WO2023181844A1

WO2023181844A1 - Viral infection inhibitor, viral infection inhibiting member, and viral infection inhibiting paint

Info

Publication number: WO2023181844A1
Application number: PCT/JP2023/007992
Authority: WO
Inventors: 拓也木下; 大地川村; 洋平西村; 和也西原; 太郎鈴木
Original assignee: 積水化学工業株式会社
Priority date: 2022-03-25
Filing date: 2023-03-03
Publication date: 2023-09-28
Also published as: TW202348138A

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

Virus infection inhibitors, virus infection prevention materials, and virus infection prevention paints

The present invention relates to a virus infection inhibiting agent, a virus infection inhibiting member, and a virus infection inhibiting paint.

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

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

To address these problems, Patent Document 1 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 the synthetic resin.

Japanese Patent Application Publication No. 2016-128395

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

The present invention provides a virus infection inhibitor that can generally prevent whitening of the surface of a substrate even when used in a substrate.

The virus infection inhibitor of the present invention has at least one amino group or a salt thereof selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, and has a weight average molecular weight of 1000. The main chain of the polymer compound contains no nitrogen atom.

The virus infection inhibiting member of the present invention is characterized by comprising a base material and the virus infection inhibiting agent according to any one of claims 1 to 7 contained in the base material.

Since the virus infection inhibitor of the present invention has the above-mentioned structure, it can generally prevent whitening of the surface of the base material even when it is used in a base material, and is an excellent virus infection inhibitor. It is possible to construct a virus infection prevention member that has an infection prevention effect and has an excellent appearance.

The virus infection inhibitor of the present invention has at least one amino functional group or a salt thereof selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, and has a weight average molecular weight of 1000 or more, and the main chain of the polymer compound does not contain a nitrogen atom.

[Viral infection inhibitor]
Viral infection inhibitors contain high molecular compounds as active ingredients. The virus infection inhibitor 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 thereof, and has a weight average molecular weight of 1000 or more. The content of the polymer compound that does not contain nitrogen atoms in its main chain is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass or more in the active ingredients. It is more preferably 90% by mass or more, more preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass.

The virus infection inhibitor 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 thereof, and has a weight average molecular weight of 1000 or more. The content of the polymer compound that does not contain nitrogen atoms in its 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, and 90% by mass or more. It is more preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass.

The polymer compound has at least one amino functional group or a salt of an amino functional group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group. The polymer compound is derived from at least one amino functional group or a salt of an amino functional group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, and has an excellent ability to inhibit virus infection. In particular, it has an excellent effect of inhibiting virus infection against non-enveloped viruses.

The amino functional group not only improves the virus infection inhibiting effect of the virus infection inhibitor, but also prevents whitening of the surface of the base material even when the base material contains the virus infection inhibiting effect. , preferably contains a secondary amino group. Furthermore, since the amino functional group has the effect of inhibiting virus infection against both enveloped viruses and non-enveloped viruses, it is preferable to include a secondary amino group.

The amino functional group not only improves the virus infection inhibiting effect of the virus infection inhibitor, but also prevents whitening of the surface of the base material even when the base material contains the virus infection inhibiting effect. , it is preferable that a cyclic skeleton is formed, and it is preferable that an alicyclic cyclic skeleton is formed.

Note that the primary amino group means a monovalent substituent represented by -NH ₂ . A secondary amino group means a divalent substituent (-NH-) formed by removing (withdrawing) one hydrogen atom from -NH ₂ . A tertiary amino group means a trivalent substituent [≡N, formula (a)] formed by removing (extracting) two hydrogen atoms from -NH ₂ . However, the amino functional group excludes cases where a keto group (>CO) is directly bonded to the nitrogen atom constituting the amino functional group.

The salt of the amino functional group is not particularly limited, but acid addition salts are preferred. Examples of acids for 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, palmitic acid, and oleic acid. , myristic acid, lauryl sulfate, linolenic acid, and fumaric acid, with hydrochloride being preferred.

Note that the effect of inhibiting virus infection refers to the effect of eliminating or reducing the infectivity of a virus to cells, or preventing it from proliferating in cells even if infected. Examples of methods for confirming the presence or absence of virus infectivity include ISO 18184 and JIS L1922 for textile products, and ISO 21702 for products with plastics and non-porous surfaces other than textile products. Other methods include the plaque method and the hemagglutination titer (HAU) measurement method described in "Medical and Pharmaceutical Virology" (first edition published in April 1990).

The virus infection inhibiting effect of the virus infection inhibitor can be measured, for example, in the following manner. A virus infection inhibiting paint is prepared by mixing 3 parts by mass of a virus infection inhibitor and 97 parts by mass of an ultraviolet curable acrylic paint. A coating layer is formed by applying a virus infection inhibiting paint onto a polyethylene film to a thickness of 18 μm using a wire bar coater #8.

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

For the coating film, a test piece is prepared by cutting out a planar square shape with a side of 5.0 cm. The surface of the coating film of the obtained test piece is wiped off using a square nonwoven fabric with a side of 10 cm by moving the nonwoven fabric back and forth 10 times to obtain a test coating film.

The obtained test coating film is subjected to an antiviral test in accordance with ISO21702. For the virus suspension after the reaction, the virus infectivity value (common logarithm value) (PFU/cm ² ) of the test coating is calculated by the plaque method.

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

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

Regarding virus infection inhibitors, the antiviral activity value after 10 minutes from the start of the reaction in an antiviral test based on ISO21702 is preferably 0.6 or more, more preferably 1.0 or more, and even more preferably 2.0 or more. . Regarding virus infection inhibitors, the antiviral activity value after 24 hours from the start of the reaction in an antiviral test based on SO21702 is preferably 0.6 or more, more preferably 1.0 or more, and even more preferably 2.0 or more. . Regardless of the type of virus to be evaluated, it is preferable that the antiviral activity value is 0.6 or more for at least one type of virus.

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

By not containing a nitrogen atom in the main chain of the polymer compound, the interaction with the virus in the amino functional group or its salt of the polymer compound is improved, thereby improving the virus infection inhibiting effect of the virus infection inhibitor. In addition, even when the base material contains a virus infection inhibitor, whitening of the surface of the base material can be generally prevented. It is sufficient that the polymer compound does not contain a nitrogen atom in its main chain. The polymer compound may have 0 nitrogen atoms in its main chain. The atoms constituting the main chain may be any atoms other than nitrogen atoms, such as carbon atoms, sulfur atoms, oxygen atoms, etc. Carbon atoms and sulfur atoms are preferred, and only carbon atoms or carbon atoms and sulfur atoms are preferred.

The polymer compound has an amino functional group or a salt thereof in the molecule. Examples of the polymer compound include polymers containing amino functional groups or salts thereof in the side chains of linear polymers.

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

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

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, and (meth)acrylic acid. Obtained by reacting diethylaminoethyl acid, t-butylaminoethyl (meth)acrylate, N-(aminoalkyl)acrylamide, N-(aminoalkyl)methacrylamide, glycidyl (meth)acrylate with ammonia, dimethylamine, etc. Monomers, 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, etc. can be mentioned. Note that 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 types.

Furthermore, since the polymer compound has an excellent virus infection inhibiting effect as a virus infection inhibitor, a polymer compound containing at least one of the repeating units represented by the following formulas (1) to (6) is preferable. In addition, in this invention, n shows a repeating unit and is a natural number of 2 or more. n indicates a repeating unit, and it goes without saying that the n used in the general formula need not be the same.

The polymer containing an 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. .

Monomers copolymerizable with the amino functional group-containing monomer are not particularly limited, and include, for example, 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, vinyltoluene and the like. The monomers copolymerizable with the amino functional group-containing monomer may be used alone or in combination of two or more.

The polymer compound preferably has a carboxy group or a salt thereof in the molecule, since this improves the virus infection inhibiting effect of the virus infection inhibitor.

Salts of carboxy groups are not particularly limited, and examples include potassium salts (-COOK), sodium salts (-COONa), calcium salts [(-COO ^- ) ₂ Ca ²⁺ ], ammonium salts (-COO ^- NH ₄ ⁺ ), magnesium salt [(-COO ^- ) ₂ Mg ²⁺ ], barium salt [(-COO ^- ) ₂ Ba ²⁺ ], and the like.

Examples of the polymer compound containing a carboxyl group include a polymer containing an amino functional group or a salt thereof and a carboxyl group or a salt thereof in the side chain of a linear polymer.

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 an amino functional group-containing monomer containing an amino functional group or a salt thereof, and a carboxy group or a salt thereof. Examples include polymers containing a carboxy group-containing monomer containing the salt thereof as a monomer unit. Note that the amino functional group-containing monomer containing an amino functional group or a salt thereof is the same as described above, so a description thereof will be omitted.

Carboxy group-containing monomers containing a carboxy group or a salt thereof are not particularly limited, and examples thereof include acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, and succinic acid mono( Examples include meth)acryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, carboxybetaine type monomers or salts thereof, and oxalic acid is preferred. . In addition, the carboxy group-containing monomers may be used alone or in combination of two or more types.

In addition, since a polymer compound containing an amino functional group or a salt thereof and a carboxy group has an excellent virus infection inhibiting effect as a virus infection inhibitor, it may contain a repeating unit represented by the following formula (7). preferable.

The polymer compound may be polymerized using a general-purpose polymerization method. For example, a monomer composition containing an amino functional group-containing monomer containing an amino 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 as a general-purpose radical. A polymer compound can be obtained by polymerizing in the presence of a polymerization initiator. Alternatively, 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 a monomer containing a hydroxyl group in the presence of a general-purpose radical polymerization initiator. You can. Examples of the radical polymerization initiator include thermally cleavable radical polymerization initiators such as 1-hydroxycyclohexane-1-ylphenyl ketone, t-hexyl peroxypivalate, benzoyl peroxide, and azobisisobutyronitrile. It will be done. 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 a monomer containing an amino functional group.

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 even more preferably 30% or less. When the nitrogen atom content of the polymer compound is within the above range, whitening of the surface of the substrate can be generally prevented even when the substrate contains a virus infection inhibitor.

The nitrogen atom content (%) of a polymer compound refers to the percentage of the nitrogen atomic weight 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. However, M ₁ and M ₁ 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 of polymer compounds (%)
= 100 x {(Total nitrogen atomic weight contained in M ₁ ) x m + (Total nitrogen atomic weight contained in M ₂ ) x n}
/{(Total atomic weight of M ₁ ) x m + (Total atomic weight of M ₂ ) x n}

In the present invention, the structural formula shown in formula (8) means a random copolymer, alternating copolymer, or block copolymer of monomer units _M1 and _M2 . The polymerization form of the polymer compound contained in the virus infection inhibitor is such that the charge states in the polymer chain are arranged in an average manner, and the surface of the polymer compound is in an appropriate charge state. Random copolymers are preferred because they improve the infection-inhibiting effect.

The weight average molecular weight of the polymer compound is preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more. When the weight average molecular weight of the polymer compound is 1000 or more, the polymer compound can interact with the virus at multiple points, and the virus infection prevention effect of the virus infection prevention member can be improved.

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, and more preferably 600,000 or less. When the weight average molecular weight of the polymer compound is 1,000,000 or less, whitening of the surface of the base material containing the virus infection inhibitor can be reduced, and the effect of inhibiting virus infection can be made more effective without impairing the appearance of the base material. In addition, the aggregation of the virus infection-inhibiting compound is reduced, resulting in a form in which the virus-infection-inhibiting compound and the virus are likely to interact, and the virus infection-inhibiting effect of the virus infection-inhibiting agent is improved.

When the 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.

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

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

The pH of a 5% by mass aqueous solution of a 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 higher. If 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 will be in an appropriate charge state, or the number of protons on the virus surface will increase, resulting in static interaction with the virus infection inhibitor. The electric interaction increases, and the virus infection inhibiting effect of the virus infection inhibitor improves. 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 becomes an appropriate charge state or the surface of the virus is anionized, thereby inhibiting virus infection. The electrostatic interaction with the agent increases, and the infection inhibiting effect of the virus infection inhibitor improves. Note that the pH at 25° C. of a 5% by mass aqueous solution of a polymer compound refers to the pH value at 25° C. of a mixed solution in which 5 g of a polymer compound is added to 95 g of purified water and mixed uniformly. The mixed liquid may be a saturated aqueous solution in which the entire amount of the polymer compound is dissolved in the purified water, or a portion of the polymer compound is dissolved in the purified water.

The pKa1 of the polymer compound at 25° C. is preferably 8 or more, more preferably 8.5 or more. If the pKa1 at 25°C of the polymer compound is 8 or more, the surface of the polymer compound will be in an appropriate charge state during the interaction between the polymer compound and the virus, and the virus will be effectively captured and the virus infection inhibitor will be effective. In addition to improving the virus infection inhibiting effect, whitening of the surface of the base material can be generally prevented even when the base material contains a virus infection inhibitor. The pKa1 of the polymer compound at 25° C. is preferably 12 or less, more preferably 11 or less, and even more preferably 10 or less. Here, when the electrolyte B-H ⁺ is ionized into B and H ⁺ to take the ionization equilibrium equation (b), the acid dissociation constant Ka is defined by the equation (c), and pKa is the acid dissociation constant Ka It is defined as the common logarithm (d) of the reciprocal of .
The polymer compound used herein 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 of a polymer having a hydroxyl group and an amino functional group-containing monomer.

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 that is a component of a polymer compound. In the present invention, "pKa1 of a monomer containing an amino functional group or a salt thereof that is a constituent element of a polymer compound" is referred to as "pKa1 of a polymer compound." When the monomer containing the amino functional group or its salt, which is a component of the polymer compound, is a polyvalent amine, the conjugate acid of the polyvalent amine undergoes ionization in multiple stages, and pKa1 is the ionization constant of the first stage. It refers to pKa calculated based on.

The pKa1 of a polymer compound at 25°C is a value measured by titration. Specifically, titration is performed at 25°C using the hydrochloride of an amino functional group-containing monomer, which is a constituent element of a polymer compound, and sodium hydroxide, and the titration is carried out at the half-equivalence point (half the amount at which neutralization is completed). pKa1 can be determined by measuring the pH at 25° C. at the point where the solution was dropped. When the amino functional group-containing monomer is a free amine, pKa1 can be determined by the method described above after converting it into a hydrochloride. As a method for converting free amine into hydrochloride, for example, an amino functional group-containing monomer is mixed with a 1 mol% hydrochloric acid aqueous solution, all of the amino groups contained in the amino functional group-containing monomer are converted to hydrochloride, and then frozen. Examples include a method of removing hydrochloric acid and water by a general-purpose method such as drying.

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 surface of the substrate can be generally prevented even when the substrate contains a virus infection inhibitor. Furthermore, if the polymer compound does not contain an aromatic ring, the bulk of the polymer compound will be reduced, allowing the molecular structure containing the amino functional group to efficiently interact with the virus, which will result in an excellent virus. Demonstrates infection prevention effect.

The aromatic ring includes not only a monocyclic aromatic ring but also a fused aromatic ring formed by condensing a complex of 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 has one or more hydrogen atoms removed (extracted) from the aromatic ring and the fused aromatic ring, and is 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 substrate and can impart an excellent virus infection inhibiting effect to the substrate. The D90 particle diameter 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 even more preferably 3.5 μm or more. The D90 particle diameter 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 12 μm or less. The following are more preferable. When the D90 particle size is 1 μm or more, the surface area of the entire polymer compound becomes small, the agglomeration of the virus infection inhibitor is reduced, and the polymer compound and the virus are in a form where it is easy to interact with each other. The virus infection inhibiting effect is improved, and even when the base material contains the virus infection inhibiting effect, whitening of the surface of the base material can be generally prevented. When the D90 particle size is 50 μm or less, it is possible to prevent the aggregation of the virus infection inhibitor and increase the surface area to facilitate contact with the virus, thereby improving the virus infection prevention effect of the virus infection prevention member. Even when the base material contains a virus infection inhibiting effect, whitening of the surface of the base material can be generally prevented.

As described later, the D90 particle size of a polymer compound is the particle size (90% cumulative particle size) at which the cumulative frequency (accumulation from particles with small particle size) in the volume-based particle size distribution determined by the laser scattering method is 90%. ). When the polymer compound includes multiple types of polymer compounds, the D90 particle diameter of the polymer compound is a value measured based on the entire polymer compound.

The virus infection inhibitor may be used by being attached (supported) on the surface of the base particles. By 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 whitening of the base material can be more effectively prevented. Furthermore, the surface area of the virus infection inhibitor can be increased, sufficient contact between the virus infection inhibitor and the virus can be ensured, and the virus infection inhibiting effect of the virus infection inhibitor can be fully exhibited.

The base particles to which the virus infection inhibitor is attached are not particularly limited as long as they do not inhibit the virus infection inhibiting effect of the virus infection inhibitor. The 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-butadiene rubber (NBR), etc. Synthetic rubbers may be mentioned, with styrene resins and acrylic resins being preferred.

Styrenic resins are not particularly limited, and examples include homopolymers or copolymers containing styrene monomers as monomer units, such as styrene, methylstyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, chlorostyrene, and bromostyrene. Examples include copolymers containing, as monomer units, a styrene monomer and one or more vinyl monomers copolymerizable with the styrene monomer.

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

The acrylic resin is not particularly limited, and includes, for example, a homopolymer containing an acrylic monomer such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, or pentyl (meth)acrylate as a monomer unit; Examples include copolymers, 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.

Examples of vinyl monomers that can be copolymerized with acrylic monomers include acrylonitrile, methacrylonitrile, maleic anhydride, and acrylamide.

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

It is preferable that the synthetic resin constituting the resin particles contains an aromatic ring. The aromatic ring attracts the hydrophobic part of the polymer compound attached to the surface of the resin particle and has the effect of orienting the amino functional group and carboxy group outward, thereby enhancing the virus infection inhibiting effect of the virus infection inhibitor. It can be used more effectively.

The aromatic ring may be a monocyclic aromatic ring or a complex of monocyclic aromatic rings condensed (fused aromatic ring). The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, biphenyl, and phenoxyphenyl. The aromatic ring has one or more hydrogen atoms removed (extracted) from the aromatic ring and the fused aromatic ring, and is bonded to other atoms through covalent bonds.

The amount of the 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 more preferably 10 parts by mass or more based on 100 parts by mass of the resin particles. When the amount of the 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, and the virus infection inhibiting effect of the virus infection inhibitor can be more effectively exhibited. I can do it.

The amount of the polymer compound attached to the resin particles is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, more preferably 600 parts by mass or less, and more preferably 400 parts by mass or less based on 100 parts by mass of the resin particles. When the amount of the polymer compound attached is 1000 parts by mass or less, the virus infection inhibitors are not bonded to each other, and the virus infection inhibitors are efficiently disposed on the resin particle surface, improving the virus infection inhibiting effect.

The method of adhering the virus infection inhibitor to the surface of the resin particles is not particularly limited, and for example, the adhesive force of the virus infection inhibitor may be used, or the virus infection inhibitor may be adhered to the surface of the resin particles using a binder resin. However, it is preferable that the polymer compound is attached to the surface of the resin particles by the adhesive force of the polymer compound itself, so that the virus infection inhibiting effect of the virus infection inhibitor can be effectively exhibited. .

The virus infection inhibitor has a virus infection inhibiting effect against various viruses through the action of a polymer compound, and exhibits an excellent virus infection inhibiting effect against both enveloped viruses and non-enveloped viruses.

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

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

The virus infection inhibiting agent can be incorporated into the base material described below to constitute a virus infection inhibiting member, and can impart an excellent virus infection inhibiting effect to the base material without substantially causing whitening on the surface of the base material. I can do it.

The base material containing the virus infection inhibitor is not particularly limited as long as it is desired to impart a virus infection inhibiting effect, and examples include paints, synthetic resin moldings, wallpaper, decorative sheets, flooring materials, textile products (textiles , non-woven fabrics, knitted fabrics), interior products and interior materials for vehicles (e.g. cars, airplanes, ships, etc.) (seats, child seats and the foam materials that make up these, etc.), kitchen products, baby products, architectural interior materials Examples include.

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

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

The content of the polymer compound in the base material is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and 2 parts by mass based on 100 parts by mass of the base material. The above is more preferable. 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. . When the content of the polymer compound in the base material is 0.1 parts by mass or more, the virus infection inhibiting effect of the virus infection inhibiting member can be improved. When the content of the polymer compound in the base material is 30 parts by mass or less, the polymer compound does not aggregate and is easily dispersed uniformly without affecting the physical properties of the base material, thereby improving the effect of inhibiting virus infection. will improve.

The virus infection inhibiting agent constitutes a virus infection inhibiting paint by including it in the paint. A coating film formed from a virus infection inhibiting paint exhibits an excellent virus infection inhibiting effect, and whitening of the coating film surface is generally prevented, making it possible to form a coating film with excellent appearance.

As the paint, a conventionally known paint is used. The paint has improved dispersibility of the virus infection inhibitor, can form a coating film having an excellent virus infection inhibiting effect, and can be used as both a hydrophobic paint and a hydrophilic paint. The hydrophobic paint is not particularly limited, and includes, for example, oil-based paints (eg, blended paints, oil varnishes, etc.), cellulose paints, synthetic resin paints, and the like. Paints also include photocurable paints that polymerize to produce a binder component when irradiated with radiation such as ultraviolet rays. The water-based paint is not particularly limited, and examples thereof include water-based urethane paint, water-based silicone paint, water-based fluorine paint, and water-based inorganic paint.

The paint may contain a solvent to adjust the viscosity. As the solvent, an organic solvent is preferable 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. Note that the solvents may be used alone or in combination of two or more.

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% 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 inhibiting paint exhibits an excellent virus infection inhibiting effect. When the content of the polymer compound is 10% by mass or less, the polymer compound does not aggregate and is easily dispersed uniformly, which improves the effect of inhibiting virus infection and makes it difficult to affect the physical properties of the base material, which is preferable. .

Furthermore, paints may contain additives such as pigments, plasticizers, curing agents, extenders, fillers, anti-aging agents, thickeners, surfactants, etc., as long as they do not impair their physical properties. good.

Examples of methods for incorporating the virus infection inhibitor into the paint include a method in which the virus infection inhibitor and paint are supplied to a dispersion device and mixed uniformly. Note that examples of the dispersion device include a high-speed mill, a ball mill, and a sand mill.

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

Polymer compounds 1 to 16 were prepared.

[Polymer 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.

- Polymer compound 2 [having a repeating unit represented by formula (9)]
1 part by weight of raw material polyvinyl alcohol (PVA-1, degree of saponification: 98.5 mol%, degree of polymerization: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). After that, 8.0 parts by weight of L-tyrosine methyl and 6 parts by weight of tetra t-butyl dilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were further added, and the mixture was stirred at 30°C for 6 hours. , a transesterification reaction was performed. Thereafter, the powder of polymer compound 2 was obtained by reprecipitating in tetrahydrofuran, washing with tetrahydrofuran, and drying. In formula (9), m:n=86:14.

- 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.

- 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.

- 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.

- 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.

- 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.

- 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.

- Polymer compound 9 [having a repeating unit represented by formula (15)]
1 part by weight of raw material polyvinyl alcohol (PVA-1, degree of saponification: 98.5 mol%, degree of polymerization: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). After that, 3.0 parts by weight of N,N-dimethylglycine methyl ester and 6 parts by weight of tetra t-butyl dilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13% by weight) were further added, and the mixture was heated at 30°C for 6 hours. Transesterification reaction was carried out by stirring. Thereafter, the powder was reprecipitated 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 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.

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

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

・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 its main chain.

- 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.

- Polymer compound 15 [having a repeating unit represented by formula (19)]
1 part by weight of raw material polyvinyl alcohol (PVA-1, degree of saponification: 98.5 mol%, degree of polymerization: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). After that, 1.7 parts by weight of methyl L-pyroglutamate and 6 parts by weight of tetra-t-butyl dilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) are further added, and the mixture is stirred at 30°C for 6 hours. A transesterification reaction was performed. Thereafter, the powder was reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and dried to obtain a powder of polymer compound 15. m:n=81:19.

- Polymer compound 16 [having a repeating unit represented by formula (20)]
1 part by weight of raw material polyvinyl alcohol (PVA-1, degree of saponification: 98.5 mol%, degree of polymerization: 300) was added to 49 parts by weight of dimethyl sulfoxide (DMSO) and dissolved (concentration: 2% by mass). Thereafter, 3.3 parts by weight of methyl N-acetyl-L-alanine and 6 parts by weight of tetra-t-butyl dilithium zincate (TBZL, solvent: tetrahydrofuran, concentration: 13% by mass) were further added, and the mixture was heated at 30°C for 6 hours. The transesterification reaction was carried out by stirring. Thereafter, the powder was reprecipitated in tetrahydrofuran, washed with tetrahydrofuran, and 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 all are natural numbers of 2 or more. In formula (17), x is a natural number of 2 or more.

Among the structural formulas shown above, the structural formula expressed as 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 roll press device (Seishin Enterprise Co., Ltd., product name "Model 150") under operating conditions of a rotation speed of 25 rpm and a pushing force of 25 tons, the polymer compound is coarsely pulverized using a jet mill device (Nissin Engineering Co., Ltd., product name "SJ") under operating conditions of 25 rpm and a pushing force of 25 tons. -500'') under operating conditions of a polymer compound supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa to obtain particles of a polymer compound. Table 1 shows the D90 particle diameter of the particles of the polymer compound.

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 Examples and Comparative Examples. In Table 1, "pH of 5% by mass aqueous solution at 25°C" and "pKa1 at 25°C" are simply written as "pH" and "pKa1", respectively.

(Examples 1 to 10 and Comparative Examples 1 to 6)
A virus infection inhibitor containing 5 parts by mass of particles of the polymer compound shown in Table 1 prepared in the manner described above, and 95 parts by mass of ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by Coattec Co., Ltd.). A paint for preventing virus infection was prepared by mixing the two. The virus infection inhibiting paint was applied onto a polyethylene film to a thickness of 18 μm using a wire bar coater #8 to form a coating layer.

The UV-curable acrylic paint was cured by irradiating the coating layer with ultraviolet rays with a wavelength of 365 nm at a cumulative light intensity of 500 mJ/cm ² at 25°C using a UV conveyor device (“ECS301G1” manufactured by Eye Graphics). A coating film having a thickness of 18 μm was formed.

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

[Antiviral properties]
Using the coating film obtained above, an antiviral test was conducted using feline calicivirus (non-enveloped virus) and influenza virus (enveloped virus) in the following manner.

(Antiviral test)
Regarding the coating film, a test piece was prepared by cutting out a planar square shape with each side of 5.0 cm.

The surface of the coating film of the obtained test piece was wiped 10 times with a square-shaped nonwoven fabric (manufactured by Nippon Paper Crecia Co., Ltd., trade name "Kimwipe S-200") having a side of 10 cm to obtain a test coating film.

The obtained test coating was subjected to an antiviral test for feline calicivirus and influenza virus (test time: 24 hours) in accordance with ISO21702. After the reaction, the virus infectivity of the test coating was calculated using the plaque method for the virus suspension.

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

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

[Whitening]
Whitening property evaluation was conducted in accordance with JIS A 1454 Polymer-based Floor Material Test Method Stain Resistance Test. In a test room with a temperature of 23° C. and a humidity of 50%, 2 ml of purified water was dropped onto the surface of the test coating film, covered with a watch glass, and allowed to stand for 24 hours. Thereafter, it was removed with a household neutral detergent, and the surface was further wiped with industrial alcohol, and left to stand in a test room for 1 hour. The haze of the coating film was evaluated in accordance with JIS K 7361. The haze value (%) was measured using a haze meter (trade name: HM-150, manufactured by Murakami Color Research Institute) at a room temperature of 25° C. and a relative humidity of 40%. The larger the haze value, the greater the degree of whitening of the coating surface.

The virus infection inhibitor of the present invention can be incorporated into base materials such as paint films, wallpapers, decorative sheets, flooring materials, textile products, interior and interior materials for vehicles, kitchen products, baby products, and architectural interior materials. Even if the surface of the base material is contaminated, whitening of the surface of the base material can be generally prevented, and a virus infection prevention member having an excellent virus infection prevention effect and an excellent appearance can be constructed.

(Cross reference to related applications)
This application claims priority based on Japanese Patent Application No. 2022-049777 filed on March 25, 2022, and the disclosure of this application is incorporated herein by reference in its entirety. .

Claims

Contains a polymer compound having 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 thereof and having a weight average molecular weight of 1000 or more. , a virus infection inhibitor characterized in that the main chain of the polymer compound does not contain a nitrogen atom.
The virus infection inhibitor according to claim 1, wherein the nitrogen atom content of the polymer compound is 0.1 to 50%.
The virus infection inhibitor according to claim 1 or 2, wherein the amino functional group contains a secondary amino group.
The virus infection inhibitor according to any one of claims 1 to 3, wherein the polymer compound has a weight average molecular weight of 1,000 to 1,000,000.
The virus infection inhibitor according to any one of claims 1 to 4, wherein the polymer compound contains a carboxy group or a salt thereof.
The virus infection inhibitor according to any one of claims 1 to 5, wherein the pH of the 5% by mass aqueous solution of the polymer compound at 25°C is 4 or less or 9 or more.
The virus infection inhibitor according to any one of claims 1 to 6, wherein the polymer compound has a pKa1 of 8 or more.
The virus infection inhibitor according to any one of claims 1 to 7, wherein the amino functional group forms a cyclic skeleton.
A virus infection inhibiting member comprising a base material and the virus infection inhibiting agent according to any one of claims 1 to 8 contained in the base material.
A virus infection inhibiting paint comprising a paint and the virus infection inhibiting agent according to any one of claims 1 to 8, which is contained in the paint.