtained, the acid dissociation constant Ka is defined by the formula (c), and pKa is the common logarithm of the inverse of the acid dissociation constant Ka ( d) to define. The polymer compound in this specification is synthesized by polymerizing an amine functional group-containing monomer containing an amine functional group or a salt thereof, or by condensation reaction or transesterification of a polymer having a hydroxyl group and an amine functional group-containing monomer. .

pKa1 in the present invention is defined as the acid dissociation constant of the conjugate acid of the amine in the monomer containing an amine functional group or its salt that becomes a constituent element of the polymer compound. In addition, in the present invention, "pKa1 of the monomer containing an amine functional group or a salt thereof that becomes a constituent element of the polymer compound" is set to "pKa1 of the polymer compound". When the monomer containing an amine functional group or its salt that becomes a constituent element of the polymer compound is a polyamine, the conjugate acid of the polyamine is released in multiple stages, and pKa1 refers to the pKa calculated based on the free constant of the first stage. .

The pKa1 of a polymer compound at 25°C refers to the value measured by titration. Specifically, the hydrochloride and sodium hydroxide of the amine functional group-containing monomer that are the constituent elements of the polymer compound are used, the titration is performed at 25°C, and the half-equivalent point (half of the amount of "half the amount after neutralization is added dropwise") is measured. ” time point) the pH at 25°C, from which pKa1 can be calculated. In the case where the amine functional group-containing monomer is a free amine, the pKa1 can be determined using the above method after conversion to the hydrochloride. An example of a method for converting a free amine into a hydrochloride salt is to mix the amine functional group-containing monomer with a 1 mol % hydrochloric acid aqueous solution, and then remove all the amines contained in the amine functional group-containing monomer. The base is converted into hydrochloride, and then the hydrochloric acid and water are removed by common methods such as freeze-drying.

The polymer compound preferably does not contain aromatic rings in the molecule. If the polymer compound does not contain an aromatic ring, whitening of the surface of the base material can be substantially prevented even when the base material is used containing a virus infection inhibitor. Furthermore, if the polymer compound does not contain an aromatic ring, the volume of the polymer compound is reduced, so the molecular structure part containing the amine functional group can interact with the virus efficiently and exert an excellent virus infection inhibitory effect.

In addition to monocyclic aromatic rings, aromatic rings also include condensed aromatic rings in which monocyclic aromatic rings are compounded and condensed. The aromatic ring is not particularly limited, and examples thereof include benzene ring, naphthalene ring, anthracene ring, biphenyl, phenoxyphenyl group, and the like. In the aromatic ring, any one or more hydrogen atoms in the aromatic ring and the condensed aromatic ring are removed (taken away) and bonded to other atoms through covalent bonds.

The polymer compound is preferably formed in the form of particles because it can be uniformly dispersed on the surface of the base material and can provide an excellent virus infection inhibitory effect to the base material. The D90 particle size of the polymer compound is preferably 1 μm or more, more preferably 2 μm or more, more preferably 2.5 μm or more, more preferably 3 μm or more, more preferably 3.5 μm or more. The D90 particle size of the polymer compound is preferably 50 μm or less, more preferably 25 μm or less, more preferably 22 μm or less, more preferably 20 μm or less, more preferably 18 μm or less, more preferably 16 μm or less, more preferably It is preferably 14 μm or less, more preferably 12 μm or less. If the D90 particle size is 1 μm or more, the overall surface area of the polymer compound becomes smaller, the agglutination of the virus infection inhibitor decreases, and the polymer compound and the virus easily interact with each other, and the virus infection inhibitory effect of the virus infection inhibitory component increases. , and even when the base material is used containing a virus infection inhibitor, whitening of the surface of the base material can be substantially prevented. If the D90 particle size is 50 μm or less, it can prevent the aggregation of the virus infection inhibitor and increase the surface area so that it can easily come into contact with the virus, thereby improving the virus infection inhibitory effect of the virus infection inhibitory member, and making it easy to make the base material contain the virus infection inhibitor When used as an agent, it can also generally prevent the whitening of the surface of the substrate.

As described below, the D90 particle size of a polymer compound is the particle size at which frequency accumulation (accumulation starting from particles with small particle sizes) reaches 90% (90% cumulative particle size) of the volume-based particle size distribution obtained by the laser scattering method. ). When the polymer compound contains a plurality of polymer compounds, the D90 particle diameter of the polymer compound is a value measured based on the entire polymer compound.

Viral infection inhibitors can also be attached (carried) to the surface of base particles for use. By pre-attaching the virus infection inhibitor to the surface of the base particles, the virus infection inhibitor can be more uniformly dispersed in the base material, and the whitening of the base material can be prevented more effectively. Furthermore, the surface area of the virus infection inhibitor can be increased, the contact between the virus infection inhibitor and the virus can be fully ensured, and the virus infection inhibitory effect of the virus infection inhibitor can be fully exerted.

The base particles on which the viral infection inhibitor is attached to the surface are not particularly limited as long as they do not hinder the viral infection inhibitory effect of the viral infection inhibitor. Base particles include resin particles and inorganic particles. The base particles may be used alone or in combination of two or more types.

Examples of the synthetic resin constituting the resin particles include styrene resin, acrylic resin, urethane resin, vinyl chloride resin, ABS resin; styrene-butadiene rubber (SBR), nitrile- Synthetic rubber such as butadiene rubber (NBR), styrenic resin and acrylic resin are preferred.

The styrenic resin is not particularly limited, and examples thereof include benzene, such as styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, chlorostyrene, and bromostyrene. Homopolymers or copolymers of vinyl monomers as monomer units; copolymers including styrene monomers and one or more vinyl monomers copolymerizable with the styrene monomers as monomer units Things etc.

Examples of vinyl monomers copolymerizable with styrene-based monomers include acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, and acrylates (methyl acrylate, ethyl acrylate, butyl acrylate, etc.) , acrylic monomers such as methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.), maleic anhydride, acrylamide, etc.

The acrylic resin is not particularly limited, and examples thereof include acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. Homopolymers or copolymers of monomer units; copolymers including acrylic monomers and one or more vinyl monomers copolymerizable with the acrylic monomers as monomer units. Furthermore, (meth)acrylate means acrylate or methacrylate.

Examples of the vinyl monomer copolymerizable with the acrylic monomer include acrylonitrile, methacrylonitrile, maleic anhydride, acrylamide, and the like.

The inorganic material constituting the inorganic particles is not particularly limited, and examples thereof include zeolite, hydrotalcite, calcium carbonate, calcium citrate, magnesium carbonate, and magnesium hydroxide.

The synthetic resin constituting the resin particles preferably contains an aromatic ring. The aromatic ring can attract the hydrophobic part of the polymer compound attached to the surface of the resin particles, and play a role in aligning the amine functional groups and carboxyl groups outward, thereby more effectively exerting the virus infection inhibitory effect of the virus infection inhibitor.

The aromatic ring can be a monocyclic aromatic ring, or it can be formed by compounding and condensing monocyclic aromatic rings (condensed aromatic ring). The aromatic ring is not particularly limited, and examples thereof include benzene ring, naphthalene ring, anthracene ring, biphenyl, phenoxyphenyl group, and the like. In the aromatic ring, any one or more hydrogen atoms in the aromatic ring and the condensed aromatic ring are removed (taken away) and bonded to other atoms through covalent bonds.

The adhesion amount of the polymer compound to the resin particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and more preferably 10 parts by mass or more based on 100 parts by mass of the resin particles. If the adhesion amount of the polymer compound is 1 part by mass or more, the virus infection inhibitor can be uniformly attached to the surface of the resin particles, and the virus infection inhibitory effect of the virus infection inhibitor can be more effectively exerted.

The adhesion amount of the polymer compound to the resin particles is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, more preferably 600 parts by mass or less, more preferably 400 parts by mass or less based on 100 parts by mass of the resin particles. If the adhesion amount of the polymer compound is 1000 parts by mass or less, the virus infection inhibitors will not be bonded to each other, the virus infection inhibitors will be efficiently arranged on the surface of the resin particles, and the virus infection inhibitory effect will be improved.

The method of adhering the viral infection inhibitor to the surface of the resin particles is not particularly limited. For example, it can be attached by the adhesion force of the viral infection inhibitor, or an adhesive resin can be used to adhere the viral infection inhibitor to the surface of the resin particles. Preferably The polymer compound adheres to the surface of the resin particles through the adhesive force of the polymer compound itself. The reason is that it can effectively exert the virus infection inhibitory effect of the virus infection inhibitor.

Viral infection inhibitors have viral infection inhibitory effects on various viruses due to the action of polymer compounds, and exhibit excellent viral infection inhibitory effects on both mantle viruses and non-mantle viruses.

Examples of the mantle virus include influenza virus (such as type A, type B, etc.), rubella virus, Ebola virus, coronavirus (such as SARS virus, novel coronavirus (SARS-CoV-2)), measles virus, Varicella-zoster virus, herpes simplex virus, mumps virus, arthropod-borne virus, RS virus, hepatitis virus (such as hepatitis B virus, hepatitis C virus, etc.), yellow fever virus, HIV, rabies Viruses, hantavirus, dengue virus, Nipah virus, Lisa virus, etc.

Examples of non-enveloped viruses include: feline calicivirus, adenovirus, norovirus, rotavirus, human papillomavirus, poliovirus, enterovirus, coxsackievirus, human parvovirus, cerebral parvovirus, Myocarditis virus, rhinovirus, etc.

The viral infection inhibitor can be included in the following base material to constitute a viral infection inhibitory member, and can provide an excellent viral infection inhibitory effect to the base material without causing almost any whitening of the surface of the base material.

The base material containing the virus infection inhibitor is not particularly limited as long as it is intended to provide a virus infection inhibitory effect. Examples thereof include paints, synthetic resin molded articles, wallpapers, decorative boards, flooring materials, fiber products (fabric, Non-woven fabrics, knitted fabrics), interior products and interior materials for vehicles (such as cars, airplanes, ships, etc.) (seats, child seats and foams constituting them, etc.), kitchen supplies, baby products, construction Interior materials, etc.

Building interior materials are not particularly limited, and examples thereof include: floor materials, wallpaper, ceiling materials, paint, door handles, switches, switch covers, wax, etc.

Vehicle interior supplies and vehicle interior materials are not particularly limited. Examples include: seats, child seats, seat belts, car floor mats, seat covers, doors, ceiling materials, carpets, door trims, and instruments. Panels, consoles, passenger seat storage boxes, lifting rings, armrests, etc.

The content of the polymer compound in the base material is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass or more based on 100 parts by mass of the base material. The content of the polymer compound in the base material is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 7 parts by mass or less based on 100 parts by mass of the base material. If the content of the polymer compound in the base material is 0.1 parts by mass or more, the virus infection inhibitory effect of the virus infection inhibitory member can be improved. If the content of the polymer compound in the base material is 30 parts by mass or less, the physical properties of the base material will not be affected. The polymer compound will not agglomerate and can easily be dispersed uniformly, thereby improving the virus infection inhibitory effect.

The virus infection inhibitor is included in the paint to constitute the virus infection inhibiting paint. The coating film formed by the viral infection-inhibiting paint can exert an excellent virus infection-inhibiting effect and substantially prevent the surface of the coating film from whitening, forming a coating film with excellent appearance.

As the paint, a conventionally known paint is used. The coating improves the dispersibility of the virus infection inhibitor and can form a coating film with excellent virus infection inhibition effect. Both hydrophobic paint and hydrophilic paint can be used. The hydrophobic paint is not particularly limited, and examples thereof include oily paints (such as mixed paints, oily varnishes, etc.), cellulose paints, and synthetic resin paints. Coatings also include photocurable coatings that are polymerized by irradiation with ultraviolet rays and other radiation to produce a binder component. The water-based paint is not particularly limited, and examples thereof include water-based urethane paint, water-based polysilicone paint, water-based fluorine paint, and water-based inorganic paint.

To adjust the viscosity, the coating may also contain solvents. As the solvent, an organic solvent is preferred because the dispersibility of the virus infection inhibitor in the paint is improved. The organic solvent is not particularly limited, and examples thereof include toluene, xylene, methyl ethyl ketone, acetone, ethyl acetate, benzene, isopropyl alcohol, and the like. In addition, a solvent may be used individually or in combination of 2 or more types.

The content of the polymer compound in the virus infection inhibiting paint is preferably 1% by mass or more, more preferably 2% by mass or more. The content of the polymer compound in the virus infection-inhibiting paint is preferably 10 mass% or less, more preferably 7 mass% or less, and more preferably 5 mass% or less. If the content of the polymer compound is 1% by mass or more, the coating film formed of the virus infection-inhibiting paint exhibits an excellent virus infection-inhibiting effect. If the content of the polymer compound is 10% by mass or less, the polymer compound will not agglomerate and is easily dispersed uniformly, thereby improving the virus infection inhibitory effect and not easily affecting the physical properties of the base material, so it is preferable.

Furthermore, the coating may also contain additives such as pigments, plasticizers, hardeners, extenders, fillers, anti-aging agents, tackifiers, and surfactants within the range that does not impair its physical properties.

An example of a method for containing a virus infection inhibitor in the coating material is a method of supplying the virus infection inhibitor and the coating material to a dispersing device and mixing them uniformly. Examples of the dispersing device include a high-speed grinder, a ball mill, and a sand mill. [Example]

Hereinafter, the present invention will be described more specifically using examples, but the present invention is not limited thereto.

Prepare polymer compounds 1 to 16.

[Polymer compounds] ・Polymer compound 1 [polymer compound having a repeating unit represented by formula (1)] A polymer compound sold under the trade name "PAA-15C" by Nittobo Medical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 1.

・Polymer compound 2 [having a repeating unit represented by formula (9)] 1 part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, degree of polymerization: 300) was added to 49 parts by weight of dimethylsulfoxide (DMSO) and dissolved (concentration: 2 mass%). Subsequently, 8.0 parts by weight of L-tyrosine methyl ester and 6 parts by weight of tetratertiary butyl dilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13 mass%) were added, and the mixture was stirred at 30° C. for 6 hours. Carry out transesterification reaction. Thereafter, it was reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and then dried, thereby obtaining a powder of polymer compound 2. In formula (9), m:n=86:14.

・Polymer compound 3 [having a repeating unit represented by formula (10)] A polymer compound manufactured by Nittobo Medical Co., Ltd. and sold under the trade name "PAS-21CL" was freeze-dried to obtain a powder of polymer compound 3.

・Polymer compound 4 [having a repeating unit represented by formula (3)] The polymer compound sold under the trade name "PAS-21" by Nittobo Medical Co., Ltd. was freeze-dried to obtain the powder of polymer compound 4.

・Polymer compound 5 [having a repeating unit represented by formula (11)] The polymer compound sold by Nittobo Medical under the trade name "PAA-D19-HCl" was freeze-dried to obtain the powder of polymer compound 5. m:n=1:9.

・Polymer compound 6 [having a repeating unit represented by formula (12)] A polymer compound sold under the trade name "PAS-92" by Nittobo Medical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 6.

・Polymer compound 7 [having a repeating unit represented by formula (13)] A polymer compound sold under the trade name "PAS-410C" by Nittobo Medical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 7. m:n=1:1.

・Polymer compound 8 [having a repeating unit represented by formula (14)] A polymer compound sold under the trade name "PAS-411C" by Nittobo Medical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 8. m:n=3:1.

・Polymer compound 9 [having a repeating unit represented by formula (15)] 1 part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, degree of polymerization: 300) was added to 49 parts by weight of dimethylsulfoxide (DMSO) and dissolved (concentration: 2 mass%). Subsequently, 3.0 parts by mass of N,N-dimethylglycinate methyl ester and 6 parts by mass of tetrakis-tert-butyldilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13 mass%) were added, and the mixture was stirred at 30°C. 6 hours, thereby carrying out transesterification reaction. Thereafter, the solution was precipitated in tetrahydrofuran, washed with tetrahydrofuran, and dried to obtain a powder of polymer compound 9. m:n=86:14.

・Polymer compound 10 [having a repeating unit represented by formula (16)] A polymer compound sold under the trade name "PAS-M-1" by Nittobo Medical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 10.

・Polymer compound 11 [having a repeating unit represented by formula (17)] A polymer compound sold under the trade name "Polyhexamethylene biguanide hydrochloride" by Dafeng Yuelong Chemical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 12. In formula (17), x is a natural number greater than 2.

・Polymer compound 12 Use a polymer compound (liquid) sold by Nippon Shokubai Co., Ltd. under the trade name "SP-200". Polymer compound 12 contains nitrogen atoms in the main chain.

・Polymer compound 13 A polymer compound sold under the trade name "P-1000" by Nippon Shokubai Co., Ltd. was freeze-dried and then thawed to obtain liquid polymer compound 13. Polymer compound 13 contains nitrogen atoms in the main chain.

・Polymer compound 14 [having a repeating unit represented by formula (18)] A polymer compound sold under the trade name "PAS-H-5L" by Nittobo Medical Co., Ltd. was freeze-dried to obtain a powder of polymer compound 14.

・Polymer compound 15 [having a repeating unit represented by formula (19)] Add 1 part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, degree of polymerization: 300) to 49 parts by weight of dimethylstyrene (DMSO) and dissolve it (concentration: 2 mass%) . Subsequently, 1.7 parts by weight of L-pyroglutamate methyl ester and 6 parts by weight of tetrakis-tert-butyldilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13 mass%) were added, and the mixture was stirred at 30° C. for 6 hours. This undergoes a transesterification reaction. Thereafter, the solution was precipitated in tetrahydrofuran, washed with tetrahydrofuran, and then dried to obtain a powder of polymer compound 15. m:n=81:19.

・Polymer compound 16 [having a repeating unit represented by formula (20)] Add 1 part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, degree of polymerization: 300) to 49 parts by weight of dimethylstyrene (DMSO) and dissolve it (concentration: 2 mass%) . Subsequently, 3.3 parts by weight of N-ethyl-L-alanine methyl ester and 6 parts by weight of tetrakis-tert-butyldilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were added, and the mixture was stirred at 30°C. 6 hours, thereby carrying out transesterification reaction. Thereafter, the solution was precipitated in tetrahydrofuran, washed with tetrahydrofuran, and then dried to obtain a powder of polymer compound 16. m:n=85:15.

In the structural formula shown above, m, n and p represent repeating units, and they are all natural numbers above 2. In formula (17), x is a natural number greater than 2.

Among the structural formulas shown above, the structural formula shown in formula (8) means a random copolymer, alternating copolymer or block copolymer of monomer unit M ₁ and monomer unit M ₂ .

[Preparation of polymer compound particles] After coarsely pulverizing the polymer compound using a roller press device (trade name "Model 150" manufactured by Seishin Enterprise Co., Ltd.) under operating conditions of rotation speed 25 rpm and extrusion force 25 t, a jet mill device (trade name "Model 150" manufactured by Nisshin Engineering Co., Ltd. SJ-500"), pulverizes to obtain polymer compound particles under operating conditions of a polymer compound supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa. Table 1 shows the D90 particle diameter of the polymer compound particles.

Table 1 shows the nitrogen atom content, weight average molecular weight Mw, pH of a 5% by mass aqueous solution at 25°C, and pKa1 at 25°C for the polymer compounds used in the Examples and Comparative Examples. Furthermore, in Table 1, "pH of 5 mass% aqueous solution at 25°C" and "pKa1 at 25°C" are abbreviated as "pKa1" and "pKa1" respectively.

(Examples 1 to 10 and Comparative Examples 1 to 6) A viral infection inhibitor containing 5 parts by mass of the "polymer compound particles shown in Table 1" produced according to the above method, and 95 parts by mass of ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by COATTEC Corporation) Mix to make virus infection inhibiting paint. Using wire bar applicator #8, apply the viral infection-inhibiting paint on the polyethylene film to a thickness of 18 μm to form a coating layer.

Using a UV delivery device ("ECS301G1" manufactured by EYE GRAPHICS), the coating layer is irradiated with ultraviolet rays of wavelength 365 nm at 25°C until the cumulative light intensity reaches 500 mJ/cm ² to harden the ultraviolet curable acrylic paint to form a thickness It is an 18 μm coating.

The antiviral properties and whitening properties of the viral infection inhibitors were measured according to the following method, and the results are shown in Table 1.

[Antiviral properties] Using the coating film obtained above, antiviral tests were conducted using feline calicivirus (non-mantle virus) and influenza virus (mantle virus) according to the following methods.

(Antiviral test) Cut out a flat square shape with a side of 5.0 cm from the coating film to prepare a test piece.

The surface of the obtained test piece coating film was wiped back and forth 10 times with a flat square non-woven fabric (trade name "Kimwipe S-200" manufactured by NIPPON PAPER CRECIA Co., Ltd.) with a side of 10 cm, and a test coating film was prepared.

The obtained test coating was subjected to an antiviral test against feline calicivirus and influenza virus in accordance with ISO21702 (test time: 24 hours). For the virus suspension after the reaction, the virus infection titer of the test coating was calculated by the plaque lysis method.

Except that it does not contain viral infection inhibitors, make a blank coating film according to the same method as above. Based on the blank coating film, calculate the viral infection titer (common logarithmic value) (PFU/cm ² ) according to the same method as above. . The virus infection titer (commonly used logarithmic value) of the blank coating film is 6.5 PFU/cm ² .

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

[Albinism] The whitening property evaluation was carried out in accordance with JIS A 1454 Polymer Flooring Test Method - Contamination Resistance Test. In a test room with a temperature of 23°C and a humidity of 50%, drop 2 ml of purified water onto the surface of the test coating, cover it with a watch glass and let it sit for 24 hours. Thereafter, the purified water was removed with household neutral detergent, the surface was wiped with industrial alcohol, and left to stand in the laboratory for 1 hour. The haze of the coating film was evaluated in accordance with JIS K 7361. Regarding the haze, the haze value (%) was measured using a haze meter (trade name "HM-150" manufactured by Murakami Color Technology Research Institute Co., Ltd.) at a room temperature of 25°C and a relative humidity of 40%. The greater the haze value, the greater the whitening degree of the coating surface.

[Table 1] Nitrogen atoms in the main chain Amine functionality Nitrogen atom content rate (%) weight average molecular weight pKa1 pH D90 particle size (μm) Antiviral activity value Albinism (%) feline calicivirus flu virus Example 1 Polymer compound 1 without primary amine group 25 15000 9.5 11～12 9～11 4.1 0.6 7.3 2 Polymer compound 2 without primary amine group 2 20000 9.1 9～11 9～11 4.1 0.6 4.7 3 Polymer compound 3 without Secondary amine hydrochloride 10 50000 9.3 2～3 11 4.5 4.6 4.2 4 Polymer compounds 4 without secondary amine group 14 5000 9.3 11～12 10 4.5 4.5 3.9 5 Polymer compounds 5 without Primary amine hydrochloride Secondary amine hydrochloride 11 40000 9.3～9.5 2～3 9 4.6 4.6 4.5 6 Polymer compound 6 without Secondary amine hydrochloride 7 5000 9.3 1～2 10 4.5 4.6 3.8 7 Polymer Compound 7 without Secondary amine hydrochloride 6 10000~ 1000000 9.3 1～2 11 4.6 4.6 4.0 8 Polymer compounds 8 without Secondary amine hydrochloride 8 10000～1000000 9.3 1 11 4.6 4.6 3.9 9 Polymer Compound 9 without Tertiary amine group 3 18000 9.9 10～11 9 4.2 0.9 4.5 10 Polymer compounds 10 without Tertiary amine hydrochloride 9 20000 8.0 2～3 10 3.4 0.8 4.5 Comparative example 1 Polymer compounds 11 have Secondary amine secondary amine hydrochloride 18～39 2300～3100 - 7～8 11 4.7 1.6 37.0 2 Polymer compounds 12 have Primary amine Secondary amine Tertiary amine 33 10000 8.0 10～12 - 4.4 0.8 40.0 3 Polymer compounds 13 have 33 70000 8.0 10～12 - 4.4 0.8 39.0 4 Polymer compounds 14 without Quaternary ammonium salt 9 30000 - 3～4 10 0.7 0.8 4.6 5 Polymer compounds 15 without amide 4 20000 - 4～6 11 0.6 0.9 18.0 6 Polymer compounds 16 without amide 3 18000 - 4～6 11 0.6 0.9 21.0 [Industrial availability]

The virus infection inhibitor of the present invention can be used even if it is contained in base materials such as coating films, wallpapers, decorative boards, flooring materials, fiber products, interior products and interior materials for vehicles, kitchen products, baby products, and building interior materials. In this case, whitening of the surface of the base material can be substantially prevented, and a virus infection-inhibiting member having excellent virus infection-inhibiting effect and excellent appearance can be constructed.

(Cross-reference of related applications) This application claims priority based on Japanese Patent Application No. 2022-049777 filed on March 25, 2022, the contents of which are incorporated into this specification in its entirety by reference.

without

without

Claims (10)

A viral infection inhibitor, characterized by: comprising a polymer compound having at least one amine functional group or a salt thereof selected from the group consisting of a primary amine group, a secondary amine group and a tertiary amine group, And the weight average molecular weight is more than 1000, and the main chain of the above-mentioned polymer compound does not contain nitrogen atoms. Such as the viral infection inhibitor of claim 1, wherein the nitrogen atom content of the above-mentioned polymer compound is 0.1 to 50%. The viral infection inhibitor of claim 1 or 2, wherein the above-mentioned amine functional group includes a secondary amine group. The viral infection inhibitor according to any one of claims 1 to 3, wherein the weight average molecular weight of the above-mentioned polymer compound is 1,000 to 1,000,000. The viral infection inhibitor according to any one of claims 1 to 4, wherein the above-mentioned polymer compound contains a carboxyl group or a salt thereof. The viral infection inhibitor according to any one of claims 1 to 5, wherein the pH of the 5% by mass aqueous solution of the above-mentioned polymer compound at 25°C is 4 or less or 9 or more. The viral infection inhibitor according to any one of claims 1 to 6, wherein the pKa1 of the above-mentioned polymer compound is 8 or more. The viral infection inhibitor according to any one of claims 1 to 7, wherein the above-mentioned amine functional groups form a cyclic skeleton. A virus infection inhibitory member, characterized by comprising a base material and the virus infection inhibitory agent contained in any one of claims 1 to 8 contained in the base material. A virus infection-inhibiting coating, characterized in that it includes a coating and the viral infection inhibitor contained in any one of claims 1 to 8 contained in the coating.