TW202348136A - Viral infection inhibitor, viral infection-inhibiting particles, and viral infection-inhibiting paint - Google Patents

Abstract

The present invention provides a viral infection inhibitor capable of exhibiting excellent viral infection-inhibiting effects as well as having excellent dispersibility in paints and being capable of forming a coating film with excellent surface properties without generating clumps in the paint. This viral infection inhibitor comprises as an active ingredient a polymer compound comprising repeating units that have a carboxyl group or salt thereof. Said polymer compound has a pKa1 of 5.5 or less and a cross-linked structure, and even when included in a paint, exhibits excellent dispersibility in the paint and can disperse favorably in the paint.

Description

Viral infection inhibitors, viral infection inhibitory particles and viral infection inhibitory coatings

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

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

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

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

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

[Problem to be solved by the invention]

However, the above-mentioned antiviral synthetic resin composition has the following problem: when it is dispersed in a paint and used, the antiviral synthetic resin composition forms lumps in the paint, and when the paint is applied, the antiviral synthetic resin composition becomes lumpy. When applied to the object to be coated, stripe-like irregularities are formed on the surface of the coating film, and stripe-like irregularities are formed on the surface of the obtained coating film.

In addition, the above-mentioned antiviral synthetic resin composition only contains a sulfonic acid-based surfactant in the synthetic resin, and the sulfonic acid-based surfactant does not have sufficient antiviral properties (viral infection inhibitory effect). It is expected that the antiviral synthetic resin composition will have an excellent virus infection inhibitory effect. Viral infection inhibitors.

The present invention provides a virus infection inhibitor that exhibits an excellent virus infection inhibitory effect, has excellent dispersibility in paint, and can form a coating film with excellent surface properties without clumping in the paint. [Technical means to solve the problem]

The virus infection inhibitor of the present invention is characterized in that it contains a polymer compound, the polymer compound contains a repeating unit having a carboxyl group or a salt thereof, and the polymer compound has a pKa1 of 5.5 or less and has a cross-linked structure.

The viral infection-inhibiting particles of the present invention are characterized by including base particles and the above-mentioned polymer compound attached to the surface of the base particles.

The viral infection inhibitory product of the present invention is characterized by containing a base material and the above-mentioned viral infection inhibitory agent. [Effects of the invention]

The viral infection inhibitor of the present invention contains a polymer compound. The polymer compound contains a repeating unit having a carboxyl group or a salt thereof. The pKa1 of the polymer compound is 5.5 or less and has a cross-linked structure. Therefore, even if it is contained in a paint When used, it can also exhibit excellent dispersibility in coatings and be well dispersed into coatings.

Therefore, a coating film containing the viral infection inhibitor of the present invention is applied to an object to be coated, and the coating film obtained has excellent surface properties, and the coating film obtained by drying the coating film has excellent appearance properties.

The viral infection inhibitor of the present invention contains a polymer compound as an active ingredient. The polymer compound contains a repeating unit having a carboxyl group or a salt thereof, and the polymer compound has a pKa1 of 5.5 or less and has a cross-linked structure.

The viral infection inhibitor of the present invention contains a polymer compound containing a repeating unit having a carboxyl group or a salt thereof as an active ingredient.

In the viral infection inhibitor, the content of the polymer compound containing a repeating unit having a carboxyl group or a salt thereof and having a pKa1 of 5.5 or less and a cross-linked structure is preferably 80 mass% or more, more preferably 85 mass% or more, even more preferably It is 90 mass % or more, more preferably 95 mass % or more, more preferably 99 mass % or more, more preferably 100 mass %.

In the viral infection inhibitor, the content of the polymer compound containing a repeating unit having a carboxyl group or a salt thereof and having a pKa1 of 5.5 or less and a cross-linked structure is preferably 80 mass % or more, more preferably 85 mass % in the active ingredient. Above, more preferably 90 mass% or more, more preferably 95 mass% or more, more preferably 99 mass% or more, still more preferably 100 mass%.

The polymer compound has a carboxyl group (-COOH) or its salt in the molecule. The polymer compound exhibits a virus infection inhibitory effect because it contains a structural moiety of a carboxyl group or a salt thereof. Polymer compounds have excellent viral infection inhibitory effects especially on viruses with envelopes.

The salt of the carboxyl group contained in the polymer compound is not particularly limited, and examples include 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⁺ ], etc.

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

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

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

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

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

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

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

Regarding the viral infection inhibitor, the antiviral activity value 10 minutes after the reaction in the antiviral test based on ISO21702 is preferably 2.0 or more. Regarding viral infection inhibitors, the antiviral activity value 24 hours after the reaction in the antiviral test conducted in accordance with ISO21702 is preferably 2.0 or more. Regardless of the types of viruses to be evaluated, it is preferred that the antiviral activity value for at least one virus reaches 2.0 or above.

The pKa1 of the polymer compound is 5.5 or less, preferably 5.0 or less, more preferably 4.7 or less. If the pKa1 of the polymer compound is 5.5 or less, the virus infection inhibitory effect of the virus infection inhibitor is improved. When the polymer compound is a polybasic acid, the polymer compound dissociates in multiple stages, and pKa1 refers to the pKa calculated based on the dissociation constant of the first stage. Here, when the electrolyte HA dissociates into H ⁺ and A ^- and achieves dissociation equilibrium (1), the acid dissociation constant Ka is defined by formula (2), and pKa is the common logarithm of the inverse of the acid dissociation constant Ka (3 ) to define.

The pKa1 of a polymer compound refers to the value measured by titration. Specifically, pKa1 can be determined by titrating a polymer compound and sodium hydroxide at 25°C and measuring the pH at 25°C at the half-equivalence point (the point at which half the amount of neutralization is dropped).

Furthermore, when the polymer compound contains a salt of a carboxyl group, the pKa1 of the polymer compound is the pKa1 of the polymer compound measured by the above method after converting the salt of the carboxyl group into a carboxyl group. An example of a method for converting salts of carboxyl groups into carboxyl groups is a method in which a polymer compound is mixed with a 1 mol % aqueous hydrochloric acid solution, and all salts of carboxyl groups contained in the polymer compound are converted into carboxyl groups, and then Hydrochloric acid and water are removed by common methods such as freeze-drying.

The weight average molecular weight of the polymer compound is 3,000 or more, preferably 5,000 or more, more preferably 10,000 or more, more preferably 100,000 or more. If the weight average molecular weight of the polymer compound is more than 3000, the adsorption point between each molecule of the polymer compound and the virus will increase, and the interaction between the polymer compound and the virus will become stronger, which can improve the virus infection inhibitory effect of the virus infection inhibitor. .

The weight average molecular weight of the polymer contained in the polymer compound is preferably 1,000,000 or less, more preferably 900,000 or less, more preferably 800,000 or less, still more preferably 500,000 or less. If the weight average molecular weight of the polymer compound is 1,000,000 or less, the dispersibility of the polymer compound in the paint is improved, resulting in a form in which the polymer compound and viruses easily interact, and the virus infection inhibitory effect of the virus infection inhibitor is improved.

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

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

The pH of the polymer compound at 25°C is preferably 2 or more, more preferably 3 or more, and more preferably 4 or more. The pH of the polymer compound at 25°C is preferably below 4.5. If the pH of the polymer compound is 2 or more, the virus infection inhibitory effect of the virus infection inhibitor will be improved. If the pH of the polymer compound is 4.5 or less, the virus infection inhibitory effect on viruses that do not have a mantle is improved. Furthermore, the pH of a polymer compound refers to the pH value at 25°C of a mixed solution obtained by adding 0.5 g of the polymer compound to 99.5 g of purified water and uniformly mixing. Regarding the mixed liquid, the total amount of the polymer compound can be dissolved in purified water or a part of the polymer compound can be dissolved in purified water to form a saturated aqueous solution.

The polymer compound contains a repeating unit having a carboxyl group or a salt thereof. Examples of the repeating unit include a monomer unit containing a carboxyl group-containing derivative of a carboxyl group or a salt thereof. The polymer compound may be a homopolymer of a monomer containing a carboxyl derivative, or a copolymer of a monomer containing a carboxyl derivative and a monomer copolymerizable therewith.

The monomer of the carboxyl group-containing derivative is not particularly limited, and examples thereof include: acrylic acid, methacrylic acid, (meth)acrylic acid β-carboxyethyl ester, (meth)acrylic acid 5-carboxypentyl ester, succinic acid mono( Methacryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, carboxyl Betaine type monomers or salts thereof are preferably acrylic acid, methacrylic acid, sodium acrylate, or sodium methacrylate. In addition, the carboxyl derivative-containing monomer may be used alone or in combination of two or more types.

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

The content of the carboxyl derivative-containing monomer unit in the polymer compound is preferably 80 mass% or more, more preferably 85 mass% or more, and more preferably 90 mass% or more. The content of the carboxyl derivative-containing monomer unit in the polymer compound is preferably 99 mass% or less, more preferably 97 mass% or less, and more preferably 95 mass% or less. If the content of the carboxyl derivative-containing monomer unit in the polymer compound is 80% by mass or more, the virus infection inhibitory effect of the virus infection inhibitor is improved. If the content of monomer units containing carboxyl derivatives in the polymer compound is less than 99% by mass, the dispersibility of the polymer compound in the paint can be improved, which can reduce the caking of virus infection inhibitors in the paint and can form The coating film has excellent surface properties and forms a form in which polymer compounds and viruses can easily interact, thereby improving the virus infection inhibitory effect of the virus infection inhibitor.

Polymer compounds can be polymerized using general polymerization methods. For example, a polymer compound can be obtained by polymerizing a monomer composition containing a carboxyl derivative-containing monomer in the presence of a general-purpose radical polymerization initiator. Furthermore, examples of the radical polymerization initiator include: 1-hydroxycyclohexan-1-ylphenyl ketone, t-hexyl peroxypivalate, benzoyl peroxide, Thermal cracking free radical polymerization initiators such as azobisisobutyronitrile, etc.

The polymer compound preferably does not contain aromatic rings in the molecule. If the polymer compound does not contain an aromatic ring, the volume of the polymer compound is reduced, so the molecular structure part containing a carboxyl group or its salt can interact with viruses efficiently and exert an excellent virus infection inhibitory effect.

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

The total content of the carboxyl group and the salt of the carboxyl group in the polymer compound is preferably 5 mmol/g or more, preferably 7 mmol/g or more, preferably 9 mmol/g or more, preferably 11 mmol/g or more, and preferably 11 mmol/g or more. Preferably, it is above 13 mmol/g. The total content of the carboxyl group and the salt of the carboxyl group in the polymer compound is preferably 20 mmol/g or less, preferably 18 mmol/g or less, preferably 17 mmol/g or less, and preferably 16 mmol/g or less. If the total content of the carboxyl group and the salt of the carboxyl group in the polymer compound is 5 mmol/g or more, the virus infection inhibitory effect of the virus infection inhibitor will be improved. If the total content of the carboxyl group and the salt of the carboxyl group in the polymer compound is less than 20 mmol/g, the dispersibility of the virus infection inhibitor in the paint of the polymer compound will be improved, and the virus infection inhibitor will not be easy to agglomerate in the paint, and can It forms a coating film with excellent surface properties and becomes a form in which polymer compounds and viruses can easily interact, thereby improving the virus infection inhibitory effect of the virus infection inhibitor.

In polymer compounds, by adjusting both the gel fraction and the total content of the carboxyl group and the salt of the carboxyl group, the carboxyl group and the salt of the carboxyl group can be effectively aligned toward the outside, thereby improving the virus infection inhibitory effect of the virus infection inhibitor. .

In addition, the total content of the carboxyl group and the salt of the carboxyl group in the polymer compound refers to the value measured by titration. Specifically, accurately weigh about 1 g (A g) of the dried polymer compound, add 200 mL of purified water to the polymer compound, and then titrate with 0.1 mol/L sodium hydroxide aqueous solution at 25°C. , calculate the consumption of sodium hydroxide aqueous solution (B mL) up to the half-equivalence point (the point at which half of the amount of dripping and neutralization is completed), and calculate the carboxyl group content (mmol/g) in the polymer compound using the following formula ). Furthermore, when the polymer compound contains a salt of a carboxyl group, the polymer compound is mixed into a 1 mol% hydrochloric acid aqueous solution, and all the salts of the carboxyl groups contained in the polymer compound are converted into carboxyl groups, and then the polymer compound is Determine the carboxyl group content according to the above method, and set the obtained carboxyl group content (mmol/g) as the total content of the carboxyl group and the salt of the carboxyl group (mmol/g). Carboxyl content (mmol/g) = 0.1×A/B

The active ingredients of viral infection inhibitors, namely polymer compounds, have a cross-linked structure. Because the polymer compound has a cross-linked structure, when the virus infection inhibitor is dispersed in the paint, it can reduce the situation where the polymer compound absorbs the paint and swells, and reduces the decrease in dispersion in the paint caused by the swelling of the polymer compound. Polymer compounds have excellent dispersibility in coatings. Therefore, stripe-like unevenness will not be formed in the coating film obtained by applying the coating material containing the virus infection inhibitor to the object to be coated, and the coating film obtained will have excellent surface properties and excellent appearance.

The method of introducing a cross-linked structure into the polymer compound is not particularly limited. For example, a method of adding an organic peroxide to the polymer compound and heating the polymer compound to a temperature higher than the decomposition temperature of the organic peroxide to cross-link the polymer compound, etc. .

The organic peroxide is not particularly limited, and examples thereof include: tert-hexyl pivalate peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and tert-butyl peroxybenzoate. Ester, cumyl hydroperoxide, tert-butyl hydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylhexane, 4, 4-Di(tert-butylperoxy)n-butyl valerate, α,α'-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5- Di(tert-butylperoxy)hexyne-3, tert-butylperoxycumyl, etc.

The degree of introducing a cross-linked structure into the polymer compound can be controlled by adjusting the amount of organic peroxide added to the polymer compound. The amount of the organic peroxide added to the polymer compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the polymer compound.

Cross-linking assistants can also be used when cross-linking polymer compounds with organic peroxides. Examples of crosslinking aids include divinylbenzene, trimethylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, and 1,10-decanediol dimethacrylate. , triallyl benzenetricarboxylate, triallyl isocyanurate, ethyl vinylbenzene, neopentyl glycol dimethacrylate, triallyl 1,2,4-benzenetricarboxylate, 1,6 -Hexylene glycol dimethacrylate, lauryl methacrylate, stearyl methacrylate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, etc. .

The degree of introducing a cross-linked structure into the polymer compound can be controlled by adjusting the amount of cross-linking auxiliary added to the polymer compound. The amount of the cross-linking auxiliary added to the polymer compound is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more based on 100 parts by mass of the polymer compound. The amount of the cross-linking auxiliary added to the polymer compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less based on 100 parts by mass of the polymer compound.

The gel fraction of the polymer compound is preferably 65 mass% or more, more preferably 70 mass% or more, more preferably 75 mass% or more, and more preferably 80 mass% or more. The gel fraction of the polymer compound is preferably 99 mass% or less, more preferably 98 mass% or less, more preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 85 mass% or less. If the gel fraction of the polymer compound is 65% by mass or more, when the viral infection inhibitor is dispersed in the paint, the polymer compound absorbs the paint and swells, thereby reducing the risk of the polymer compound swelling in the paint. The dispersion of the polymer compound is reduced. The polymer compound has excellent dispersion in the coating and can form a coating film with excellent surface properties. If the gel fraction of the polymer compound is 99% by mass or less, the carboxyl group and the salt of the carboxyl group can be effectively aligned outward, thereby improving the virus infection inhibitory effect of the virus infection inhibitor.

In addition, the gel fraction of a polymer compound refers to a value measured according to the following method. Weigh the polymer compound A g, immerse it in purified water at 60°C for 24 hours, filter the insoluble components using a 200-mesh wire mesh, vacuum dry the residue on the wire mesh, and measure the weight of the dried residue (B g), calculate the gel fraction by the following formula. Gel fraction of polymer compound (mass %) = (B/A) × 100

The swelling rate of the polymer compound in water is preferably more than 800%, more preferably more than 850%, more preferably more than 1000%, more preferably more than 1200%, more preferably more than 1300%. The swelling rate of the polymer compound in water is preferably 3000% or less, more preferably 2900% or less, more preferably 2800% or less, more preferably 2700% or less, still more preferably 2600% or less. Viruses often exist in liquids containing moisture such as saliva. If the swelling rate of a polymer compound in water is more than 800%, the polymer compound will swell effectively due to contact with the liquid containing the virus and moisture, thereby increasing the surface area. By increasing the amount, it becomes a form that easily interacts with viruses, and the virus infection inhibitory effect of the virus infection inhibitor is improved. If the swelling rate of the polymer compound in water is less than 3000%, the shape change of the polymer compound during use can be reduced, the shedding of the virus infection inhibitor from the coating film can be reduced, and the excellence of the coating film can be stably maintained. Virus infection inhibitory effect.

The swelling rate of polymer compounds in water refers to the value measured according to the following methods. That is, the polymer compound C g was weighed, immersed in purified water at 60°C for 24 hours, and the insoluble components were filtered through a 200-mesh wire mesh. After leaving it at 25°C for 2 hours, the residue on the wire mesh was measured. Weight (D g), calculate the swelling rate according to the following formula. Swelling rate of polymer compounds in water (mass %) = (D/C) × 100

The viral infection inhibitor contains a polymer compound as an active ingredient, but the manufacturing method of the viral infection inhibitor is not particularly limited. The viral infection inhibitor can be produced by mixing the polymer compound with compounds added as needed according to general methods.

Viral infection inhibitors can also be attached (carried) to the surface of base particles for use. By attaching the virus infection inhibitor to the surface of the base particles in advance, the virus infection inhibitor does not become lumpy and can be evenly dispersed in the paint. Therefore, the virus infection inhibitor can be dispersed well in the paint without clumping, a coating film can be formed without stripe-like unevenness on the object to be coated, and a coating film with excellent surface properties can be formed. Furthermore, the surface area of the virus infection inhibitor can be increased, the contact between the virus infection inhibitor and the virus can be fully ensured, and the virus infection inhibitory effect of the virus infection inhibitor can be fully exerted.

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

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

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

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

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

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

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

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

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

The adhesion amount of the polymer compound 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. If the adhesion amount of the polymer compound is 1 part by mass or more, the virus infection inhibitor can be uniformly attached to the surface of the base particles, and the virus infection inhibitory effect of the virus infection inhibitor can be more effectively exerted.

The adhesion amount of the polymer compound to the 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. If the adhesion amount of the polymer compound is 50 parts by mass or less, the virus infection inhibitors will not be bonded to each other, the virus infection inhibitors will be efficiently arranged on the surface of the resin particles, and the virus infection inhibitory effect will be improved.

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

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

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

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

The viral infection inhibitory paint is included in the paint to form a virus infection-inhibiting paint. The coating film formed by the virus infection-inhibiting paint exhibits excellent virus infection-inhibiting effects.

The content of the polymer compound in the virus infection inhibiting paint is preferably 1% by mass or more, more preferably 2% by mass or more. The content of the polymer compound in the virus infection-inhibiting paint is preferably 10 mass% or less, more preferably 7 mass% or less, and more preferably 5 mass% or less. If the content of the polymer compound is 1% by mass or more, the coating film formed of the virus infection-inhibiting paint exhibits an excellent virus infection-inhibiting effect. If the content of the polymer compound is 10% by mass or less, the surface properties of the coating film formed by the virus infection-inhibiting paint will be improved.

As mentioned above, the viral infection inhibitor has a cross-linked structure in the polymer compound, which reduces the absorption of the paint and is well dispersed in the paint. By applying the viral infection inhibitory paint containing the virus infection inhibitor It can form a coating film with excellent surface properties without unevenness such as streaks on the object to be coated. By drying the coating film and hardening it if necessary, a coating film having excellent surface properties (appearance) without irregularities such as streaks can be obtained.

Furthermore, there is no particular limitation on the object to be coated with the viral infection-inhibiting paint, as long as it is intended to impart a virus infection-inhibiting effect. Examples thereof include: synthetic resin molded articles, wallpapers, decorative boards, flooring materials, and fibers. Products (fabrics, non-woven fabrics, knitted fabrics), interior products and interior materials for vehicles (such as cars, airplanes, ships, etc.) (seats, child seats and foams constituting them, etc.), kitchen supplies, Baby products, building interior materials, etc.

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

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

As the paint, a conventionally known paint is used. The coating is preferably a hydrophobic coating because the dispersibility of the virus infection inhibitor is improved and a coating film with excellent surface properties can be formed. The hydrophobic paint is not particularly limited, and examples thereof include oily paints (such as mixed paints, oily varnishes, etc.), cellulose paints, and synthetic resin paints. Coatings also include photocurable coatings that are polymerized by irradiation with ultraviolet rays and other radiation to produce a binder component.

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

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

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

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

Carboxyl group-containing polymer compounds 1 to 13 were prepared as polymer compounds, and these polymer compounds were used as viral infection inhibitors.

・Carboxyl group-containing polymer compound 1 (polyacrylic acid with a cross-linked structure, manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., trade name "HIVISWAKO 103") ・Carboxyl group-containing polymer compound 2 (polyacrylic acid with a cross-linked structure, manufactured by Sumitomo Seika Co., Ltd., trade name "HV-803ERK") ・Carboxyl group-containing polymer compound 3 (polyacrylic acid with a cross-linked structure, manufactured by Sumitomo Seika Co., Ltd., trade name "SW-705ER") ・Carboxyl group-containing polymer compound 4 (polyacrylic acid with a cross-linked structure, manufactured by Toagosei Co., Ltd., trade name "PW-120") ・Carboxyl group-containing polymer compound 5 (polyacrylic acid with a cross-linked structure, manufactured by Sumitomo Seika Co., Ltd., trade name "SW-703ER") ・Carboxyl group-containing polymer compound 6 (polyacrylic acid with a cross-linked structure, manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., trade name "HIVISWAKO 104") ・Carboxyl group-containing polymer compound 7 (polyacrylic acid with a cross-linked structure, manufactured by Nippon Surfactant Industries, trade name "NTC-CARBOMER 381") ・Carboxyl group-containing polymer compound 8 (polyacrylic acid with a cross-linked structure, manufactured by Nippon Surfactant Industries, trade name "NTC-CARBOMER 380") ・Carboxyl group-containing polymer compound 9 (polyacrylic acid with a cross-linked structure, manufactured by Sumitomo Seika Co., Ltd., trade name "SW-705E") ・Carboxyl group-containing polymer compound 10 (polyacrylic acid with a cross-linked structure, manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., trade name "HIVISWAKO 105") ・Carboxyl group-containing polymer compound 11 (polyacrylic acid, manufactured by Nippon Shokubai Co., Ltd., trade name "AS-58") ・Carboxyl group-containing polymer compound 12 (polyacrylic acid, manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., trade name "Polyacrylic Acid 250,000") ・Carboxyl group-containing polymer compound 13 (polyacrylic acid, manufactured by Toagosei Co., Ltd., trade name "AC-10P")

[Preparation of particles of carboxyl group-containing polymer compounds 1 to 13] The carboxyl group-containing polymer compound was coarsely pulverized using a roller press (trade name "Model 150" manufactured by Seishin Enterprise Co., Ltd.) under operating conditions of rotation speed 25 rpm and extrusion force 25 t, and then a jet mill device (manufactured by Nisshin Engineering Co., Ltd. Trade name "SJ-500"), the carboxyl group-containing polymer compound particles are pulverized under operating conditions of a supply rate of 1 kg/h and a compressed air pressure of 0.75 MPa to obtain carboxyl group-containing polymer compound particles.

[Preparation of polymer compound 8 containing carboxyl groups attached to particles] 0.05 parts by mass of particles of carboxyl group-containing polymer compound 8 and 0.1 part by mass of polystyrene particles (primary particles) having an average particle diameter of 4 μm were supplied to 100 parts by mass of water, and a spray dryer was used at an atomizer rotation speed Powder was carried out at 20,000 rpm, and all the particles of the carboxyl group-containing polymer compound 8 were attached (supported) to the surface of the polystyrene particles, and then a jet mill device (trade name "SJ-500" manufactured by Nisshin Engineering Co., Ltd. ), pulverized under operating conditions of raw material supply rate 1 kg/h and compressed air pressure 0.75 MPa to obtain polystyrene particles with particles of carboxyl group-containing polymer compound 8 attached to the surface. In addition, in Table 1, "polystyrene particles with particles of the carboxyl group-containing polymer compound 8 attached to the surface" are described as "particles with the carboxyl group-containing polymer compound 8 attached."

For the carboxyl group-containing polymer compounds used in the examples and comparative examples, the weight average molecular weight Mw, pKa1, pH at 25°C [pH (25°C)], the total content of the carboxyl group and the salt of the carboxyl group, and the The swelling rate and gel fraction are shown in Table 1. Furthermore, in Table 1, "swelling rate in water" is abbreviated as "swelling rate". Furthermore, since the carboxyl group-containing polymer compounds 1 to 10 have a cross-linked structure, the weight average molecular weight Mw cannot be measured.

(Examples 1 to 11 and Comparative Examples 1 to 3) A viral infection inhibitor containing 3 parts by mass of the "carboxyl group-containing polymer compound particles shown in Table 1" produced according to the above method, and an ultraviolet curable acrylic paint (trade name "AI-N2" manufactured by COATTEC) 97 parts by mass were mixed to prepare a virus infection inhibiting paint. Using wire bar applicator #8, apply the viral infection-inhibiting paint on the polyethylene film to a thickness of 18 μm to form a coating layer. Furthermore, in Example 11, the particles of the carboxyl group-containing polymer compound 8 were adjusted to 3 parts by mass.

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

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

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

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

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

The obtained test coating was subjected to antiviral tests for influenza virus and feline calicivirus according to ISO21702. For the virus suspension after the reaction, the virus infection titer of the test coating was calculated by the plaque lysis method.

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

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

[Dispersion] The obtained virus infection-inhibiting paint was observed using a grind gauge in accordance with JIS K5600-2-5 to observe the position where spots began to appear.

[Table 1] polymer compounds Weight average molecular weight Mw pKa1 pH（25℃） Total content of carboxyl group and carboxyl salt (mmol/g) Swelling rate (%) Gel fraction (mass %) Antiviral activity value Dispersity ( μm) flu virus feline calicivirus Example 1 Carboxyl-containing polymer compounds 1 - 4.2～5.0 3.35 13.1～15 2590 95 2.3 2.3 47 Example 2 Carboxyl-containing polymer compounds 2 - 4.2～5.0 3.23 13.1～15 2509 94 2.2 2.1 46 Example 3 Carboxyl-containing polymer compounds 3 - 4.2～5.0 3.28 13.1～15 1527 93 2.1 2.0 44 Example 4 Carboxyl-containing polymer compounds 4 - 4.2～5.0 3.3 13.1～15 2538 93 2.2 2.2 45 Example 5 Carboxyl-containing polymer compounds 5 - 4.2～5.0 3.37 13.1～15 1527 92 2.1 2.0 44 Example 6 Carboxyl-containing polymer compounds 6 - 4.2～5.0 3.32 13.1～15 2445 91 2.1 2.4 40 Example 7 Polymer compounds containing carboxyl groups 7 - 4.2～5.0 3.09 13.1～15 2354 85 2.2 2.1 29 Example 8 Polymer compounds containing carboxyl groups 8 - 4.2～5.0 3.08 13.1～15 2275 84 2.2 2.1 28 Example 9 Carboxyl-containing polymer compounds 9 - 4.2～5.0 3.3 13.1～15 1955 81 2.1 2.0 25 Example 10 Polymer compounds containing carboxyl groups 10 - 4.2～5.0 3.31 13.1～15 901 72 2.2 2.1 60 Example 11 Particles are attached with carboxyl-containing polymer compounds 8 - 4.2～5.0 3.08 13.1～15 2275 84 2.2 2.1 29 Comparative example 1 Carboxyl-containing polymer compounds 11 800000 4.2～5.0 3.0 13.1～15 40 0 2.5 2.3 90 Comparative example 2 Carboxyl-containing polymer compounds 12 250000 4.2～5.0 2.8 13.1～15 5 0 2.1 2.1 95 Comparative example 3 Carboxyl-containing polymer compounds 13 5000 4.2～5.0 2.9 13.1～15 0 0 2.4 2.1 >100 [Industrial availability]

When the viral infection inhibitor of the present invention is contained in a paint, it exhibits excellent dispersibility and is well dispersed into the paint. Therefore, a coating film containing the viral infection inhibitor of the present invention is applied to an object to be coated, and the coating film obtained has excellent surface properties, and the coating film obtained by drying the coating film has excellent appearance properties.

(Cross-reference of related applications) This application claims priority based on Japanese Patent Application No. 2022-037394 filed on March 10, 2022, the contents of which are incorporated into this specification in its entirety by reference.

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Claims (9)

A viral infection inhibitor, characterized in that it contains a polymer compound, the polymer compound contains a repeating unit having a carboxyl group or a salt thereof, and the polymer compound has a pKa1 of 5.5 or less and has a cross-linked structure. For example, the viral infection inhibitor of claim 1, wherein the gel fraction of the above-mentioned polymer compound is 65 to 99 mass%. For example, the viral infection inhibitor of claim 1 or 2, wherein the swelling rate of the above-mentioned polymer compound in water is 800-3000%. The viral infection inhibitor according to any one of claims 1 to 3, wherein the pH of the above-mentioned polymer compound at 25°C is 4.5 or less. The viral infection inhibitor according to any one of claims 1 to 4, wherein the total content of the carboxyl group and the salt of the carboxyl group of the above-mentioned polymer compound is 5 to 20 mmol/g. Such as the viral infection inhibitor of claim 5, wherein the total content of the carboxyl group and the salt of the carboxyl group of the above-mentioned polymer compound is 13 to 16 mmol/g. A viral infection-inhibiting particle, characterized by comprising a base particle and the viral infection inhibitor according to any one of claims 1 to 6 attached to the surface of the base particle. The viral infection-inhibiting particles of Claim 7, wherein the base particles contain an acrylic resin, a styrene resin or an inorganic compound. A virus infection-inhibiting coating, characterized by comprising a coating and the viral infection inhibitor contained in any one of claims 1 to 6 contained in the coating.