Virus infection inhibitor, virus infection inhibitor material, and virus infection inhibitor paint

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

[Technical Field]

[0001] The present invention relates to a virus infection inhibitor, a virus infection inhibitor member, and a virus infection inhibitor paint. [Background technology]

[0002] In recent years, in addition to seasonal influenza virus epidemics, the novel coronavirus (COVID-19) has become a global pandemic.

[0003] Furthermore, highly pathogenic avian influenza viruses have mutated and been confirmed to infect humans, and there are also concerns about the SARS virus, which has an extremely high mortality rate, so anxiety about viruses is only increasing.

[0004] To address these problems, Patent Document 1 proposes an antiviral synthetic resin composition containing 0.5 parts by mass or more of a sulfonic acid surfactant per 100 parts by mass of synthetic resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-128395 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the antiviral synthetic resin composition has a problem in that when dispersed in a substrate such as a paint or synthetic resin, the surface of the substrate becomes white.

[0007] The present invention provides a virus infection inhibitor that can generally prevent whitening of the surface of a substrate even when the agent is contained in the substrate. [Means for solving the problem]

[0008] The viral infection inhibitor of the present invention comprises a polymer compound having at least one amino group selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups, or a salt thereof, and having a weight-average molecular weight of 1,000 or more, and is characterized in that the main chain of the polymer compound does not contain a nitrogen atom.

[0009] The viral infection-blocking material of the present invention is characterized by comprising a substrate and the viral infection-blocking agent according to any one of claims 1 to 7 contained in the substrate. [Effects of the Invention]

[0010] Because the virus infection inhibitor of the present invention has the above-described configuration, even when it is contained in a substrate and used, it can generally prevent the surface of the substrate from whitening, and it is possible to form a virus infection inhibitor component that has excellent virus infection inhibitory effect and excellent appearance. DETAILED DESCRIPTION OF THE INVENTION

[0011] The viral infection inhibitor of the present invention comprises a polymer compound having at least one amino functional group selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups, or a salt thereof, and having a weight-average molecular weight of 1,000 or more, wherein the main chain of the polymer compound does not contain a nitrogen atom.

[0012] [Virus infection inhibitor] The virus infection inhibitor contains a polymer compound as an active ingredient. In the virus infection inhibitor, the content of the polymer compound having at least one amino functional group selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups or a salt thereof, having a weight-average molecular weight of 1000 or more, and containing no nitrogen atoms in the main chain 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, more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and more preferably 100% by mass, of the active ingredient.

[0013] In the virus infection inhibitor, the content of the polymeric compound having at least one amino functional group selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups, or a salt thereof, having a weight-average molecular weight of 1000 or more, and containing no nitrogen atoms in the main chain 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, more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and more preferably 100% by mass.

[0014] The polymer compound has at least one amino functional group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, or a salt of the amino functional group. The polymer compound exhibits an excellent viral infection-inhibiting effect due to the at least one amino functional group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, or a salt of the amino functional group, and has particularly excellent viral infection-inhibiting effect against non-enveloped viruses.

[0015] The amino functional group preferably contains a secondary amino group because it improves the viral infection inhibitory effect of the viral infection inhibitor and can generally prevent whitening of the substrate surface even when the viral infection inhibitor is incorporated into the substrate.Furthermore, the amino functional group preferably contains a secondary amino group because it has a viral infection inhibitory effect against both enveloped and non-enveloped viruses.

[0016] The amino functional group preferably forms a cyclic skeleton, and more preferably an alicyclic cyclic skeleton, because this improves the viral infection inhibitory effect of the viral infection inhibitor and can generally prevent whitening of the substrate surface even when the viral infection inhibitor is contained in a substrate.

[0017] A primary amino group refers to a monovalent substituent represented by -NH2. A secondary amino group refers to a divalent substituent (-NH-) resulting from removing (pulling out) one hydrogen atom from -NH2. A tertiary amino group refers to a trivalent substituent [≡N, formula (a)] resulting from removing (pulling out) two hydrogen atoms from -NH2. However, the amino functional group does not include a case where a keto group (>CO) is directly bonded to the nitrogen atom constituting the amino functional group.

[0018] [ka]

[0019] The salt of the amino functional group is not particularly limited, but an acid addition salt is preferred. Examples of the acid for the acid addition salt 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, palmitic acid, oleic acid, myristic acid, lauryl sulfuric acid, linolenic acid, and fumaric acid, and hydrochloride is preferred.

[0020] The term "viral infection inhibitory effect" refers to the effect of eliminating or reducing the infectivity of a virus to a cell, or of preventing the virus from replicating in the cell even if it infects. Examples of methods for confirming the infectivity of such a virus include ISO 18184 and JIS L 1922 for textile products, and ISO 21702 for plastics and non-porous surface products other than textile products. Other methods include the plaque method and hemagglutination assay (HAU) method described in "Medical and Pharmaceutical Virology" (first published April 1990).

[0021] The viral infection inhibitory effect of a viral infection inhibitor can be measured, for example, as follows: 3 parts by mass of the viral infection inhibitor and 97 parts by mass of an ultraviolet-curing acrylic paint are mixed to prepare a viral infection inhibitor paint. The viral infection inhibitor paint is applied to a polyethylene film using a wire bar coater #8 to a thickness of 18 μm to form a coating layer.

[0022] At 25°C, the coating layer is exposed to ultraviolet light with a wavelength of 365 nm, with an integrated light intensity of 500 mJ / cm 2 The UV-curable acrylic paint is cured by irradiating it so that a coating film with a thickness of 18 μm is formed.

[0023] A test piece is prepared by cutting out a flat square piece of coating film with a side of 5.0 cm. The surface of the coating film on the obtained test piece is wiped with a flat square piece of nonwoven fabric with a side of 10 cm by moving the nonwoven fabric back and forth 10 times to obtain the test coating film.

[0024] The obtained test coating film is subjected to an antiviral test in accordance with ISO 21702. After the reaction, the virus suspension is subjected to the plaque method to measure the virus infectivity (common logarithm) (PFU / cm 2 ) is calculated.

[0025] A blank coating was prepared in the same manner as above, except that no virus infection inhibitor was added, and the virus infectivity (common logarithm) (PFU / cm) was calculated based on this blank coating in the same manner as above. 2 ) is calculated.

[0026] The antiviral activity value is calculated by subtracting the viral infectivity of the test coating from the viral infectivity of the blank coating.

[0027] For a viral infection inhibitor, the antiviral activity value 10 minutes after the start of the reaction in an antiviral test in accordance with ISO 21702 is preferably 0.6 or higher, more preferably 1.0 or higher, and more preferably 2.0 or higher. For a viral infection inhibitor, the antiviral activity value 24 hours after the start of the reaction in an antiviral test in accordance with ISO 21702 is preferably 0.6 or higher, more preferably 1.0 or higher, and more preferably 2.0 or higher. Regardless of the type of virus being evaluated, it is preferable that the antiviral activity value be 0.6 or higher for at least one type of virus.

[0028] A polymer compound having an amino functional group or a salt thereof has an amino functional group or a salt thereof in a side chain, but does not contain a nitrogen atom in the main chain. The main chain of a polymer compound refers to the longest chain in the polymer compound, and the length of the chain can be determined by the number of atoms contained in the chain, and the greater the number of atoms contained in the chain, the longer the chain is considered to be. The atoms contained in the main chain refer to the atoms that directly constitute the main chain. Therefore, for example, when a vinyl polymer constitutes the main chain, the main chain contains carbon atoms, but the hydrogen bonded to the carbon atom is not included in the atoms that directly constitute the main chain and is not contained in the main chain.

[0029] Since the polymer compound does not contain a nitrogen atom in the main chain, the interaction of the amino functional group or a salt thereof with viruses is improved, thereby improving the viral infection inhibitory effect of the viral infection inhibitor, and whitening of the substrate surface can be largely prevented even when the viral infection inhibitor is incorporated into a substrate. The polymer compound need not contain a nitrogen atom in the main chain. The polymer compound need not contain a nitrogen atom in the main chain. The number of nitrogen atoms contained in the main chain of the polymer compound must be zero. The atoms constituting the main chain may be any other than nitrogen atoms, such as carbon atoms, sulfur atoms, oxygen atoms, etc., with carbon atoms and sulfur atoms being preferred, and carbon atoms only, or carbon atoms and sulfur atoms being preferred.

[0030] The polymer compound has an amino functional group or a salt thereof in the molecule, and examples of the polymer compound include a polymer having an amino functional group or a salt thereof in the side chain of a linear polymer.

[0031] In the polymer containing an amino functional group or a salt thereof in the side chain of a linear polymer, the linear polymer is not particularly limited, and for example, vinyl polymers and polyesters are preferred, with vinyl polymers being more preferred.

[0032] Examples of polymers containing an amino functional group or a salt thereof in the side chain of a linear polymer include polymers containing, as monomer units, an amino functional group-containing monomer containing an amino functional group or a salt thereof.

[0033] The amino functional group-containing monomer containing an amino functional group or a salt thereof is not particularly limited, and examples thereof include 2-vinylpyridine, 4-vinylpyridine, vinylimidazole, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, N-(aminoalkyl)acrylamide, N-(aminoalkyl)methacrylamide, a monomer obtained by reacting glycidyl (meth)acrylate with ammonia or dimethylamine, allylamine, diallylamine, methyldiallylamine, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, or salts of these amino functional groups. The amino functional group-containing monomer containing an amino functional group or a salt thereof may be used alone or in combination of two or more.

[0034] Furthermore, because the polymeric compound has an excellent viral infection inhibitory effect as a viral infection inhibitor, a polymeric compound containing at least one of the repeating units represented by the following formulas (1) to (6) is preferred. In the present invention, n represents a repeating unit and is a natural number of 2 or more. It goes without saying that n represents a repeating unit, and the n's used in each general formula do not have to be the same.

[0035] [ka]

[0036] The polymer containing the amino functional group-containing monomer as a monomer unit may be a homopolymer of the amino functional group-containing monomer, or a copolymer of the amino functional group-containing monomer and a monomer copolymerizable therewith.

[0037] The monomer copolymerizable with the amino functional group-containing monomer is not particularly limited, and examples thereof include alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, 2-vinylnaphthalene, styrene, acrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, vinyl toluene, etc. The monomer copolymerizable with the amino functional group-containing monomer may be used alone or in combination of two or more.

[0038] The polymer compound preferably has a carboxy group or a salt thereof in the molecule, as this improves the viral infection inhibitory effect of the viral infection inhibitor.

[0039] The salt of the carboxy group is not particularly limited, and examples thereof include potassium salt (-COOK), sodium salt (-COONa), calcium salt [(-COO - )2Ca 2+ ], ammonium salt (-COO - NH4 + ), magnesium salt [(-COO - )2Mg 2+ ], barium salts [(-COO - )2Ba 2+ ] etc.

[0040] Examples of polymer compounds containing a carboxy group include polymers containing an amino functional group or a salt thereof and a carboxy group or a salt thereof in the side chain of a linear polymer.

[0041] Examples of polymers containing an amino functional group or a salt thereof and a carboxy group or a salt thereof in the side chain of a linear polymer include polymers containing, as monomer units, an amino functional group-containing monomer containing an amino functional group or a salt thereof and a carboxy group-containing monomer containing a carboxy group or a salt thereof. Note that the amino functional group-containing monomer containing an amino functional group or a salt thereof is the same as described above, and therefore further explanation will be omitted.

[0042] 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, succinic acid mono(meth)acryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, carboxybetaine type monomers or salts thereof, with oxalic acid being preferred. The carboxyl group-containing monomers may be used alone or in combination of two or more.

[0043] Furthermore, a polymer compound containing an amino functional group or a salt thereof and a carboxy group has an excellent viral infection inhibitory effect as a viral infection inhibitor, and therefore preferably contains a repeating unit represented by the following formula (7).

[0044] [ka]

[0045] The polymer compound may be polymerized using a general-purpose polymerization method. For example, a polymer compound can be obtained by polymerizing a monomer composition containing an amino-functional group-containing monomer containing an amino functional group or a salt thereof, and optionally a carboxy-group-containing monomer containing a carboxy group or a salt thereof, and other monomers, in the presence of a general-purpose radical polymerization initiator. Alternatively, a polymer compound may be obtained by polymerizing a monomer composition containing an amino-functional group-containing monomer containing an amino functional group or a salt thereof, and a hydroxyl-containing monomer, in the presence of a general-purpose radical polymerization initiator. Examples of radical polymerization initiators include thermal cleavage radical polymerization initiators such as 1-hydroxycyclohexane-1-yl phenyl ketone, t-hexyl peroxypivalate, benzoyl peroxide, and azobisisobutyronitrile. Alternatively, a polymer containing an amino-functional group may be synthesized by a condensation reaction or transesterification reaction between a polymer having a hydroxyl group and an amino-functional group-containing monomer.

[0046] The nitrogen atom content 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, more preferably 40% or less, more preferably 35% or less, and more preferably 30% or less. When the nitrogen atom content of the polymer compound is within the above range, whitening of the substrate surface can be largely prevented even when the viral infection inhibitor is incorporated into the substrate.

[0047] The nitrogen atom content (%) of a polymer compound refers to the percentage of the nitrogen atom weight relative to the total atomic weight of the repeating units constituting the polymer compound.

[0048] 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: where M1 and M1 represent monomer units. In the present invention, n, m, and p represent repeating units and are natural numbers of 2 or more.

[0049] [ka]

[0050] Nitrogen atom content (%) of polymer compounds = 100 × {(total amount of nitrogen atoms contained in M1) × m + (total amount of nitrogen atoms contained in M2) × n} / {(total atomic weight of M1) × m + (total atomic weight of M2) × n}

[0051] In the present invention, the structural formula shown in formula (8) means a random copolymer, alternating copolymer, or block copolymer of the monomer unit M1 and the monomer unit M2. The polymer form of the polymer compound contained in the virus infection inhibitor is preferably a random copolymer, because the charge state in the polymer chain is evenly distributed, the surface of the polymer compound has an appropriate charge state, and the virus infection inhibitory effect of the virus infection inhibitor is improved.

[0052] The weight-average molecular weight of the polymer compound is preferably at least 1000, more preferably at least 2000, and even more preferably at least 3000. When the weight-average molecular weight of the polymer compound is 1000 or more, the polymer compound can interact with viruses at multiple points, thereby improving the viral infection-blocking effect of the viral infection-blocking material.

[0053] The weight-average molecular weight of the polymer compound is preferably not more than 1,000,000, more preferably not more than 900,000, more preferably not more than 800,000, and even more preferably not more than 600,000. When the weight-average molecular weight of the polymer compound is 1,000,000 or less, whitening of the surface of a substrate containing the virus infection inhibitor can be reduced, and the virus infection inhibitory effect can be more effectively exerted without impairing the appearance of the substrate, and the aggregation tendency of the virus infection inhibitory compound is reduced, resulting in a form that facilitates interaction between the virus infection inhibitory compound and the virus, and improving the virus infection inhibitory effect of the virus infection inhibitor.

[0054] When a polymer compound is a mixture of multiple types of polymers, the weight average molecular weight of the polymer compound is the weight average molecular weight of the entire polymer compound.

[0055] In the present invention, the weight average molecular weight of the polymer compound is a value measured by GPC (gel permeation chromatography) and converted into polystyrene.

[0056] For example, the measurement can be performed using the following measurement device and under the following measurement conditions. Gel permeation chromatograph: Waters, product name "2690SeparationsModel" Column: Showa Denko Co., Ltd., product name "GPCKF-806L" Detector: differential refractometer Sample flow rate: 1 mL / min Column temperature: 40℃ Eluent: THF

[0057] The pH of a 5% by mass aqueous solution of a polymer compound at 25°C is preferably 4 or less. The pH of a 5% by mass aqueous solution of a polymer compound at 25°C is preferably 9 or more. When the pH of a 5% by mass aqueous solution of a polymer compound at 25°C is 4 or less, the surface of the polymer compound is appropriately charged, or the number of protons on the virus surface increases, thereby increasing the electrostatic interaction with the virus infection inhibitor, and improving the virus infection inhibitory effect of the virus infection inhibitor. When the pH of a 5% by mass aqueous solution of a polymer compound at 25°C is 4 or less or 10 or more, the surface of the polymer compound is appropriately charged, or the virus surface is anionized, thereby increasing the electrostatic interaction with the virus infection inhibitor, and improving the infection inhibitory effect of the virus infection inhibitor. The pH of a 5% by mass aqueous solution of a polymer compound at 25°C refers to the pH value at 25°C of a mixture obtained by adding 5 g of the polymer compound to 95 g of purified water and uniformly mixing. The mixture may be either completely dissolved in purified water, or partially dissolved in purified water to form a saturated aqueous solution.

[0058] The pKa1 of the polymer compound at 25°C is preferably 8 or more, more preferably 8.5 or more. When the pKa1 of the polymer compound at 25°C is 8 or more, the surface of the polymer compound is in an appropriate charge state in the interaction between the polymer compound and the virus, the virus is effectively captured, the virus infection inhibitor's viral infection inhibitory effect is improved, and even when the viral infection inhibitor is used by being contained in a substrate, whitening of the substrate surface can be largely prevented. The pKa1 of the polymer compound at 25°C is preferably 12 or less, more preferably 11 or less, and more preferably 10 or less. Here, the electrolyte BH + But B and H + When an acid dissociates into ions and the ionization equilibrium is obtained as shown in equation (b), the acid dissociation constant Ka is defined by equation (c), and pKa is defined as the common logarithm (d) of the reciprocal of the acid dissociation constant Ka. The polymer compound in this specification is synthesized by polymerizing an amino functional group-containing monomer containing an amino functional group or a salt thereof, or by a condensation reaction or transesterification reaction between a polymer having a hydroxyl group and an amino functional group-containing monomer.

[0059] In the present invention, pKa1 is defined as the acid dissociation constant of the conjugate acid of an amine in a monomer containing an amino functional group or a salt thereof, which is a constituent element of a polymer compound. In the present invention, the "pKa1 of a monomer containing an amino functional group or a salt thereof, which is a constituent element of a polymer compound," is referred to as the "pKa1 of the polymer compound." When the monomer containing an amino functional group or a salt thereof, which is a constituent element of a polymer compound, is a polyamine, the conjugate acid of the polyamine undergoes multi-stage ionization, and pKa1 refers to the pKa calculated based on the ionization constant of the first stage.

[0060]

number

[0061] The pKa1 of a polymer compound at 25°C is a value measured by titration. Specifically, the pKa1 can be determined by titrating the hydrochloride of an amino-functional group-containing monomer, which is a component of the polymer compound, with sodium hydroxide at 25°C and measuring the pH at 25°C at the half-equivalent point (the point at which half the amount required for complete neutralization is added dropwise). If the amino-functional group-containing monomer is a free amine, it can be converted to its hydrochloride salt and then the pKa1 can be determined by the method described above. A method for converting a free amine to its hydrochloride salt includes, for example, mixing the amino-functional group-containing monomer with a 1 mol% aqueous hydrochloric acid solution, converting all of the amino groups contained in the amino-functional group-containing monomer to their hydrochloride salts, and then removing the hydrochloric acid and water by a commonly used method such as freeze-drying.

[0062] It is preferable that the polymer compound does not contain an aromatic ring in the molecule. If the polymer compound does not contain an aromatic ring, whitening of the substrate surface can be largely prevented even when the virus infection inhibitor is contained in the substrate. Furthermore, if the polymer compound does not contain an aromatic ring, the bulkiness of the polymer compound is reduced, so that the molecular structure portion containing the amino functional group can efficiently interact with the virus, thereby exhibiting an excellent virus infection inhibitory effect.

[0063] The aromatic ring includes not only a monocyclic aromatic ring but also a fused aromatic ring formed by condensing monocyclic aromatic rings. The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, biphenyl, and phenoxyphenyl. The aromatic ring is formed by removing (abtracting) one or more hydrogen atoms from either the aromatic ring or the fused aromatic ring, and is bonded to other atoms by a covalent bond.

[0064] The polymer compound is preferably formed into particles, since it can be uniformly dispersed on the surface of the substrate and can impart an excellent viral infection-blocking effect to the substrate. The D90 particle size of the polymer compound is preferably 1 μm or more, more preferably 2 μm or more, preferably 2.5 μm or more, more preferably 3 μm or more, and 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, 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 14 μm or less, and more preferably 12 μm or less. When the D90 particle size is 1 μm or more, the surface area of ​​the polymer compound as a whole is reduced, the agglomeration of the viral infection inhibitor is reduced, and the polymer compound and viruses are in a form that facilitates interaction, thereby improving the viral infection-blocking effect of the viral infection-blocking member and generally preventing whitening of the substrate surface even when the viral infection-blocking effect is incorporated into the substrate. When the D90 particle size is 50 μm or less, aggregation of the virus infection inhibitor is prevented and the surface area is increased, facilitating contact with the virus, thereby improving the virus infection inhibitory effect of the virus infection inhibitor material, and whitening of the substrate surface can be largely prevented even when the virus infection inhibitor is incorporated into the substrate.

[0065] As will be described later, the D90 particle size of a polymer compound is the particle size (90% cumulative particle size) at which the cumulative frequency (cumulative from particles with small particle sizes) in the volume-based particle size distribution measured by a laser scattering method is 90%. When a polymer compound contains multiple types of polymer compounds, the D90 particle size of the polymer compound is a value measured based on the entire polymer compound.

[0066] The virus infection inhibitor may be used by adhering (supporting) it to the surface of the base particle. By adhering the virus infection inhibitor to the surface of the base particle, the virus infection inhibitor can be more uniformly dispersed in the substrate, and whitening of the substrate can be more effectively prevented. Furthermore, the surface area of ​​the virus infection inhibitor can be increased, ensuring sufficient contact between the virus infection inhibitor and the virus, allowing the virus infection inhibitor to fully exert its virus infection inhibitory effect.

[0067] The base particles to which the virus infection inhibitor is attached on the surface are not particularly limited as long as they do not inhibit the virus infection inhibitory effect of the virus 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.

[0068] Examples of synthetic resins constituting the resin particles include styrene-based resins, acrylic-based resins, urethane-based resins, vinyl chloride-based resins, ABS resins; and synthetic rubbers such as styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR). Of these, styrene-based resins and acrylic-based resins are preferred.

[0069] The styrene-based resin is not particularly limited, and examples thereof include homopolymers or copolymers containing, as monomer units, styrene-based monomers such as styrene, methylstyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, chlorostyrene, and bromostyrene, and copolymers containing, as monomer units, a styrene-based monomer and one or more vinyl monomers copolymerizable with the styrene-based monomer.

[0070] Examples of vinyl monomers copolymerizable with styrene-based monomers include acrylic monomers such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.), maleic anhydride, and acrylamide.

[0071] The acrylic resin is not particularly limited, and examples thereof include homopolymers or copolymers containing, as monomer units, acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate, and copolymers containing, as monomer units, an acrylic monomer and one or more vinyl monomers copolymerizable with the acrylic monomer. Note that (meth)acrylate means acrylate or methacrylate.

[0072] Examples of vinyl monomers copolymerizable with acrylic monomers include acrylonitrile, methacrylonitrile, maleic anhydride, and acrylamide.

[0073] 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.

[0074] The synthetic resin constituting the resin particles preferably contains an aromatic ring, which attracts the hydrophobic portion of the polymer compound attached to the surface of the resin particles and orients the amino functional group and carboxyl group outward, thereby enabling the virus infection inhibitor to more effectively exert its virus infection inhibitory effect.

[0075] The aromatic ring may be a monocyclic aromatic ring, or may be a fused monocyclic aromatic ring (fused aromatic ring). The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, biphenyl, and phenoxyphenyl. The aromatic ring is formed by removing (abtracting) one or more hydrogen atoms from either the aromatic ring or the fused aromatic ring, and is bonded to other atoms via a covalent bond.

[0076] The amount of polymer compound attached 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 even more preferably 10 parts by mass or more, per 100 parts by mass of the resin particles. When the amount of polymer compound attached is 1 part by mass or more, the virus infection inhibitor can be uniformly attached to the surface of the resin particles, allowing the virus infection inhibitor to more effectively exert its virus infection inhibitory effect.

[0077] The amount of polymer compound attached 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, and even more preferably 400 parts by mass or less, per 100 parts by mass of resin particles. When the amount of polymer compound attached is 1,000 parts by mass or less, the virus infection inhibitors do not bond to each other, and the virus infection inhibitors are efficiently distributed on the surfaces of the resin particles, improving the virus infection inhibitory effect.

[0078] The method for adhering the virus infection inhibitor to the surface of the resin particles is not particularly limited, and may be, for example, by relying on the adhesive strength of the virus infection inhibitor, or by adhering the virus infection inhibitor to the surface of the resin particles using a binder resin. However, since this allows the virus infection inhibitor to effectively exert its virus infection inhibitory effect, it is preferable that the polymer compound be adhered to the surface of the resin particles by the adhesive strength of the polymer compound itself.

[0079] The viral infection inhibitor has an inhibitory effect on various viruses due to the action of the polymer compound, and exhibits excellent inhibitory effect on both enveloped and non-enveloped viruses.

[0080] Examples of enveloped viruses include influenza viruses (e.g., influenza A, B, etc.), rubella viruses, Ebola viruses, coronaviruses (e.g., SARS virus, novel coronavirus (SARS-CoV-2)), measles viruses, varicella-zoster viruses, herpes simplex viruses, mumps viruses, arboviruses, respiratory syncytial viruses, hepatitis viruses (e.g., hepatitis B virus, hepatitis C virus, etc.), yellow fever viruses, AIDS viruses, rabies viruses, hantaviruses, dengue viruses, Nipah viruses, and lyssaviruses.

[0081] Examples of non-enveloped viruses include feline calicivirus, adenovirus, norovirus, rotavirus, human papillomavirus, poliovirus, enterovirus, coxsackievirus, human parvovirus, encephalomyocarditis virus, and rhinovirus.

[0082] The virus infection inhibitor can be contained in the substrate described below to form a virus infection-blocking member, and can impart an excellent virus infection-blocking effect to the substrate without causing any whitening on the substrate surface.

[0083] The substrate to be incorporated with the virus infection inhibitor is not particularly limited as long as it is desired to impart a virus infection inhibitory effect, and examples include paints, synthetic resin molded products, wallpaper, decorative sheets, flooring materials, textile products (woven fabrics, nonwoven fabrics, knitted fabrics), interior and interior materials for vehicles (for example, cars, airplanes, ships, etc.) (seats, child seats, and the foams that make up these), kitchenware, baby products, and building interior materials.

[0084] The building interior materials are not particularly limited, and examples thereof include flooring materials, wallpaper, ceiling materials, paints, doorknobs, switches, switch covers, wax, and the like.

[0085] The vehicle interior goods and materials are not particularly limited, and examples thereof include seats, child seats, seat belts, car mats, seat covers, doors, ceiling materials, floor mats, door trim, instrument panels, consoles, glove boxes, handrails, and the like.

[0086] The content of the polymer compound in the substrate 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, per 100 parts by mass of the substrate. The content of the polymer compound in the substrate 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, per 100 parts by mass of the substrate. When the content of the polymer compound in the substrate is 0.1 parts by mass or more, the viral infection-blocking effect of the viral infection-blocking member can be improved. When the content of the polymer compound in the substrate is 30 parts by mass or less, the polymer compound is more likely to be uniformly dispersed without agglomeration, without affecting the physical properties of the substrate, thereby improving the viral infection-blocking effect.

[0087] The virus infection inhibitor is contained in a paint to form a virus infection-preventing paint. The paint film formed from the virus infection-preventing paint not only exhibits an excellent virus infection-preventing effect, but also largely prevents whitening of the paint film surface, resulting in a paint film with excellent appearance.

[0088] Conventionally known paints can be used as the paint. The paint can improve the dispersibility of the virus infection inhibitor and form a coating film with excellent virus infection prevention effects, and can be used for both hydrophobic and hydrophilic paints. Hydrophobic paints are not particularly limited, and examples thereof include oil-based paints (e.g., blended paints, oil varnishes, etc.), cellulose paints, and synthetic resin paints. Paints also include photocurable paints that polymerize upon irradiation with radiation such as ultraviolet rays to produce a binder component. Water-based paints are not particularly limited, and examples thereof include water-based urethane paints, water-based silicone paints, water-based fluorine paints, and water-based inorganic paints.

[0089] The paint may contain a solvent to adjust the viscosity. As the solvent, an organic solvent is preferred because it improves the dispersibility of the virus infection inhibitor in the paint. The organic solvent is not particularly limited, and examples thereof include toluene, xylene, methyl ethyl ketone, acetone, ethyl acetate, benzene, and isopropyl alcohol. The solvent may be used alone or in combination of two or more.

[0090] The content of the polymer compound in the virus infection preventing paint is preferably 1% by mass or more, and more preferably 2% by mass or more. The content of the polymer compound in the virus infection preventing paint is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less. When the content of the polymer compound is 1% by mass or more, the coating film formed from the virus infection preventing paint exhibits excellent virus infection preventing effect. When the content of the polymer compound is 10% by mass or less, the polymer compound is easily dispersed uniformly without agglomeration, which is preferable because it improves the virus infection preventing effect and is less likely to affect the physical properties of the substrate.

[0091] Furthermore, the paint may contain additives such as pigments, plasticizers, curing agents, extenders, fillers, antioxidants, thickeners, and surfactants, within the range that does not impair the physical properties of the paint.

[0092] Examples of methods for incorporating the virus infection inhibitor into a paint include a method in which the virus infection inhibitor and the paint are supplied to a dispersing device and mixed uniformly. Examples of dispersing devices include a high-speed mill, a ball mill, and a sand mill. [Example]

[0093] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0094] Polymer compounds 1 to 16 were prepared.

[0095] [High molecular compound] Polymer compound 1 [polymer compound having a repeating unit represented by formula (1)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAA-15C" was freeze-dried to obtain a powder of polymer compound 1.

[0096] [ka]

[0097] Polymer compound 2 [having a repeating unit represented by formula (9)] One part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, polymerization degree: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). Subsequently, 8.0 parts by weight of L-tyrosine methyl ester and 6 parts by weight of tetra-t-butylzinc dilithium (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were further added, and the mixture was stirred at 30°C for 6 hours to carry out an ester exchange reaction. The resulting mixture was then reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and dried to obtain a powder of polymer compound 2. In formula (9), m:n = 86:14.

[0098] [ka]

[0099] Polymer compound 3 [having a repeating unit represented by formula (10)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-21CL" was freeze-dried to obtain a powder of polymer compound 3.

[0100] [ka]

[0101] Polymer compound 4 [having a repeating unit represented by formula (3)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-21" was freeze-dried to obtain a powder of polymer compound 4.

[0102] [ka]

[0103] Polymer compound 5 [having a repeating unit represented by formula (11)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAA-D19-HCl" was freeze-dried to obtain a powder of polymer compound 5. m:n=1:9.

[0104] [ka]

[0105] Polymer compound 6 [having a repeating unit represented by formula (12)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-92" was freeze-dried to obtain a powder of polymer compound 6.

[0106] [ka]

[0107] Polymer compound 7 [having a repeating unit represented by formula (13)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-410C" was freeze-dried to obtain a powder of polymer compound 7. m:n=1:1.

[0108] [ka]

[0109] Polymer compound 8 [having a repeating unit represented by formula (14)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-411C" was freeze-dried to obtain a powder of polymer compound 8. m:n=3:1.

[0110] [ka]

[0111] Polymer compound 9 [having a repeating unit represented by formula (15)] One part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, polymerization degree: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). Subsequently, 3.0 parts by mass of N,N-dimethylglycine methyl ester and 6 parts by weight of tetra-t-butylzinc dilithium (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were further added, and the mixture was stirred at 30°C for 6 hours to carry out an ester exchange reaction. The resulting mixture was then reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and dried to obtain a powder of polymer compound 9. The m:n ratio was 86:14.

[0112] [ka]

[0113] Polymer compound 10 [having a repeating unit represented by formula (16)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-M-1" was freeze-dried to obtain a powder of polymer compound 10.

[0114] [ka]

[0115] Polymer compound 11 [having a repeating unit represented by formula (17)] A polymer compound commercially available from Dafeng Yuelong Chemical Co., Ltd. under the trade name "Polyhexamethylene biguanide hydrochloride" was freeze-dried to obtain a powder of polymer compound 12. In formula (17), x is a natural number of 2 or more.

[0116] [ka]

[0117] ·High molecular compound 12 A polymer compound (liquid) commercially available under the trade name "SP-200" from Nippon Shokubai Co., Ltd. was used. Polymer compound 12 contained a nitrogen atom in the main chain.

[0118] ·High molecular compound 13 A polymer compound commercially available from Nippon Shokubai Co., Ltd. under the trade name "P-1000" was freeze-dried and then thawed to obtain liquid polymer compound 13. Polymer compound 13 contained a nitrogen atom in the main chain.

[0119] Polymer compound 14 [having a repeating unit represented by formula (18)] A polymer compound commercially available from Nittobo Medical Co., Ltd. under the trade name "PAS-H-5L" was freeze-dried to obtain a powder of polymer compound 14.

[0120] [ka]

[0121] Polymer compound 15 [having a repeating unit represented by formula (19)] One part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, polymerization degree: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). Subsequently, 1.7 parts by weight of methyl L-pyroglutamate and 6 parts by weight of tetra-t-butylzinc dilithium (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were further added, and the mixture was stirred at 30°C for 6 hours to carry out an ester exchange reaction. The resulting mixture was then reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and dried to obtain a powder of polymer compound 15. The m:n ratio was 81:19.

[0122] [ka]

[0123] Polymer compound 16 [having a repeating unit represented by formula (20)] One part by weight of raw material polyvinyl alcohol (PVA-1, saponification degree: 98.5 mol%, polymerization degree: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). Subsequently, 3.3 parts by weight of N-acetyl-L-alanine methyl ester and 6 parts by weight of tetra-t-butylzinc dilithium (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were further added, and the mixture was stirred at 30°C for 6 hours to carry out an ester exchange reaction. The resulting mixture was then reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and dried to obtain a powder of polymer compound 16. The m:n ratio was 85:15.

[0124] [ka]

[0125] In the structural formula shown above, m, n, and p represent repeating units and are all natural numbers of 2 or more. In formula (17), x is a natural number of 2 or more.

[0126] Of the structural formulae shown above, the structural formula shown as formula (8) means a random copolymer, an alternating copolymer, or a block copolymer of a monomer unit M1 and a monomer unit M2.

[0127] [ka]

[0128] [Preparation of polymer compound particles] The polymer compound was coarsely crushed using a roll press (Seishin Enterprise Co., Ltd., product name "150 type") at a rotation speed of 25 rpm and a pressure of 25 tons, and then crushed using a jet mill (Nisshin Engineering, product name "SJ-500") at a polymer compound feed rate of 1 kg / h and a compressed air pressure of 0.75 MPa to obtain polymer compound particles. The D90 particle size of the polymer compound particles is shown in Table 1.

[0129] For the polymer compounds used in the examples and comparative examples, 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 are shown in Table 1. In Table 1, "pH of a 5% by mass aqueous solution at 25°C" and "pKa1 at 25°C" are simply abbreviated as "pH" and "pKa1," respectively.

[0130] (Examples 1 to 10 and Comparative Examples 1 to 6) A virus infection-preventing paint was prepared by mixing a virus infection-preventing agent containing 5 parts by mass of particles of the polymer compound shown in Table 1, prepared as described above, with 95 parts by mass of an ultraviolet-curing acrylic paint (manufactured by Coattec Co., Ltd., product name "AI-N2") The virus infection-preventing paint was applied to a polyethylene film using a wire bar coater #8 to a thickness of 18 μm to form a coating layer.

[0131] Using a UV conveyor device (Eye Graphics "ECS301G1"), ultraviolet light with a wavelength of 365 nm was applied to the coating layer at 25°C with an integrated light intensity of 500 mJ / cm. 2The ultraviolet-curable acrylic paint was cured by irradiating it so as to form a coating film with a thickness of 18 μm.

[0132] The antiviral activity and whitening activity of the virus infection inhibitor were measured in the following manner, and the results are shown in Table 1.

[0133] [Antiviral] The coating film obtained above was used to carry out an antiviral test using feline calicivirus (non-enveloped virus) and influenza virus (enveloped virus) in the following manner.

[0134] (Antiviral test) A test piece was prepared by cutting out a flat square piece with each side measuring 5.0 cm from the coating film.

[0135] The surface of the coating film on the obtained test piece was wiped with a flat square nonwoven fabric (trade name "Kimwipe S-200" manufactured by Nippon Paper Crecia Co., Ltd.) with a side of 10 cm, moving it back and forth 10 times to obtain a test coating film.

[0136] The obtained test coating film was subjected to antiviral tests (test time: 24 hours) against feline calicivirus and influenza virus in accordance with ISO 21702. After the reaction, the virus suspension was used to calculate the virus infectivity of the test coating film by the plaque method.

[0137] A blank coating was prepared in the same manner as above, except that no virus infection inhibitor was added, and the virus infectivity (common logarithm) (PFU / cm) was calculated based on this blank coating in the same manner as above. 2 The virus infectivity titer (common logarithm) of the blank coating was 6.5 PFU / cm 2 It was.

[0138] The antiviral activity value was calculated by subtracting the viral infectivity of the test coating from the viral infectivity of the blank coating.

[0139] [Whitening] Whitening evaluation was performed in accordance with JIS A 1454, Test Method for Stain Resistance of Polymer-Based Flooring Materials. In a test room at 23°C and 50% humidity, 2 ml of purified water was dropped onto the surface of the test coating, covered with a watch glass, and left to stand for 24 hours. The water was then removed with a mild household detergent, and the surface was wiped with industrial alcohol and left to stand in the test room for 1 hour. The haze of the coating was evaluated in accordance with JIS K 7361. The haze value (%) was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) at a room temperature of 25°C and a relative humidity of 40%. The higher the haze value, the greater the degree of whitening of the coating surface.

[0140] [Table 1] [Industrial Applicability]

[0141] The virus infection inhibitor of the present invention can generally prevent the surface of a substrate from whitening even when it is incorporated into a substrate such as a coating film, wallpaper, decorative sheet, flooring material, textile product, interior and trim materials for vehicles, kitchenware, baby products, or building interior materials, and can form a virus infection inhibitor component that has excellent virus infection inhibitory effect and excellent appearance.

[0142] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to Japanese Patent Application No. 2022-049777, filed on March 25, 2022, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A viral infection inhibitor comprising a polymeric compound having a secondary amino group and a weight-average molecular weight of 1000 or more, wherein the main chain of the polymeric compound does not contain a nitrogen atom, and wherein a 5% by mass aqueous solution of the polymeric compound has a pH of 9 or more at 25°C.

2. The virus infection inhibitor according to claim 1, wherein the polymer compound has a nitrogen atom content of 0.1 to 50%.

3. 3. The virus infection inhibitor according to claim 1, wherein the polymer compound has a weight-average molecular weight of 1,000 to 1,000,000.

4. 3. The virus infection inhibitor according to claim 1, wherein the polymer compound contains a carboxy group or a salt thereof.

5. 3. The virus infection inhibitor according to claim 1, wherein the polymer compound has a pKa1 of 8 or more.

6. The virus infection inhibitor according to claim 1 or 2, characterized in that the amino functional group forms a cyclic skeleton.

7. A virus infection-blocking member comprising a substrate and the virus infection-blocking agent according to claim 1 or 2 contained in the substrate.

8. A virus infection-preventing paint comprising a paint and the virus infection-preventing agent according to claim 1 or 2 contained in the paint.

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