WO2023171556A1

WO2023171556A1 - Viral infection inhibitor, viral infection inhibiting product, viral infection inhibiting paint, and resin composition

Info

Publication number: WO2023171556A1
Application number: PCT/JP2023/007989
Authority: WO
Inventors: 大地川村; 活志山崎; 信緒松木; 和也西原; 太郎鈴木
Original assignee: 積水化学工業株式会社
Priority date: 2022-03-10
Filing date: 2023-03-03
Publication date: 2023-09-14
Also published as: TW202348137A

Abstract

The present invention provides a viral infection inhibitor exhibiting excellent ethanol resistance and having an excellent viral infection inhibiting effect (antiviral property) even after contact with an ethanol solution for sterilization. The viral infection inhibitor of the present invention is characterized by comprising a viral infection inhibiting compound having one or more acidic functional groups with the one or more acidic functional groups being bonded to a nitrogen atom through one or more carbon atoms. Therefore, the viral infection inhibitor exhibits excellent ethanol resistance and has an excellent viral infection inhibiting effect (antiviral property) even after contact with an ethanol solution for sterilization, and maintains the viral infection inhibiting effect against various types of viruses over a long period of time.

Description

Virus infection inhibitors, virus infection prevention products, virus infection prevention paints and resin compositions

The present invention relates to a virus infection inhibiting agent, a virus infection inhibiting product, a virus infection inhibiting paint, and a resin composition.

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.

In order to solve these problems, Patent Document 1 discloses that the paint is made of a paint containing an antiviral agent that is calcium carbonate supported on a sulfonic acid surfactant, and that the paint is an ultraviolet curable paint or an electron beam curable paint. An antiviral surface treatment agent is disclosed.

Japanese Patent Application Publication No. 2020-139165

On the other hand, even with antiviral products such as articles whose surfaces are treated with antiviral agents or antiviral films containing antiviral agents, antiviral products are used to remove viruses and prevent viral infections. It is common practice to disinfect surfaces with a disinfectant ethanol solution.

However, when an antiviral product treated with the above-mentioned antiviral surface treatment agent is disinfected with a disinfecting ethanol solution, there is a problem in that the antiviral properties of the antiviral surface treatment agent are significantly reduced. are doing.

The present invention provides a virus infection inhibiting agent with excellent ethanol resistance that has an excellent virus infection inhibiting effect (antiviral property) even when contacted with a disinfectant ethanol solution, and a virus infection inhibiting particle using this virus infection inhibiting agent. provides virus infection prevention products, virus infection prevention coatings, and resin compositions.

The virus infection inhibiting agent of the present invention includes a virus infection inhibiting compound that has one or more acidic functional groups and the acidic functional group is bonded to a nitrogen atom via one or more carbon atoms.

The virus infection inhibiting particles of the present invention include a base particle and the virus infection inhibiting agent attached to the surface of the base particle.

The virus infection inhibiting product of the present invention includes a base material and the virus infection inhibiting agent attached to the surface of the base material.

The virus infection inhibiting paint of the present invention includes a paint and the virus infection inhibiting agent contained in the paint.

The resin composition of the present invention includes a synthetic resin and the virus infection inhibitor contained in the synthetic resin.

The virus infection inhibiting agent of the present invention contains a virus infection inhibiting compound that has one or more acidic functional groups and the acidic functional group is bonded to a nitrogen atom via one or more carbon atoms, so it can be used for disinfection. It has excellent ethanol resistance and has an excellent virus infection prevention effect (antiviral property) even after contact with an ethanol solution, and maintains virus infection prevention effect for a long period of time against various types of viruses.

The virus infection inhibiting agent of the present invention contains as an active ingredient a virus infection inhibiting compound that has one or more acidic functional groups and the acidic functional group is bonded to a nitrogen atom via one or more carbon atoms. Note that the virus infection inhibiting compounds may be used alone or in combination of two or more.

The virus infection inhibiting agent contains a virus infection inhibiting compound that has one or more acidic functional groups, and the acidic functional group is bonded to a nitrogen atom via one or more carbon atoms. The virus infection inhibitor can maintain an excellent virus infection inhibiting effect even after coming into contact with a disinfectant ethanol solution (ethanol resistance). Note that the ethanol solution for disinfection is an aqueous solution containing 80% by volume of ethanol.

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

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

For example, a paint is prepared by supplying a virus infection inhibitor containing 30 mg of a virus infection inhibiting compound into 970 mg of a solvent-free ultraviolet curable acrylic resin and uniformly mixing the mixture. The obtained paint is applied onto a polyethylene film to a thickness of 18 μm to form a coating layer. This coating layer is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 500 mJ/cm ² to cure the ultraviolet curable acrylic resin to form a coating film with a thickness of 18 μm, which is used as 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 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. By subtracting the virus infection value of the test coating film from the virus infection value of the blank coating film, the difference in the common logarithm value of the virus infection titer (antiviral activity value) is calculated.

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 content of the virus infection inhibiting compound in the virus infection inhibitor is preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and 99% by mass or more. is more preferable, and 100% by mass is more preferable.

The content of the virus infection inhibiting compound in the virus infection inhibitor is preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, based on the active ingredients. More preferably 99% by mass or more, and even more preferably 100% by mass.

The number of acidic functional groups in the virus infection inhibiting compound is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, since the ethanol resistance of the virus infection inhibitor is improved. The number of acidic functional groups in the virus infection inhibiting compound is preferably 5 or less since the ethanol resistance of the virus infection inhibiting agent is improved.

The acidic functional group refers to a functional group that can release hydrogen ions (protons) in an aqueous solution. The acidic functional group is not particularly limited, and includes, for example, a carboxy group (-COOH), a sulfo group (sulfonic acid group) (-SO ₃ H), a phosphonic acid group [-P(=O)(OH) ₂ ], Examples include phosphoric acid group [-OPO(OH) ₂ ], and carboxy groups, sulfo groups, and phosphonic acid groups are preferred because the virus infection inhibitor has excellent ethanol resistance. A group is more preferable, and a carboxy group is more preferable.

The acidic functional group contained in the virus infection inhibiting compound may be a salt. Salts of acidic functional groups are not particularly limited, and include, for example, sodium salts, calcium salts, ammonium salts, magnesium salts, barium salts, and the like.

The salt of the carboxy group contained in the virus infection inhibiting compound is not particularly limited, and includes, for example, sodium salt (-COONa), calcium salt [(-COO ^- ) ₂ Ca ²⁺ ], ammonium salt (-COO ^- NH ₄ ⁺ ), magnesium salt [(-COO ^- ) ₂ Mg ²⁺ ], barium salt [(-COO ^- ) ₂ Ba ²⁺ ], and the like.

The sulfo group salt contained in the virus infection inhibiting compound is not particularly limited, and includes, for example, sodium salt (-SO ₃ Na), calcium salt [(-SO ₃ ^- ) ₂ Ca ²⁺ ], ammonium salt ( -SO ₃ ^- NH ₄ ⁺ ), magnesium salt [(-SO ₃ ^- ) ₂ Mg ²⁺ ], barium salt [-(SO ₃ ^- ) ₂ Ba ²⁺ ], and the like.

The salt of the phosphonic acid group contained in the virus infection inhibiting compound is not particularly limited, and includes, for example, the sodium salt [-P(=O)(ONa) ₂ ], the calcium salt [-P(=O)(O ^- ) ₂ Ca ²⁺ ], ammonium salt (-P(=O)(O ^- NH ₄ ⁺ ) ₂ ), magnesium salt [-P(=O)(O ^- ) ₂ Mg ²⁺ ], barium salt [- P(=O)(O ^- ) ₂ Ba ²⁺ ] and the like.

In the viral infection inhibiting compound, the acidic functional group is bonded to the nitrogen atom via one or more carbon atoms. In other words, in a virus infection inhibiting compound, if the acidic functional group is directly connected to the nitrogen atom by the shortest route, there is one or more carbon atoms between the acidic functional group and the nitrogen atom. Existing. Note that "connecting by the shortest route" refers to a route that minimizes the number of atoms existing between the atom to which the acidic functional group is directly bonded and the nitrogen atom. The types of bonds connecting atoms in the route are not particularly limited. The acidic functional group only needs to be bonded to a nitrogen atom through one or more carbon atoms, and the carbon atom may be a carbon atom that constitutes a chain skeleton or a carbon atom that constitutes a cyclic skeleton. Any atom may be used, but since the virus infection inhibitor has excellent ethanol resistance, it is preferable to include a carbon atom that constitutes a chain skeleton, and carbon atoms that constitute a chain skeleton are preferred. It is more preferable that As the cyclic skeleton, an alicyclic skeleton is preferable, and a cycloalkane skeleton is preferable. The chain skeleton also includes cases where the number of carbon atoms is one. In compounds that inhibit virus infection, when the acidic functional group directly connects the atom to the nitrogen atom via the shortest route, there is a particularly limited upper limit on the number of carbon atoms that can exist between the acidic functional group and the nitrogen atom. Not done. The number of carbon atoms present between the acidic functional group and the nitrogen atom is preferably 10 or less, for example. In the viral infection inhibiting compound, the acidic functional group may be attached to the nitrogen atom through up to 10 carbon atoms.

The content of nitrogen atoms in the virus infection inhibiting compound is preferably 5% or more, more preferably 6% or more. The nitrogen atom content in the virus infection inhibiting compound is preferably 12% or less, more preferably 11% or less. When the nitrogen atom content in the virus infection inhibiting compound is within the above range, the acidic functional group and nitrogen atom of the virus infection inhibiting compound will interact appropriately within the molecule, and the solubility in ethanol solution for disinfection will be reduced. The ethanol resistance of the virus infection inhibitor improves.

Note that the content (%) of nitrogen atoms in the virus infection inhibiting compound refers to a value calculated based on the following formula. When the virus infection inhibiting compound forms a hydrate, the number of atoms of water (H ₂ O) molecules is not included in the total atomic weight of all atoms constituting the virus infection inhibiting compound.
Content of nitrogen atoms (%)
=100×(sum of atomic weights of all nitrogen atoms in the virus infection inhibiting compound)
/ (sum of atomic weights of all atoms constituting the virus infection inhibiting compound)

The pH of the 0.5% by mass aqueous solution of the virus infection inhibiting compound at 25°C is such that even if the virus infection inhibiting compound comes into contact with a disinfecting ethanol solution, the acidity of the acidic functional group of the virus infection inhibiting compound is easily maintained; Since the ethanol resistance of the virus infection inhibitor is improved, it is preferably 4.5 or less. The pH at 25°C of a 0.5% by mass aqueous solution of a virus infection inhibiting compound is the pH value at 25°C of a mixed solution in which 0.5 g of the virus infection inhibiting compound is added to 99.5 g of purified water and mixed uniformly. say. The mixed solution may be a saturated aqueous solution in which the entire amount of the virus infection inhibiting compound is dissolved in purified water, or a portion of the virus infection inhibiting compound is dissolved in purified water.

As the virus infection inhibiting compound, compounds represented by the following formulas (1) and (2) are preferred. First, the virus infection inhibiting compound having the structural formula represented by formula (1) will be explained.

In formula (1), R ¹ each independently represents a hydrogen atom, -CH ₂ -R ³ or -A ¹ -R ³ . The virus infection inhibiting compound has two R ^1s , and the two R ^1s may be the same or different from each other. R ³ represents a carboxyl group, a phosphonic acid group, or a sulfo group, and a carboxy group and a phosphonic acid group are preferable because they improve the ethanol resistance of the virus infection inhibitor.

A ¹ represents a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a 4-, 5-, or 6-membered ring. Carbon atoms other than hydrogen atoms may be the same or different from each other. The carbon atom from which a hydrogen atom is removed (withdrawn) is a carbon atom that directly constitutes a 4-, 5-, or 6-membered ring, and is not bonded to a 4-, 5-, or 6-membered ring. Carbon atoms constituting substituents are not included. Hydrogen bonded to carbon atoms of the 4-membered ring, 5-membered ring and 6-membered ring may be substituted with a substituent. A ¹ is a divalent substituent formed by removing (withdrawing) two hydrogen atoms from the carbon atoms of a 4-membered alicyclic ring, 5-membered alicyclic ring, or 6-membered alicyclic ring. preferable. A ¹ is more preferably a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of cyclobutane, cyclopentane or cyclohexane.

R ² represents -CH ₂ -R ⁴ or -A ² -R ⁴ . R ⁴ represents a carboxy group, a phosphonic acid group, or a sulfo group, and a carboxy group or a phosphonic acid group is preferable since the ethanol resistance of the virus infection inhibitor is improved.

A ² represents a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a 4-, 5-, or 6-membered ring. Carbon atoms other than hydrogen atoms may be the same or different from each other. The carbon atom from which a hydrogen atom is removed (withdrawn) is a carbon atom that directly constitutes a 4-, 5-, or 6-membered ring, and is not bonded to a 4-, 5-, or 6-membered ring. Carbon atoms constituting substituents are not included. Hydrogen bonded to carbon atoms of the 4-membered ring, 5-membered ring and 6-membered ring may be substituted with a substituent. A ² is a divalent substituent formed by removing (withdrawing) two hydrogen atoms from the carbon atoms of a 4-membered alicyclic ring, 5-membered alicyclic ring, or 6-membered alicyclic ring. preferable. A ² is preferably a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of cyclobutane, cyclopentane or cyclohexane.

In ^formula (1), at least one of the two R ^1s is preferably -CH ₂ -R ³ because the ethanol resistance of the virus infection inhibitor is improved, and -CH ₂ --COOH or --CH ₂ --P(=O)(OH) ₂ is more preferred, and --CH ₂ --COOH is more preferred. Two R ¹ 's may be the same or different.

In formula (1), R ² is preferably -CH ₂ -R ⁴ , and -CH ₂ -COOH or -CH ₂ -P(=O), since the ethanol resistance of the virus infection inhibitor is improved. (OH) ₂ is more preferred, and -CH ₂ -COOH is more preferred.

In formula (1), R ¹ and R ² are preferably -CH ₂ -COOH, since this improves the ethanol resistance of the virus infection inhibitor. That is, as the virus infection inhibiting compound represented by formula (1), triglycolamic acid [formula (5)] is preferable.

In formula (1), two or more substituents of R ¹ and R ² are preferably -CH ₂ -COOH, since the ethanol resistance of the virus infection inhibitor is improved; Preferably, one R ¹ ^and R ² out of R 1 are -CH ₂ -COOH. As the virus infection inhibiting compound represented by formula (1), iminodiacetic acid [formula (15)] is preferable.

In formula (1), A ² is a divalent compound produced by removing (withdrawing) two hydrogen atoms from a 4- or 5-membered ring carbon atom because it improves the ethanol resistance of the virus infection inhibitor. A substituent is preferable, and a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of cyclobutane or cyclopentane is more preferable.

In formula (1), it is preferable that R ² is -A ² -R ⁴ and both R ¹ are hydrogen atoms, since this improves the ethanol resistance of the virus infection inhibitor. In formula (1), R ² is -A ² -R ⁴ and A ² is a divalent substituent formed by removing (withdrawing) two hydrogen atoms from a carbon atom of a 5-membered or 6-membered ring. , it is more preferable that both R ¹ are hydrogen atoms. In formula (1), R ² is -A ² -R ⁴ and A ² is an alicyclic 5-membered ring or an alicyclic 6-membered ring in which two hydrogen atoms are removed (extracted). ) In the resulting divalent substituent, it is more preferable that both R ¹ are hydrogen atoms. In formula (1), R ² is -A ² -R ⁴ and A ² is a divalent substituent formed by removing (withdrawing) two hydrogen atoms from the carbon atoms of cyclopentane or cyclohexane, and two It is preferable that both R ¹ are hydrogen atoms. In formula (1), R ² is -A ² -R ⁴ and A ² is a divalent substituent formed by removing (withdrawing) two hydrogen atoms from the carbon atoms of cyclohexane, and two R ¹ It is more preferable that both are hydrogen atoms.

In formula (1), the virus infection inhibiting compound in which R ² is -A ² -R ⁴ and both R ¹ are hydrogen atoms is, for example, 1-amino-1-cyclobutanecarboxylic acid [formula (6 )], cycloleucine [formula (7)], 1-aminocyclohexanecarboxylic acid [formula (8)], 3-aminocyclohexanecarboxylic acid [formula (9)], etc.; ], 1-aminocyclohexanecarboxylic acid [formula (8)], and 3-aminocyclohexanecarboxylic acid [formula (9)] are preferred.

Next, a virus infection inhibiting compound having the structural formula represented by formula (2) will be explained.

In formula (2), R ⁵ each independently represents a hydrogen atom, -CH ₂ -R ⁷ or a structure represented by formula (3). At least two of R ⁵ have a structure represented ^by -CH ₂ -R ⁷ or formula (3). The four R ⁵ 's may be the same or different. R ⁷ represents a carboxy group, a phosphonic acid group or a sulfo group. R ⁶ represents -(CH ₂ )n- or a structure represented by formula (4). However, n is an integer from 1 to 3.

R ⁸ represents a carboxy group, a phosphonic acid group or a sulfo group. R ⁹ represents a carboxy group, a phosphonic acid group or a sulfo group. R ⁷ to R ⁹ may be the same or different.

In formula (4), R ¹⁰ represents a carboxy group, a phosphonic acid group or a sulfo group. However, m is an integer from 1 to 3. p is an integer from 1 to 3.

In formula (2), R ⁷ is preferably a carboxy group or a phosphonic acid group since the ethanol resistance of the virus infection inhibitor is improved.

In formula (2), the four R ⁵ groups are preferably -CH ₂ -R ⁷ because this improves the ethanol resistance of the virus infection inhibitor.

In formula (2), since the ethanol resistance of the virus infection inhibitor is improved, it is necessary that two ^R5s have the structure shown in formula (3) and the other two ^R5s are hydrogen atoms. Preferably, a substituent having a structure represented by formula (3) as R ⁵ to one nitrogen atom and a substituent having a hydrogen atom bonded to the other nitrogen atom and having a structure represented by formula (3) as R ⁵ and More preferably, hydrogen atoms are bonded.

In formula (2), since the ethanol resistance of the virus infection inhibitor is improved, one R ⁵ of the two R ⁵ bonded to the same nitrogen atom has a structure represented by formula (3). In addition, it is preferable that the other R ⁵ is a hydrogen atom.

In formula (3), R ⁸ and R ⁹ are preferably a carboxy group or a phosphonic acid group, and more preferably a carboxy group, since the ethanol resistance of the virus infection inhibitor is improved.

In formula (2), R ⁶ is preferably -(CH ₂ )n-, and -(CH ₂ ) ₂ - or -(CH ₂ ) ₃ - is more preferable because R 6 improves the ethanol resistance of the virus infection inhibitor. preferable.

In formula (4), R ¹⁰ is preferably a carboxy group or a phosphonic acid group, more preferably a carboxy group, since the ethanol resistance of the virus infection inhibitor is improved.

Examples of the virus infection inhibiting compound represented by formula (2) include ethylenediaminetetraacetic acid [formula (10)], 1,3-diaminopropanetetraacetic acid [formula (11)], ethylenediaminesuccinic acid [formula (12)], Diethylenetriaminepentaacetic acid [formula (13)] and ethylenediaminetetra(methylenephosphonic acid) [formula (14)] are preferred.

The virus infection inhibitor contains a virus infection inhibiting compound as an active ingredient, but the method for producing the virus infection inhibitor is not particularly limited. A viral infection inhibitor can be produced by mixing in the following manner.

The virus infection inhibitor has a virus infection inhibiting effect against various viruses due to the action of the virus infection inhibiting 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 inhibitor may be used by being attached (supported) on the surface of the base particles. By attaching the virus infection inhibiting compound to the surface of the base particles, the virus infection inhibiting agent can be uniformly dispersed in the substrate described below without forming lumps. Therefore, 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. Examples include synthetic rubbers, acrylic resins and styrene resins are preferred, and polystyrene is more 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 compound (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 virus infection-inhibiting compound attached to the surface of the resin particle and acts to orient the acidic functional groups outward, making the virus infection-inhibiting agent more effective. can be demonstrated 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. An aromatic ring is one in which one or more hydrogen atoms bonded to carbon atoms that directly constitute the aromatic ring or fused aromatic ring are removed, and the hydrogen atoms are bonded to other atoms through covalent bonds. are combined.

The amount of the virus infection inhibiting compound attached to the base 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 base particles. . When the amount of the virus infection inhibiting compound attached is 1 part by mass or more, the virus infection inhibiting agent can be uniformly attached to the surface of the base particles, and the virus infection inhibiting effect of the virus infection inhibiting agent can be more effectively exhibited. be able to.

The amount of the virus infection inhibiting compound attached to the base particles is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less based on 100 parts by mass of the base particles. . When the amount of the virus infection inhibiting compound attached is 50 parts by mass or less, the virus infection inhibiting agents are not bonded to each other, and the virus infection inhibiting agent is efficiently disposed on the surface of the base particle, thereby improving the virus infection inhibiting effect.

The method of attaching the virus infection inhibitor to the surface of the base 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 attached to the surface of the base particles using a binder resin. However, in order to effectively exhibit the virus infection inhibiting effect of the virus infection inhibiting agent, the virus infection inhibiting compound must be attached to the surface of the base particle by the adhesive force of the virus infection inhibiting compound itself. is preferred.

The virus infection inhibiting agent and the virus infection inhibiting particles are used by being included in a base material to which it is desired to impart a virus infection inhibiting effect, and the base material containing the virus infection inhibiting agent exhibits the virus infection inhibiting effect as a virus infection inhibiting product. .

The base material containing the virus infection inhibitor or virus infection prevention particles is not particularly limited as long as it can contain the virus infection inhibitor, and examples thereof include synthetic resin molded bodies such as films, paints, wallpapers, decorative sheets, Flooring materials, textile products (woven, non-woven, knitted), internal 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 utensils , baby products, architectural interior materials, etc.

The synthetic resin constituting the synthetic resin molded article is not particularly limited, and includes, for example, thermoplastic resins (e.g., polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, Teflon (registered trademark), acrylonitrile butadiene styrene). Resin, acrylonitrile styrene resin, acrylic resin, polyvinyl alcohol, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyester, polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyether sulfone, polyarylate, polyetheretherketone, thermoplastic polyimide, polyamideimide, etc.), thermosetting resins (e.g., phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, silicone resins, polyurethanes, thermal curable polyimide, etc.). Note that the synthetic resins may be used alone or in combination of two or more kinds.

The virus infection inhibitor may be used by kneading it into a synthetic resin. The method for kneading the virus infection inhibitor into synthetic resin is to mix the virus infection inhibitor with the synthetic resin as a raw material to create a resin composition, and then use this resin composition to mold it using a general-purpose synthetic resin molding method. A virus infection inhibiting product in a desired shape can be obtained as a molded article. Examples of general-purpose synthetic resin molding methods include extrusion molding, injection molding, and blow molding. A resin composition containing a synthetic resin and a virus infection inhibitor is used as a synthetic resin molding masterbatch, and the synthetic resin molding masterbatch is mixed with the raw material synthetic resin to prevent viral infection using a general-purpose synthetic resin molding method. The blocking product may also be manufactured as a molded article.

[Masterbatch for synthetic resin molding]
A masterbatch for synthetic resin molding contains a synthetic resin and a virus infection inhibitor. Only one type of synthetic resin may be used, or two or more types may be used in combination. The synthetic resin may be a thermoplastic resin or a thermosetting resin, but a thermoplastic resin is preferable. Thermoplastic resins include polyolefin resin, polyvinyl chloride resin, polyamide resin, polycarbonate resin, polystyrene resin, polyester resin, acrylonitrile-butadiene-styrene resin (ABS resin), polyethylene terephthalate (PET), polyurethane resin, and polymethacrylic acid. Examples include methyl (PMMA).

The content of synthetic resin in the synthetic resin molding masterbatch is preferably 10% by mass or more, more preferably 20% by mass or more. The content of the synthetic resin in the synthetic resin molding masterbatch is preferably 80% by mass or less, more preferably 60% by mass or less.

The content of the virus infection inhibitor in the masterbatch for synthetic resin molding is preferably 10% by mass or more, more preferably 15% by mass or more. The content of the virus infection inhibitor in the masterbatch for synthetic resin molding is preferably 80% by mass or less, more preferably 70% by mass or less.

It is preferable that the resin composition, especially the masterbatch for synthetic resin molding, further contains a surfactant. The surfactant is not particularly limited and includes, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and anionic surfactants and nonionic surfactants. Agents are preferred. When a masterbatch for synthetic resin molding further contains a surfactant, the virus infection inhibiting compound is likely to be segregated on the surface of the resulting virus infection inhibiting product (molded product), and the ethanol resistance of the virus infection inhibiting product (molded product) is increased. You can further improve your sexuality.

Examples of anionic surfactants include, but are not limited to, alkyl phosphates such as sodium dodecyl phosphate, potassium dodecyl phosphate, sodium stearyl phosphate, and potassium stearyl phosphate, and polyoxyethylene (3) lauryl ether phosphate. Sodium, polyoxyethylene alkyl ether phosphate ester salts such as polyoxyethylene (3) potassium lauryl ether phosphate, polyoxyethylene (3) sodium lauryl phenyl ether phosphate, polyoxyethylene (3) potassium lauryl phenyl ether phosphate Polyoxyethylene alkyl phenyl ether phosphates, alkylbenzene sulfonates (e.g., dodecylbenzenesulfonic acid sodium salt, dodecylbenzenesulfonic acid potassium salt, dodecylbenzenesulfonic acid ammonium salt, dodecylbenzenesulfonic acid triethanolammonium salt, etc.) , α-olefin sulfonate, alkyldiphenyl ether sulfonate, polyoxyalkylene alkyl ether sulfate salt, etc., with alkylbenzene sulfonate being preferred.

Nonionic surfactants are not particularly limited, and include, for example, polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester (for example, polyethylene glycol distearate, etc.), Oxyethylene distyrenated phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene Alkylamines, polyoxyethylene fatty acid amides, fatty acid alkanolamides (e.g., coconut fatty acid alkanolamides such as coconut fatty acid dimethanolamide, coconut fatty acid diethanolamide, coconut fatty acid dipropanolamide, etc.), fatty acid alkylolamides, alkyl alkanolamides, acetylene Examples include glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer, and polyoxyethylene distyrenated phenyl ether, polyoxyethylene fatty acid ester, and fatty acid alkanolamide are preferred.

The amphoteric surfactant is not particularly limited and includes, for example, alkylaminoacetate betaine, alkylamidopropyl betaine, sulfobetaine, alkylamino (mono- or di)propionate, imidazolinium betaine, alkylamine oxide, alkylaminoethyl Glycine, alkyldi(aminoethyl)glycine, glycine n-(3-aminopropyl) C10-16 derivative, alkylpolyaminoethylglycine, alkylβ-alanine, alkyldiethanolamine, polyoxyalkylenealkylamine, oxyethylene-added surfactant of diamine Examples include.

The content of the surfactant in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more. The content of the surfactant in the resin composition is preferably 40% by mass or less, more preferably 30% by mass or less.

The masterbatch for synthetic resin molding is preferably a resin pellet because it has excellent moldability. By melting and molding resin pellets, it is possible to obtain a virus infection prevention product (molded article) with excellent virus infection prevention effects.

The shape of the resin pellet is not particularly limited, and examples include spherical, cylindrical, and prismatic shapes. From the viewpoint of stability of the pellet shape, a cylindrical shape is preferable. The maximum length dimension of the resin pellet is preferably 1 mm or more, more preferably 3 mm or more. The maximum length dimension of the resin pellet is preferably 10 mm or less, more preferably 7 mm or less.

The masterbatch for synthetic resin molding can be used by mixing it with other resin materials. The other resin material may be resin pellets. After mixing the synthetic resin molding masterbatch and the other resin materials to obtain a mixed resin material, the mixed resin material is molded to produce a virus infection prevention product (molded products) can be obtained.

A virus infection inhibiting paint can be constructed by including a virus infection inhibiting agent in the paint. As the paint, conventionally known paints are used, such as 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 paint may contain additives such as pigments, plasticizers, curing agents, extenders, fillers, anti-aging agents, thickeners, and surfactants within the range that does not impair its physical properties. In addition, as a method of incorporating the virus infection inhibitor into the paint, for example, a method of supplying the virus infection inhibitor and the paint to a dispersion device and uniformly mixing them can be mentioned. Note that examples of the dispersion device include a high-speed mill, a ball mill, and a sand mill.

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

The following compound was prepared as a virus infection inhibiting compound. These viral infection inhibiting compounds were used as viral infection inhibiting agents.

・Triglycolamic acid [formula (5)]
・1-amino-1-cyclobutanecarboxylic acid [formula (6)]
・Cycloleucine [Formula (7)]
・1-Aminocyclohexanecarboxylic acid [Formula (8)]
・3-Aminocyclohexanecarboxylic acid [Formula (9)]
・Ethylenediaminetetraacetic acid [Formula (10)]
・1,3-diaminopropanetetraacetic acid [formula (11)]
・(S,S)-ethylenediaminesuccinic acid trihydrate [formula (12-1)]
・Diethylenetriaminepentaacetic acid [Formula (13)]
・Ethylenediaminetetra (methylenephosphonic acid) [Formula (14)]
・Iminodiacetic acid [formula (15)]
・Citric acid, maleic acid, citraconic acid

(Preparation of particles of virus infection inhibiting compound)
The virus infection inhibiting compound was coarsely pulverized 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 t, and then crushed using a jet mill device (Nissin Engineering Co., Ltd., product name "150 type") under operating conditions of 25 rpm and a pushing force of 25 tons. Particles of the virus infection inhibiting compound were obtained by pulverizing the particles using a machine (SJ-500) under operating conditions of a supply rate of the virus infection inhibiting compound of 1 kg/h and a compressed air pressure of 0.75 MPa.

Table 1 shows the nitrogen atom content in the virus infection inhibiting compound and the pH of a 0.5% by mass aqueous solution of the virus infection inhibiting compound at 25°C.

(Examples 1 to 11 and Comparative Examples 1 to 3)
A virus infection inhibitor containing 3 parts by mass of the particulate virus infection inhibiting compound shown in Table 1 prepared in the manner described above, and 97 mass parts of an ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by Coattec Co., Ltd.) A coating composition was prepared by mixing the following parts. The coating composition 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.

(Example 12)
5 parts by mass of particles of triglycolamic acid [formula (5)] and 10 parts by mass of polystyrene resin particles (primary particles) having an average particle diameter of 4 μm were supplied to 100 parts by mass of water, and the mixture was heated to an atomizer using a spray dryer. After powdering at a rotation speed of 20,000 rpm and adhering (supporting) the entire amount of triglycolamic acid [formula (5)] to the surface of polystyrene particles, a jet mill device (manufactured by Nisshin Engineering Co., Ltd., product name "SJ-") was used. 500'') under the operating conditions of a raw material supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa to obtain polystyrene particles with triglycolamic acid [formula (5)] particles attached to the surface. Ta. In Table 1, "polystyrene particles with particles of triglycolamic acid [formula (5)] attached to the surface" was written as "particle-attached triglycolamic acid [formula (5)]".

An antiviral test was conducted on a virus infection inhibitor containing a virus infection inhibiting compound using influenza virus (enveloped virus) and feline calicivirus (nonenveloped virus), and the results are shown in Table 1.

(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.

On the surface of the coating film of the obtained test piece, a square nonwoven fabric (manufactured by Nippon Paper Crecia Co., Ltd., trade name ``Kimwipe S-200'') with a side of 10 cm was moved back and forth 10 times to obtain a test coating film.

The obtained test coating was subjected to an antiviral test against influenza virus and feline calicivirus in accordance with ISO21702. For the virus suspension after the reaction, the virus infectivity value of the test coating (before immersion in the disinfectant ethanol solution) was calculated by the plaque method.

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

The antiviral activity value (before immersion in the ethanol solution for disinfection) was calculated by subtracting the virus infection value of the test coating from the virus infection value of the blank paint.

In addition, a test coating film was prepared in the manner described above, and the test coating film was immersed in 50 mL of a disinfecting ethanol solution (25° C.) for 17 hours. After removing the test coating film from the ethanol solution for disinfection, a nonwoven fabric (manufactured by Nippon Paper Crecia Co., Ltd., trade name "Kimwipe S-200") was moved back and forth 10 times to adhere to the surface of the test coating film. The ethanol solution for disinfection was removed.

For the test coating film after immersion in the disinfectant ethanol solution, the virus infectivity value of the test coating film (after immersion in the disinfection ethanol solution) was calculated in the same manner as described above.

The antiviral activity value (after immersion in ethanol solution for disinfection) was calculated by subtracting the viral infectivity value of the test coating film from the viral infectivity value of the blank coating film.

The antiviral activity values of the test coating films before and after immersion in ethanol solution for disinfection are listed in the "Before immersion in ethanol solution" and "After immersion in ethanol solution" columns of Table 1, respectively.

[Masterbatch for synthetic resin molding]
(Examples 13 to 21, Comparative Example 4)
Virus infection inhibiting compounds (A) of the types shown in Table 2 were prepared as virus infection inhibiting agents. The mass ratio of the virus infection inhibiting compound (A), the surfactant (B) of the type shown in Table 2, and the polypropylene (C) (trade name "Novatec PP BC6C" manufactured by Nippon Polypro Co., Ltd.) shown in Table 2. (% by mass) to prepare a master batch for synthetic resin molding.

The obtained synthetic resin molding masterbatch and separately prepared polypropylene (PP, manufactured by Nippon Polypro Co., Ltd., trade name "Novatec PP BC6C") were mixed at a ratio of 1:9 (mass ratio) at 180°C for 5 minutes. A resin composition was prepared by melt-kneading.

The obtained resin composition was press-molded to obtain a sheet-like resin molded product with an average thickness of 1 mm as a virus infection prevention product.

The antiviral activity value of the obtained virus infection inhibiting product was measured using the same test method as for the coating film. The antiviral activity values of the virus infection inhibiting product before and after immersion in a disinfectant ethanol solution are listed in the "Before ethanol solution immersion" and "After ethanol solution immersion" columns in Table 2, respectively.

The virus infection inhibitor of the present invention is contained in base materials (e.g., paint films, wallpapers, decorative sheets, flooring materials, textile products, vehicle internal products and interior materials, kitchen products, baby products, architectural interior materials, etc.). By doing so, it is possible to produce a virus infection prevention product that has a virus infection prevention effect. Virus infection prevention products have excellent virus infection prevention effects (antiviral properties) even after contact with disinfectant ethanol solutions.

(Cross reference to related applications)
This application claims priority based on Japanese Patent Application No. 2022-37407 filed on March 10, 2022 and Japanese Patent Application No. 2022-176658 filed on November 2, 2022. , the disclosure of which is incorporated herein by reference in its entirety.

Claims

A virus infection inhibiting agent comprising a virus infection inhibiting compound having one or more acidic functional groups and in which the acidic functional group is bonded to a nitrogen atom via one or more carbon atoms.
The virus infection inhibitor according to claim 1, wherein the acidic functional group is a carboxy group, a phosphonic acid group, or a sulfo group.
The virus infection inhibiting agent according to claim 1 or 2, wherein the virus infection inhibiting compound is represented by formula (1).

[In formula (1), each R 1 independently represents a hydrogen atom, -CH 2 -R 3 or -A 1 -R 3 , and two R 1 's are different even if they are the same. It's okay. R 3 represents a carboxy group, a phosphonic acid group or a sulfo group. A 1 represents a divalent substituent formed by removing two hydrogen atoms from a carbon atom of a 4-, 5-, or 6-membered ring. R 2 represents -CH 2 -R 4 or -A 2 -R 4 . R 4 represents a carboxy group, a phosphonic acid group or a sulfo group. A 2 represents a divalent substituent formed by removing two hydrogen atoms from a carbon atom of a 4-, 5-, or 6-membered ring. ]
The virus infection inhibiting agent according to any one of claims 1 to 3, wherein the virus infection inhibiting compound is represented by formula (2).

[In formula (2), R 5 each independently represents a hydrogen atom, -CH 2 -R 7 , or a structure represented by formula (3), and at least two R 5 are -CH 2 -R 7 or has a structure represented by formula (3). The four R 5 's may be the same or different. R 7 to R 9 each represent a carboxy group, a phosphonic acid group, or a sulfo group. R 6 represents -(CH 2 )n- or a structure represented by formula (4). However, n is an integer from 1 to 3. ]

[In formula (4), R 10 represents a carboxy group, a phosphonic acid group, or a sulfo group. However, m is an integer from 1 to 3. p is an integer from 1 to 3. ]
The virus infection inhibitor according to any one of claims 1 to 4, wherein the acidic functional group is a carboxy group or a phosphonic acid group.
The virus infection inhibiting agent according to any one of claims 1 to 5, wherein the content of nitrogen atoms in the virus infection inhibiting compound is 5 to 12%.
The virus infection inhibitor according to any one of claims 1 to 6, wherein the acidic functional group is a carboxy group.
The virus infection inhibiting agent according to any one of claims 1 to 7, wherein the pH of the 0.5% by mass aqueous solution of the virus infection inhibiting compound at 25° C. is 4.5 or less.
A virus infection inhibiting particle comprising a base particle and the virus infection inhibiting agent according to claim 1 or 2 attached to the surface of the base particle.
The virus infection inhibiting particles according to claim 9, wherein the base particles contain an acrylic resin, a styrene resin, or an inorganic compound.
A virus infection inhibiting product comprising a base material and the virus infection inhibiting agent according to any one of claims 1 to 8 attached to the surface of 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.
A resin composition comprising a synthetic resin and the virus infection inhibitor according to any one of claims 1 to 8, which is contained in the synthetic resin.
The resin composition according to claim 13, which is used as a masterbatch.