WO2024034650A1

WO2024034650A1 - Viral infection inhibitor, resin composition, and viral infection inhibitory product

Info

Publication number: WO2024034650A1
Application number: PCT/JP2023/029169
Authority: WO
Inventors: 大地川村; 拓也木下; 和也西原
Original assignee: 積水化学工業株式会社
Priority date: 2022-08-10
Filing date: 2023-08-09
Publication date: 2024-02-15

Abstract

The present invention provides a viral infection inhibitor mostly capable of preventing yellowing of the inhibitor even when placed in a high-temperature environment. This viral infection inhibitor contains: a carrier which has a specific surface area of 1 to 1,000 m²/g; and a viral infection inhibitory compound which is carried on the carrier and contains at least one kind of infection inhibitory functional group selected from the group consisting of a carboxyl group, a sulfo group, a primary amino group, a secondary amino group, and a tertiary amino group or a salt thereof, or a viral infection inhibitory compound which is carried on the carrier and contains a guanidine structure.

Description

Virus infection inhibitors, resin compositions and virus infection prevention products

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

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

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

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 has been proposed.

Japanese Patent Application Publication No. 2016-128395

However, the above antiviral surface treatment agent has the problem of yellowing when placed in a high temperature environment. Furthermore, when the above-mentioned antiviral surface treatment agent is incorporated into a paint, it causes aggregation, which causes a problem in that the coating properties of the paint are low.

The present invention provides a virus infection inhibitor that can generally prevent yellowing even when placed in a high temperature environment (hereinafter sometimes referred to as "yellowing resistance"), and the virus infection inhibitor described above. The present invention provides a resin composition and a product for inhibiting viral infection.

When the present invention is incorporated into a paint, it can be uniformly dispersed in the paint without agglomeration, and a paint with excellent coating properties can be produced (hereinafter referred to as "coatability"). ) provides a virus infection inhibitor.

The virus infection inhibitor of the present invention is
a support having a specific surface area of 1 to 1000 m ² /g;
is supported on the above carrier and contains at least one infection-inhibiting functional group selected from the group consisting of a carboxy group, a sulfo group, a primary amino group, a secondary amino group, and a tertiary amino group, or a salt thereof. A virus infection inhibiting compound, or a virus infection inhibiting compound supported on the above carrier and containing a guanidine structure.

The resin composition of the present invention includes a synthetic resin and the virus infection inhibitor described above.

The virus infection inhibiting product of the present invention includes a base material and the virus infection inhibiting agent contained in the base material.

Since the virus infection inhibitor of the present invention has the above-mentioned structure, it hardly causes yellowing even when placed in a high-temperature environment, and does not aggregate even when mixed into a paint. It is possible to produce a paint with excellent coating properties.

The virus infection inhibitor of the present invention has excellent yellowing resistance, so it does not impair the color or other appearance of the base material, and has the effect of inhibiting virus infection on the base material while maintaining the appearance of the base material. can be granted.

[Viral infection inhibiting compound]
The virus infection inhibiting agent of the present invention contains a virus infection inhibiting compound as an active ingredient. The virus infection inhibiting compound contains a carboxy group (-COOH), a salt of a carboxy group, a sulfo group (-SO ₃ H), a salt of a sulfo group, a primary amino group, a salt of a primary amino group, in the molecule. It has at least one infection-inhibiting functional group selected from the group consisting of a secondary amino group, a salt of a secondary amino group, a tertiary amino group, and a salt of a tertiary amino group, or a guanidine structure.

The virus infection inhibiting compound exhibits a virus infection inhibiting effect due to its infection inhibiting functional group and guanidine structural moiety. The virus infection inhibiting compound has particularly excellent virus infection inhibiting effects on both enveloped and non-enveloped viruses.

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. The virus infection inhibitor is used as a component of an antiviral finishing agent, and is kneaded into a resin or added to a surface coating agent such as a paint, and evaluated by the above evaluation method.

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. case is defined as a virus infection inhibitor. At that time, regardless of the type of virus to be evaluated, for at least one type of virus, the difference in the common logarithm value of the virus infectivity value (antiviral activity value) between the blank product and the processed product is 2.0 or more. Treated as a virus infection inhibitor.

For example, a paint is prepared by supplying 50 mg of a virus infection inhibitor into 950 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 salt of the carboxy group (-COOH) is not particularly limited, and includes, for example, sodium salt (-COONa), calcium salt [(-COO ^- ) ₂ Ca ²⁺ ], ammonium salt (-COO ^- NH ₄ ⁺ ), Examples include magnesium salt [(-COO ^- ) ₂ Mg ²⁺ ], barium salt [(-COO ^- ) ₂ Ba ²⁺ ], and sodium salt is preferred.

Salts of sulfo groups (-SO ₃ H) are not particularly limited, and include, for example, sodium salts (-SO ₃ Na), calcium salts [(-SO ₃ ^- ) ₂ Ca ²⁺ ], ammonium salts (-SO ₃ ^- NH ₄ ⁺ ), magnesium salt [(-SO ₃ ^- ) ₂ Mg ²⁺ ], barium salt [(-SO ₃ ^- ) ₂ Ba ²⁺ ], and the like, with sodium salt being preferred.

Virus infection inhibiting compounds having a carboxy group need only have one or more carboxy groups in the molecule, such as linear polymers having carboxy groups in their side chains, mellitic acid, aconitic acid, etc. , citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, phthalic acid, isophthalic acid, terephthalic acid, methylene Disalicylic acid, cis-Δ4-tetrahydrophthalic acid, gluconic acid, mucinic acid, 3,3'-thiodipropionic acid, 2,2'-thiodiglycolic acid, 3,3'-dithiodipropionic acid, 2,2 '-dithiodiglycolic acid, 2,2'-dithiosalicylic acid, 4,4'-dithiodibutyric acid, 3-(dodecylthio)propionic acid, picolinic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, Enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, crotonic acid, glycolic acid, lactic acid, malic acid, tartaric acid, quinic acid, salicylic acid, benzoic acid, vanillic acid, gallic acid, mandelic acid, benzylic acid, phloretic acid , coumaric acid, caffeic acid, ferulic acid, sinapinic acid, 4-aminobenzoic acid, triglycolamic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, carboxymethylcellulose, carboxymethylated chitosan, carboxymethylated chitin, carboxymethyldextran, Carboxymethyl-β-cyclodextrin, carboxysucrose, pectin, xanthan gum, alginic acid, hyaluronic acid, fulvic acid, humic acid, uronic acid, arabinonic acid, fructuronic acid, tagaturonic acid, glucuronic acid, iduronic acid, galacturonic acid, mannuronic acid, Examples include guluronic acid.

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

Examples of the linear polymer having a carboxyl group in its side chain include a polymer containing a carboxyl group-containing monomer containing a carboxyl group as a monomer unit. The polymer containing a carboxyl group-containing monomer as a monomer unit may be a homopolymer of a carboxyl group-containing monomer, or a copolymer of a carboxyl group-containing monomer and a monomer copolymerizable with it. good. In a polymer containing a carboxyl group-containing monomer containing a carboxyl group as a monomer unit, the content of the carboxyl group-containing monomer containing a carboxyl group is preferably 50 mol% or more, more preferably 75 mol% or more, and 90 mol%. % or more, more preferably 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

Carboxy group-containing monomers are not particularly limited, and examples include acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, succinic acid mono(meth)acryloyloxyethyl ester, ω -Carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, carboxybetaine type monomers, etc., and acrylic acid and methacrylic acid are preferred. Note that the carboxy group-containing monomers may be used alone or in combination of two or more types. (Meth)acrylate means acrylate or methacrylate. (Meth)acryloyl means acryloyl or methacryloyl.

A virus infection inhibiting compound containing a salt of a carboxy group may have one or more salts of a carboxy group in the molecule, for example, a polymer having a salt of a carboxy group in the side chain of a linear polymer. Coalescence, salts of mellitic acid, salts of aconitic acid, salts of citric acid, salts of oxalic acid, salts of malonic acid, salts of succinic acid, salts of glutaric acid, salts of adipic acid, salts of pimelic acid, salts of suberic acid. salts, fumaric acid salts, maleic acid salts, itaconic acid salts, citraconic acid salts, mesaconic acid salts, phthalic acid salts, isophthalic acid salts, terephthalic acid salts, methylenedisalicylic acid salts, cis- Δ4-tetrahydrophthalic acid salt, gluconic acid salt, mucilage acid salt, 3,3'-thiodipropionic acid salt, 2,2'-thiodiglycolic acid salt, 3,3'-dithiodipropion acid salts, 2,2'-dithiodiglycolic acid salts, 2,2'-dithiosalicylic acid salts, 4,4'-dithiodibutyric acid salts, 3-(dodecylthio)propionic acid salts, picolinic acid salts salts, formic acid salts, acetic acid salts, propionic acid salts, butyric acid salts, valeric acid salts, caproic acid salts, enanthic acid salts, caprylic acid salts, pelargonic acid salts, capric acid salts, lauric acid salts Acid salts, crotonic acid salts, glycolic acid salts, lactic acid salts, malic acid salts, tartaric acid salts, quinic acid salts, salicylic acid salts, benzoic acid salts, vanillic acid salts, gallic acid salts , salts of mandelic acid, salts of benzylic acid, salts of floretic acid, salts of coumaric acid, salts of caffeic acid, salts of ferulic acid, salts of sinapic acid, salts of 4-aminobenzoic acid, salts of triglycolamic acid. salts, salts of ethylenediaminetetraacetic acid, salts of diethylenetriaminepentaacetic acid, salts of carboxymethylcellulose, salts of carboxymethylated chitosan, salts of carboxymethylated chitin, salts of carboxymethyldextran, salts of carboxymethyl-β-cyclodextrin, carboxy Sucrose salts, pectin salts, xanthan gum salts, alginic acid salts, hyaluronic acid salts, fulvic acid salts, humic acid salts, uronic acid salts, arabinonic acid salts, fructuronic acid salts, tagaturonic acid salts , glucuronic acid salts, iduronic acid salts, galacturonic acid salts, mannuronic acid salts, guluronic acid salts, and the like.

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

Examples of the linear polymer having a carboxy group salt in the side chain include a polymer containing a carboxy group salt-containing monomer as a monomer unit. The polymer containing a carboxy group salt-containing monomer as a monomer unit may be a homopolymer of a carboxy group salt-containing monomer, or a copolymer of a carboxy group salt-containing monomer and a monomer copolymerizable therewith. It may also be a polymer. In a polymer containing a carboxy group salt-containing monomer as a monomer unit, the content of the carboxy group salt-containing monomer is preferably 50 mol% or more, more preferably 75 mol% or more, more preferably 90 mol% or more, More preferably 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

The carboxy group salt-containing monomer is a carboxy group salt of a carboxy group-containing monomer. Examples of the salt of the carboxy group salt-containing monomer include sodium salt, calcium salt, ammonium salt, magnesium salt, barium salt, and the like, with sodium salt being preferred. Note that the carboxy group-containing monomer is the same as described above, so a description thereof will be omitted.

The virus infection inhibiting compound containing a sulfo group only needs to have one or more sulfo groups in its molecule, and includes, for example, a linear polymer having a sulfo group in its side chain, polystyrene sulfonic acid, Formamidinesulfinic acid, 3-aminobenzenesulfonic acid, hydroxybenzenesulfonic acid, m-xylene-4-sulfonic acid, 5-sulfosalicylic acid, sulfanilic acid, 2-amino-3,5-dimethylbenzenesulfonic acid, 1,3 Examples include -phenylenediamine-4-sulfonic acid, sulfonated (styrene-divinylbenzene copolymer), carrageenan, sulfonated polyether sulfone, lignin sulfonic acid, and taurine.

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

Examples of the linear polymer having a sulfo group in its side chain include a polymer containing a sulfo group-containing monomer containing a sulfo group as a monomer unit. In a polymer containing a sulfo group-containing monomer as a monomer unit, the content of the sulfo group-containing monomer is preferably 50 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more. , more preferably 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

Examples of polymers containing sulfo group-containing monomers as monomer units include polymers containing styrene sulfonic acid units, styrene sulfonic acid homopolymers, styrene-styrene sulfonic acid copolymers, and polystyrene. Examples include compounds in which the benzene ring of a polymer containing a styrene component is sulfonated, and compounds in which the benzene ring of a polymer containing a styrene component is sulfonated.

The sulfo group-containing monomer is not particularly limited, and examples thereof include p-styrenesulfonic acid, m-styrenesulfonic acid, o-styrenesulfonic acid, and the like.

Virus infection inhibiting compounds containing sulfo group salts only need to have one or more sulfo group salts in the molecule, such as linear alkylbenzene sulfonates, α-olefin sulfonates, alkyl Diphenyl ether sulfonate, polyoxyalkylene alkyl ether sulfate, lauryl sulfate, linear polymer having a sulfo group salt in the side chain, polystyrene sulfonic acid salt, formamidine sulfinic acid salt, 3- Salts of aminobenzenesulfonic acid, salts of hydroxybenzenesulfonic acid, salts of m-xylene-4-sulfonic acid, salts of 5-sulfosalicylic acid, salts of sulfanilic acid, salts of 2-amino-3,5-dimethylbenzenesulfonic acid Examples include salts of 1,3-phenylenediamine-4-sulfonic acid, sulfonated (styrene-divinylbenzene copolymer) salts, carrageenan salts, sulfonated polyether sulfone salts, and ligninsulfonic acid salts. It will be done.

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

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

Examples of the alkyldiphenyl ether sulfonate include sodium salt, calcium salt, ammonium salt, magnesium salt, and barium salt of alkyldiphenyl ether sulfonic acid having an alkyl group of C6 to C18. Note that an alkyl group is a monovalent atomic group remaining after removing one hydrogen atom from an aliphatic saturated hydrocarbon.

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

The polymer having a sulfo group salt in the side chain of the linear polymer is not particularly limited, and includes, for example, a polymer containing a sulfo group salt-containing monomer containing a sulfo group salt as a monomer unit. It will be done. In a polymer containing a sulfo group salt-containing monomer as a monomer unit, the content of the sulfo group salt-containing monomer is preferably 50 mol% or more, more preferably 75 mol% or more, and 90 mol% or more. More preferably mol% or more, more preferably 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

Examples of the polymer containing a sulfo group salt-containing monomer as a monomer unit include a polymer containing a styrene sulfonate unit, a styrene sulfonate homopolymer, and styrene-styrene sulfone. Examples include acid salt copolymers, sulfonate salts of compounds obtained by sulfonating the benzene ring of polystyrene, and sulfonate salts of compounds obtained by sulfonating the benzene ring of a polymer containing a styrene component.

The sulfo group salt-containing monomer is not particularly limited, and includes, for example, sodium p-styrenesulfonate, sodium m-styrenesulfonate, sodium o-styrenesulfonate, calcium p-styrenesulfonate, and calcium m-styrenesulfonate. , calcium o-styrenesulfonate, ammonium p-styrenesulfonate, ammonium m-styrenesulfonate, ammonium o-styrenesulfonate, etc., and sodium styrenesulfonate is preferred, as it has less steric hindrance in reactivity with viruses. Therefore, sodium p-styrene sulfonate is more preferred.

At least one amino functional group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group or a salt of this amino functional group improves the virus infection inhibiting effect of the virus infection inhibitor. Therefore, it is preferable that a cyclic skeleton is formed, and it is preferable that an alicyclic cyclic skeleton is formed. Preferably, the amino functional group or the salt of the amino functional group forms part of the alicyclic cyclic skeleton.

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. In formula (a), *1 to 3 are bonds and mean single bonds.

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.

A virus infection inhibiting compound having an amino functional group or a salt thereof may have one or more amino functional groups or a salt thereof in the molecule. Examples of the virus infection inhibiting compound having an amino functional group or a salt thereof in the molecule include a polymer containing an amino functional group or a salt thereof in the side chain of a linear polymer.

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 the polymer containing an amino functional group or a salt thereof in the side chain of the linear polymer include a polymer containing an amino functional group-containing monomer containing an amino functional group or a salt thereof as a monomer unit. In a polymer containing an amino functional group-containing monomer containing an amino functional group or a salt thereof as a monomer unit, the content of the amino functional group-containing monomer is preferably 50 mol% or more, more preferably 75 mol% or more, and 90 mol% or more. More preferably mol% or more, more preferably 95 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.

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.

A virus infection inhibiting compound having an amino functional group or a salt thereof in its molecule does not need to be a polymer. Examples of virus infection inhibiting compounds having an amino functional group or a salt thereof in the molecule include chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, bronopol, Examples include zinc pyrithione, benzalkonium, didecyldimethylammonium, carbendazim, diuron, iodopropynyl butylcarbamate, and thiabendazole.

When the virus infection inhibiting compound is a polymer, it may be a homopolymer of a monomer having an infection inhibiting functional group (monomer containing an infection inhibiting functional group), or it may be a homopolymer of a monomer having an infection inhibiting functional group and the infection inhibiting functional group. It may be a copolymer of a monomer copolymerizable with the monomer contained therein.

Monomers that can be copolymerized with the infection-inhibiting 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, and chloride. Examples include vinylidene, 2-vinylnaphthalene, styrene, acrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, and vinyltoluene. The monomers copolymerizable with the infection-inhibiting functional group-containing monomer may be used alone or in combination of two or more.

The above-mentioned polymer that becomes the virus infection inhibiting compound may be polymerized using a general-purpose polymerization method. For example, a virus infection-inhibiting compound can be obtained by polymerizing a monomer composition containing an infection-inhibiting functional group-containing monomer in the presence of a commonly used radical polymerization initiator. 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.

Examples of compounds that inhibit virus infection include compounds that have a guanidine structure in the molecule. The guanidine structure refers to a divalent atomic group having the structural formula shown in formula (b) below. Note that *4 and *5 are bonds and mean a single bond.

Examples of virus infection inhibiting compounds containing a guanidine structure in the molecule include a polymer (polyhexamethylene biguanide) having a structure represented by the following formula (1), and a polymer having a structure represented by the following formula (2). Examples include acid addition salts of polymers (polyhexamethylene biguanide hydrochloride), polyhexamethylene guanidine, polyhexamethylene guanidine hydrochloride, polyhexamethylene guanidine phosphate, etc. An acid addition salt of a polymer having the structure shown in formula (1) is preferable, and a hydrochloride [formula (2)] of a polymer having the structure represented by formula (1) is more preferable. Note that n means a repeating unit. n is a natural number of 2 or more. x is the coefficient of added hydrochloric acid. In polyhexamethylene biguanide, the content of the structure represented by formula (1) is preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, more preferably 99 mol% or more, 100 mol% is more preferable. In the hydrochloride of polyhexamethylene biguanide, the content of the structure represented by formula (2) is preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and 99 mol% or more. More preferably, 100 mol% is more preferable.

A virus infection inhibiting compound containing at least one infection inhibiting functional group selected from the group consisting of a carboxy group, a sulfo group, a primary amino group, a secondary amino group, and a tertiary amino group or a salt thereof; and guanidine. Viral infection inhibiting compounds containing structures may be used in combination.

When the virus infection inhibiting compound contains a polymer, the weight average molecular weight of the polymer is preferably 1,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more. When the weight average molecular weight of the virus infection inhibiting compound is 1000 or more, the yellowing resistance of the virus infection inhibiting agent can be improved, and when the virus infection inhibiting agent is attached to the surface of the substrate, the appearance of the substrate can be improved. The virus infection inhibiting effect can be expressed more effectively without any damage, and the adsorption points with the virus per molecule of the virus infection inhibiting compound are increased, and the interaction between the virus infection inhibiting compound and the virus is strengthened. , the virus infection inhibiting effect of the virus infection inhibitor can be improved.

The weight average molecular weight of the polymer contained in the virus infection inhibiting compound is preferably 1,500,000 or less, more preferably 1,000,000 or less, more preferably 900,000 or less, more preferably 800,000 or less, and more preferably 500,000 or less. When the weight average molecular weight of the virus infection inhibiting compound is 1,500,000 or less, the yellowing resistance of the virus infection inhibitor can be improved, and when the virus infection inhibitor is attached to the surface of the base material, the appearance of the base material can be improved. The virus infection inhibiting effect can be more effectively expressed without any damage, and the aggregation of the virus infection inhibitor is reduced, and the coating properties are improved.

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

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

It is preferable that the virus infection inhibiting compound is formed into particles. The D90 particle diameter of the virus infection inhibiting compound is preferably 2 μm or more, 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 size of the virus infection inhibiting compound is preferably 25 μm or less, more preferably 22 μm or less, more preferably 20 μm or less, more preferably 18 μm or less, more preferably 16 μm or less, more preferably 14 μm or less, and more preferably 12 μm or less. . When the D90 particle size is 2 μm or more, the overall surface area of the virus infection inhibiting compound becomes small, the aggregation of the virus infection inhibiting agent is reduced, coating properties are improved, and the virus infection inhibiting compound and the virus interact with each other. The virus infection inhibiting effect of the virus infection inhibiting agent is improved. When the D90 particle size is 25 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 inhibiting effect of the virus infection inhibitor. , it is possible to suppress the discoloration of the virus infection inhibiting compound, which is prone to visible light scattering, and it is possible to improve the yellowing resistance of the virus infection inhibitor.Furthermore, since the number of coarse particles is reduced, Coating properties can be improved.

As described below, the D90 particle size of a virus infection inhibiting compound is the particle size at which the cumulative frequency (accumulation from particles with small particle size) in the volume-based particle size distribution determined by laser scattering method is 90% (90% cumulative particle size). diameter). By adjusting the D90 particle size of the virus infection inhibiting compound to the above-mentioned range and adjusting the particle size of the large particles in the virus infection inhibiting compound to a predetermined range, the virus infection inhibiting compound can contain coarse particles. has been reduced. The virus infection inhibiting compound has an infection inhibiting functional group on its surface, and by adjusting the particle size of the virus infection inhibiting compound to the above range, the infection inhibiting functional group present on the surface of the virus infection inhibiting compound or The amount of guanidine structure is adjusted to give the virus infection inhibitor an excellent virus infection inhibiting effect, and the interaction in the infection inhibiting functional group and/or guanidine structure is reduced to make the virus infection inhibitor resistant to yellowing. can be improved.

The D50 particle diameter of the virus infection inhibiting compound is preferably 0.5 μm or more, more preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. The D50 particle size of the virus infection inhibiting compound is preferably 14 μm or less, more preferably 12 μm or less, and even more preferably 11 μm or less.

In the virus infection inhibiting compound, by setting the D50 particle size and D90 particle size within the above ranges, the inclusion of coarse particles having a particle size significantly different from the D50 particle size in the virus infection inhibiting compound is reduced, The particle size of the virus infection inhibiting compound can be made more appropriate.

By adjusting the particle size of the virus infection inhibiting compound to a more appropriate range, we can more appropriately adjust the amount of infection inhibiting functional groups and guanidine structures present on the surface of the virus infection inhibiting compound, making it an excellent virus infection inhibitor. In addition to more effectively imparting the effect of inhibiting viral infection, it is possible to suppress the discoloration of the viral infection inhibiting compound that tends to cause scattering of visible light, and it is possible to improve the yellowing resistance of the viral infection inhibiting agent. Since the number of coarse particles is reduced, the coatability of the virus infection inhibitor can be improved.

The D90 particle size and D50 particle size of the virus infection inhibiting compound are the particle size (90 % cumulative particle size and 50% cumulative particle size). When the virus infection inhibiting compound contains multiple types of virus infection inhibiting compounds, the D90 particle diameter and D50 particle diameter of the virus infection inhibiting compound are values measured based on the entire virus infection inhibiting compound.

[Support]
The virus infection inhibiting agent contains the above virus infection inhibiting compound, and this virus infection inhibiting compound is supported on a carrier having a specific surface area of 1 to 1000 m ² /g.

A support with a specific surface area of 1 to 1000 m ² /g has a fine pore structure, and by entering a portion of the virus infection inhibiting compound into this pore structure, the virus infection can be inhibited from the surface of the support. It is configured to prevent the virus infection inhibiting compound from falling off and to stably maintain the virus infection inhibiting effect of the virus infection inhibiting agent over a long period of time.

Furthermore, by supporting the virus infection-inhibiting compound on the pore structure of a carrier having a specific surface area within a predetermined range, the interaction between the infection-inhibiting functional groups and/or guanidine structures of the virus infection-inhibiting compound is reduced, and the virus The yellowing resistance of the infection inhibitor can be improved, and the aggregation of the virus infection inhibitor can be reduced to improve the coatability.

Furthermore, by attaching the virus infection inhibiting compound to the surface of a carrier having a predetermined specific surface area, 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 carrier to which the virus infection inhibiting compound is attached is not particularly limited as long as it does not inhibit the virus infection inhibiting effect of the virus infection inhibiting agent. Particles include resin particles and inorganic particles. The 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, 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 materials constituting the inorganic particles are not particularly limited, and include, for example, silica, zeolite, diatomaceous earth, kaolin, hydrotalcite, calcium carbonate, calcium citrate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, and oxidized magnesium. Examples include titanium and talc.

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 infection-inhibiting functional group and guanidine structure outward, thereby inhibiting virus infection of the virus infection inhibitor. The effect can be exerted 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 from the aromatic ring and the fused aromatic ring, and is bonded to other atoms through covalent bonds.

The mass ratio of the virus infection inhibiting compound to the carrier (mass of the virus infection inhibiting compound/mass of the carrier) is preferably 0.01 or more, more preferably 0.02 or more, more preferably 0.05 or more, and 0. More preferably .07 or more, more preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.25 or more. The mass ratio of the virus infection inhibiting compound to the carrier (mass of the virus infection inhibiting compound/mass of the carrier) is preferably 10 or less, more preferably 7 or less, more preferably 5 or less, and more preferably 4 or less. When the mass ratio of the virus infection inhibiting compound to the carrier (mass of the virus infection inhibiting compound/mass of the carrier) is 0.05 or more, the virus infection inhibitor can be uniformly attached to the surface of the carrier. , the virus infection inhibitor can more effectively exhibit the virus infection inhibiting effect, and the virus infection inhibitor can be uniformly dispersed in the paint without agglomeration, making the virus infection inhibitor an excellent paint coating. It has good workability. When the mass ratio of the virus infection inhibiting compound to the carrier (mass of the virus infection inhibiting compound/mass of the carrier) is 10 or less, the virus infection inhibiting compounds do not bond with each other, and the virus is efficiently deposited on the surface of the resin particle. By disposing the infection inhibitor, the effect of inhibiting virus infection can be improved, and the yellowing resistance of the virus infection inhibitor can be improved.

The method of supporting the virus infection inhibiting compound on the surface of the carrier is not particularly limited, and for example, the virus infection inhibiting compound may be attached to the surface of the carrier by using the adhesive force of the virus infection inhibiting compound, or by adhering the virus infection inhibiting compound to the surface of the carrier using a binder resin. However, since the virus infection inhibiting effect of the virus infection inhibiting agent can be effectively exhibited, the virus infection inhibiting compound is attached to the surface of the carrier by the adhesive force of the virus infection inhibiting compound itself. It is preferable.

The specific surface area of the carrier is 1 m ² /g or more, preferably 50 m ² /g or more, more preferably 100 m ² /g or more, and even more preferably 200 m ² /g or more. The specific surface area of the carrier is 1000 m ² /g or less, preferably 800 m ² /g or less, preferably 700 m ² /g or less, more preferably 600 m ² /g or less, more preferably 500 m ^{2 /g or less, and 400 m 2} /g or less. ² /g or less is preferable. When the specific surface area of the carrier is 1 m ² /g or more, the virus infection inhibiting compound can be supported while being dispersed within the pore structure of the carrier, improving contact between the virus infection inhibiting agent and the virus. , the virus infection inhibiting effect of the virus infection inhibitor can be improved, and the yellowing resistance of the virus infection inhibitor can be improved. When the specific surface area of the carrier is 1000 m ² /g or less, the interaction between the carriers is reduced, the contact between the virus infection inhibitor and the virus is improved, and the virus infection inhibiting effect of the virus infection inhibitor is improved. It is also possible to reduce the aggregation of the virus infection inhibitor and improve the coating properties.

Note that the specific surface area of the support is a value measured by the BET method in accordance with JIS Z8830.

The D50 particle diameter of the support is preferably 0.1 μm or more, more preferably 0.2 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more. The D50 particle diameter of the support is preferably 200 μm or less, more preferably 100 μm or less, more preferably 80 μm or less, more preferably 60 μm or less, more preferably 40 μm or less, more preferably 20 μm or less, and more preferably 10 μm or less.

When the D50 particle size of the carrier is 0.1 μm or more, the virus infection inhibiting compound can be supported while being dispersed within the pore structure of the carrier, improving contact between the virus infection inhibitor and the virus. , the virus infection inhibiting effect of the virus infection inhibitor can be improved. Furthermore, the virus infection inhibiting compounds do not bind to each other, and the virus infection inhibiting agent is efficiently placed on the surface of the resin particles, improving the virus infection inhibiting effect and improving the yellowing resistance of the virus infection inhibiting agent. .

When the D50 particle diameter of the carrier is 200 μm or less, visible light is easily scattered and discoloration of the virus infection inhibiting compound can be suppressed, yellowing resistance of the virus infection inhibiting agent can be improved, and furthermore, coarse particles can be prevented from discoloring. As the number of particles is reduced, the applicability of virus infection inhibitors can be improved.

The D50 particle diameter of the support is the particle diameter (50% cumulative particle diameter) at which the cumulative frequency (accumulation from particles with small particle diameters) in the volume-based particle size distribution determined by the laser scattering method is 50%. When the carrier includes multiple types of carriers, the D50 particle diameter of the carrier is a value measured based on the entire carrier.

[Viral infection inhibitor]
The virus infection inhibiting agent includes a carrier having a specific surface area within a predetermined range, and a predetermined virus infection inhibiting compound supported on the carrier. The method for producing a virus infection inhibitor is not particularly limited, and the virus infection inhibitor can be produced by supporting a virus infection inhibitor compound on a carrier in a conventional manner.

In the virus infection inhibiting agent, the total amount of the carrier and the virus infection inhibiting compound supported on the carrier 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. The content is more preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.

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 is 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 inhibitor exhibits the virus infection inhibiting effect as a virus infection inhibiting product.

Since the virus infection inhibitor has excellent yellowing resistance, the base material containing the virus infection inhibitor can be used for a long period of time without yellowing due to the virus infection inhibitor. The original appearance of the base material can be maintained.

The base material containing the virus infection inhibitor is not particularly limited as long as it can contain the virus infection inhibitor, and examples thereof include synthetic resin moldings, paints, wallpapers, 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 supplies, baby products, architectural interior materials, etc. can be mentioned.

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 master batch for synthetic resin molding containing a synthetic resin and a virus infection inhibitor may be mixed with the raw material synthetic resin to produce a virus infection prevention product as a molded product using a general-purpose synthetic resin molding method. .

In the virus infection prevention product, the content of the virus infection inhibitor is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more with respect to 100 parts by mass of the base material. In the virus infection prevention product, the content of the virus infection inhibitor is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less, based on 100 parts by mass of the base material.

[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 the 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 prevention product (molded article), and the virus infection of the virus infection prevention product (molded article) is likely to be segregated. The blocking effect can be further enhanced.

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, 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.

It is preferable that the virus infection inhibitor used in the resin composition, particularly in the master batch for synthetic resin molding, contains an antioxidant. When the virus infection inhibitor contains an antioxidant, yellowing of the synthetic resin during molding using a synthetic resin molding masterbatch or in the obtained molded product (virus infection prevention product) can be reduced. .

Antioxidants are not particularly limited, and include, for example, monophenolic antioxidants, bisphenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Antioxidants and bisphenol antioxidants are preferred. Note that the antioxidants may be used alone or in combination of two or more.

Examples of monophenolic antioxidants include dibutylhydroxytoluene (BHT), didibutylhydroxyanisole (BHA), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2, 2'-methylenebis(4-methyl-6-tert-butylphenol), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[ 1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) , 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis [2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5 ] undecane, etc., and dibutylhydroxytoluene (BHT) and dibutylhydroxyanisole (BHA) are preferred because they have excellent yellowing resistance of the molded product obtained.

Examples of bisphenol antioxidants include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), and 4,4' - Thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-( 3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-dihydroxy-3,3'- Examples include di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, and 2,2'-methylenebis(4-methyl-6-t-butylphenol) ), 4,4'-thiobis(3-methyl-6-t-butylphenol) are preferred.

The melting point of the antioxidant is preferably 200°C or lower, more preferably 170°C or lower, and even more preferably 100°C or lower. The melting point of the antioxidant is preferably 50°C or higher, more preferably 60°C or higher. If the melting point of the antioxidant is below 200°C, the antioxidant will melt during the molding process using a synthetic resin molding masterbatch, and the degree of miscibility with the virus infection inhibitor and synthetic resin containing the antioxidant will be high. Therefore, it is possible to reduce yellowing of the synthetic resin during molding or in the obtained molded product (viral infection prevention product). It is preferable that the melting point of the antioxidant is 50° C. or higher, since the virus infection inhibitor containing the antioxidant can be easily handled at room temperature. Note that the melting point of the antioxidant refers to the temperature measured in accordance with JIS K0064:1992.

The content of the antioxidant in the virus infection inhibitor is preferably 0.1% by mass or more, more preferably 1% by mass or more. The content of surfactant in the virus infection inhibitor is preferably 5% by mass or less, more preferably 4% 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.

As the paint, conventionally known paints are used, such as oil-based paints (for example, 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.

Since the virus infection inhibitor has excellent coating properties, the virus infection inhibitor can be uniformly dispersed in the paint, and the coating film produced from this paint has an overall It has a substantially uniform effect of inhibiting virus infection.

Since the virus infection inhibitor has excellent yellowing resistance, the coating film produced from the paint containing the virus infection inhibitor will not yellow over a long period of time. Therefore, an article with a coating film formed on its surface can maintain its appearance for a long period of time.

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.

As virus infection inhibiting compounds, polymers 1 to 10, citric acid, N-[1-[2-(dodecylamino)ethylamino]ethyl]glycine and N-[1-[2-(dodecylamino)ethylamino]ethyl ] Glycine hydrochloride was prepared. When the virus infection inhibiting compound is a polymer, the weight average molecular weight is shown in the "Weight average molecular weight" column of Tables 1 to 3. The molecular weight of citric acid is listed in the "weight average molecular weight" column for convenience. The "guanidine structure" of the virus infection inhibiting compound is described in the "Virus infection inhibiting functional group" column for convenience.

[Viral infection inhibiting compound]
・Polymer 1 (polystyrene sulfonic acid, formula (3), manufactured by Nouryon, product name "Versa-TL72")
・Polymer 2 (polyacrylic acid, formula (4), manufactured by Nippon Shokubai Co., Ltd., product name "HL-415")
・Citric acid/polymer 3 (polyallylamine, formula (5), manufactured by Nittobo Medical Co., Ltd., product name "PAA-15C")
・Polymer 4 (diallylamine hydrochloride polymer, formula (6), manufactured by Nittobo Medical Co., Ltd., product name "PAS-21CL")
・Polymer 5 (diallylamine polymer, formula (7), manufactured by Nittobo Medical Co., Ltd., product name "PAS-21")
・Polymer 6 (copolymer of allylamine hydrochloride and diallylamine hydrochloride, formula (8), manufactured by Nittobo Medical Co., Ltd., product name "PAA-D19-JCl")
・Polymer 7 (copolymer of diallylamine hydrochloride and maleic acid, formula (9), manufactured by Nittobo Medical Co., Ltd., product name "PAS-410C")
・Polymer 8 (copolymer of diallylamine hydrochloride and maleic acid, formula (9), manufactured by Nittobo Medical Co., Ltd., product name "PAS-411C")
・Polymer 9 (methyldiallylamine hydrochloride polymer, formula (10), manufactured by Nittobo Medical Co., Ltd., product name "PAS-M-1")
・Polymer 10 (polyhexamethylene biguanide hydrochloride, formula (2), Lonza product name "VANTOCIL TG")
・N-[1-[2-(dodecylamino)ethylamino]ethyl]glycine (manufactured by Sanyo Chemical Co., Ltd., trade name "Levon S") (In the table, it is written as "dodecylaminoethylaminoethylglycine.")
・N-[1-[2-(dodecylamino)ethylamino]ethyl]glycine hydrochloride (manufactured by Sanyo Kasei Co., Ltd., trade name "Levon T-2") (in the table, "dodecylaminoethylaminoethylglycine hydrochloride") )

In formulas (3) to (10), n, m and p represent repeating units and are natural numbers of 2 or more.

Among the structural formulas shown above, the structural formula expressed as formula (11) means a random copolymer, alternating copolymer, or block copolymer of monomer unit M ₁ and monomer unit M ₂ . n, m and p represent repeating units and are natural numbers of 2 or more. In formulas (1) to (11), n, m and p only mean repeating units. In formulas (1) to (11), n, m, and p each take independent values. In formula (2), x is the coefficient of added hydrochloric acid.

[Support (particles)]
・Silica particles 1 (manufactured by Fuji Silysia Co., Ltd., product name "SYLOSPHERE C-1504")
・Silica particles 2 (manufactured by Admatex, product name "SO-C1")
・Silica particles 3 (manufactured by Admatex, product name "SO-C6")
・Silica particles 4 (manufactured by Fuji Silysia Co., Ltd., product name "SYLYSIA 250")
・Silica particles 5 (manufactured by Fuji Silysia Co., Ltd., product name "SYLYSIA 730")
・Silica particles 6 (manufactured by AGC SITEC, product name "Sunsphere H-51")
・Zeolite particles (manufactured by Tosoh Corporation, product name "930NHA")
・Diatomaceous earth particles (product name “Radiolite 100” manufactured by Hayashi Kasei Co., Ltd.)
・Kaolin particles (manufactured by BASF, product name “Satintone 5HB”)
・Calcium carbonate particles 1 (manufactured by Sankyo Seifun Co., Ltd., product name “Escalon #200”)
・Calcium carbonate particles 2 (manufactured by Sankyo Seifun Co., Ltd., product name “Escalon (A)”)
・Talc particles (manufactured by Nippon Talc Co., Ltd., product name “Micro Ace P-8”)
・Aluminum hydroxide particles (product name “A-43-L” manufactured by Showa Denko)
・Titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd., product name “PT-301”)
・Hydrotalcite particle 1 (Mg ₄ Al ₂ (OH) ₁₂ CO ₃ 3H ₂ O, Mg-Al type, manufactured by Sakai Chemical Co., Ltd., product name "HT-1")
・Hydrotalcite particles 2 (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ mH ₂ O, Mg-Al type, manufactured by Sakai Chemical Co., Ltd., product name “HT-6”)
・Hydrotalcite particles 3 (Mg _4.5 Al ₂ (OH) ₁₃ CO ₃・3.5 H ₂ O, Mg-Al type, manufactured by Sakai Chemical Co., Ltd., product name "HT-P")
・Hydrotalcite particles 4 (Mg _3.5 Zn _0.5 Al ₂ (OH) ₁₂ CO ₃ 3H ₂ O, Mg-Zn-Al type, manufactured by Sakai Chemical Co., Ltd., product name "HT-7")
・Acrylic resin particles 1 (manufactured by Sekisui Plastics Co., Ltd., product name "MBP-8HP")
・Acrylic resin particles 2 (manufactured by Sekisui Plastics Co., Ltd., product name "MBP-8")

[Antioxidant]
[Monophenolic antioxidant]
・Dibutylhydroxytoluene (BHT)
・Dibutylhydroxyanisole (BHA)
[Bisphenol antioxidant]
・Bisphenol antioxidant 1 (2,2'-methylenebis(4-methyl-6-tert-butylphenol), manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Nocrac NS-6")
・Bisphenol antioxidant 2 (4,4'-thiobis(3-methyl-6-tert-butylphenol), manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Nocrac 300")

(Examples 1 to 31, Comparative Example 11)
Seven times the mass of water was prepared relative to the total mass of the virus infection inhibiting compound and the carrier. Virus infection inhibiting compounds and carriers (particles) of the types shown in Tables 1 and 2 were supplied to water and mixed uniformly to prepare a dispersion. The particles used for the carrier had the D50 particle diameter and specific surface area shown in Tables 1 and 2. The mass ratio of the virus infection inhibiting compound and the carrier supplied to the water (mass of the virus infection inhibiting compound/mass of the carrier) is shown in the "compound/support" column of Tables 1 and 2.

Next, the dispersion liquid was pulverized using a spray dryer at an atomizer rotation speed of 20,000 rpm, and the entire amount of the virus infection inhibiting compound was attached (supported) on the surface of the carrier, and then a jet mill device (manufactured by Nissin Engineering Co., Ltd.) was used. The carrier with the virus infection inhibiting compound supported (attached) on its surface was crushed using a machine (trade name "SJ-500") under operating conditions of a raw material supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa. Obtained as a virus infection inhibitor.

5 parts by mass of the virus infection inhibitor shown in Tables 1 and 2 and 95 parts by mass of an ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by Coattec Co., Ltd.) were mixed to form a coating composition (virus infection inhibitor). product) was produced. 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.

(Comparative example 1)
The virus infection inhibiting compounds shown in the "Type" column of Table 2 were used without being supported on a carrier. In detail, the virus infection inhibiting compound (polymer 1) was processed using a jet mill device (manufactured by Nisshin Engineering Co., Ltd., trade name "SJ-500") at a raw material supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa. The particles were pulverized under the following conditions to obtain particles of the virus infection inhibiting compound. 5 parts by mass of the virus infection inhibiting compound (polymer 1) shown in Table 2 and 95 parts by mass of an ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by Coattec Co., Ltd.) were mixed to form a coating composition (virus Infection prevention product) was created. Using this coating composition, a coating film having a thickness of 18 μm was formed in the same manner as in Example 1.

(Comparative Examples 2 to 9)
The virus infection inhibiting compounds shown in the "Type" column of Table 2 were used without being supported on a carrier. Specifically, the virus infection inhibiting compound obtained by freeze-drying the virus infection inhibiting compound was processed using a roll press device (Seishin Enterprise Co., Ltd., product name "150 type") under operating conditions of a rotation speed of 25 rpm and a pushing force of 25 t. After coarse pulverization, the virus infection is prevented by pulverizing using a jet mill device (manufactured by Nisshin Engineering Co., Ltd., product name "SJ-500") under operating conditions of a raw material supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa. Particles of the compound were obtained. A coating composition is prepared by mixing 5 parts by mass of the virus infection inhibiting compound shown in the "Type" column of Table 2 and 95 parts by mass of an ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by Coattec Co., Ltd.). Created. Using this coating composition, a coating film having a thickness of 18 μm was formed in the same manner as in Example 1.

(Comparative example 10)
The virus infection inhibiting compounds shown in the "Type" column of Table 2 were used without being supported on a carrier. Specifically, the virus infection inhibiting compound was freeze-dried to obtain a paste of the virus infection inhibiting compound. A coating composition is prepared by mixing 5 parts by mass of the virus infection inhibiting compound shown in the "Type" column of Table 2 and 95 parts by mass of an ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by Coattec Co., Ltd.). Created. Using this coating composition, a coating film having a thickness of 18 μm was formed in the same manner as in Example 1.

The antiviral test, yellowing resistance, and coatability of the obtained coating film were measured as follows, and the results are shown in Tables 1 and 2.

(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 soaked in 1 mL of water with a square non-woven fabric (manufactured by Nippon Paper Crecia Co., Ltd., product name "Kimwipe S-200") with a side of 10 cm, and the surface of the coating film was covered with the non-woven fabric for 10 minutes. It was wiped back and forth and used as a test coating.

The obtained test coating was subjected to an antiviral test against influenza virus and feline calicivirus 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 value of the test coating from the virus infection value of the blank paint.

(yellowing resistance)
A durability test was conducted at 120° C. for 1000 hours on the test coating obtained in the same manner as the antiviral test. The yellow index of the test coating before and after the test was measured using a spectrophotometer ("CM-5" manufactured by Konica Minolta) in accordance with ASTM E313-73. The yellowing index (ΔYI) was calculated by subtracting the yellow index before the test from the yellow index after the test. It can be judged that the smaller the value of ΔYI, the less yellowing after the test and the higher the yellowing resistance.

[Coatability]
Regarding the coating composition, the depth at which streaks appear was measured using a grind gauge in accordance with JIS K5600-2-5, and evaluation was made based on the maximum value of the streak depth. It can be determined that the smaller the maximum value of the streak depth, the higher the dispersibility of the virus infection inhibitor in the paint and the higher the coatability of the virus infection inhibitor.

[Masterbatch for synthetic resin molding]
(Examples 32 to 46, Comparative Example 12)
Seven times the mass of water was prepared relative to the total mass of the virus infection inhibiting compound and the carrier. The virus infection inhibiting compounds and carriers (particles) shown in Table 3 were supplied to water in predetermined amounts and mixed uniformly to prepare a dispersion. The particles used for the carrier had the D50 particle diameter and specific surface area shown in Table 3.

Next, the dispersion liquid was pulverized using a spray dryer at an atomizer rotation speed of 20,000 rpm, and the entire amount of the virus infection inhibiting compound was attached (supported) on the surface of the carrier, and then a jet mill device (manufactured by Nissin Engineering Co., Ltd.) was used. The carrier with the virus infection inhibiting compound supported (attached) on its surface was crushed using a machine (trade name "SJ-500") under operating conditions of a raw material supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa. Obtained. The mass ratio of the virus infection inhibiting compound to the carrier (mass of the virus infection inhibiting compound/mass of the carrier) is shown in the "Compound/Support" column of Table 3.

In Examples 32 to 40 and Comparative Example 12, the obtained carrier was used as a virus infection inhibitor. In Examples 41 to 46, an antioxidant was added to the obtained carrier and mixed uniformly to prepare a virus infection inhibitor. The amounts of the virus infection inhibiting compound, carrier, and antioxidant in the virus infection inhibitor were adjusted as shown in Table 3.

50 parts by mass of the obtained virus infection inhibitor and 50 parts by mass of polypropylene (manufactured by Nippon Polypro Co., Ltd., trade name "Novatec PP BC6C") were uniformly melt-kneaded and mixed to produce a masterbatch 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 obtained virus infection inhibiting product was subjected to an antiviral test using the same test method as the coating film, and the antiviral activity value was measured, and the results are shown in Table 3.

The yellowing resistance of the obtained virus infection inhibiting product was measured in the same manner as the coating film, and the results are shown in Table 3.

The virus infection inhibitor of the present invention can produce a coating material with excellent coating properties. The virus infection inhibitor of the present invention makes it possible to produce a paint that hardly yellows even when placed in a high temperature environment and produces a coating film that has an excellent virus infection inhibiting effect.

Since the virus infection inhibitor of the present invention has excellent yellowing resistance, it is possible to produce a virus infection prevention product that maintains the appearance such as the color of the base material and has an excellent virus infection prevention effect. .

(Cross reference to related applications)
This application claims priority based on Japanese Patent Application No. 2022-128501 filed on August 10, 2022 and Japanese Patent Application No. 2022-176594 filed on November 2, 2022. , the disclosure of which is incorporated herein by reference in its entirety.

Claims

a support having a specific surface area of 1 to 1000 m 2 /g;
is supported on the above carrier and contains at least one infection-inhibiting functional group selected from the group consisting of a carboxy group, a sulfo group, a primary amino group, a secondary amino group, and a tertiary amino group, or a salt thereof. A virus infection inhibiting agent comprising a virus infection inhibiting compound, or a virus infection inhibiting compound supported on the carrier and containing a guanidine structure.
The virus infection inhibitor according to claim 1, wherein the carrier has a D50 particle diameter of 0.1 to 200 μm.
Claim 1 or Claim 2, wherein the mass ratio of the virus infection inhibiting compound to the carrier (mass of the virus infection inhibiting compound/mass of the carrier) is 0.02 to 10. virus infection inhibitor.
The virus infection inhibitor according to claim 1 or 2, wherein the carrier has a specific surface area of 50 to 1000 m 2 /g.
The virus infection inhibiting agent according to claim 1 or 2, wherein the virus infection inhibiting compound is a polymer having a weight average molecular weight of 1000 or more.
The virus infection inhibiting agent according to claim 1 or 2, wherein the virus infection inhibiting compound is a polymer having a secondary amino group or a guanidine structure.
The virus infection inhibitor according to claim 1 or 2, which contains an antioxidant.
A resin composition comprising a synthetic resin and the virus infection inhibitor according to claim 1 or 2.
The resin composition according to claim 8, which is used as a masterbatch for synthetic resin molding.
The resin composition according to claim 9, wherein the virus infection inhibitor contains an antioxidant.
11. The resin composition according to claim 10, wherein the antioxidant has a melting point of 200°C or less.
A virus infection inhibiting product comprising a base material and the virus infection inhibiting agent according to claim 1 or 2 contained in the base material.
The virus infection prevention product according to claim 12, wherein the base material is a paint.