JP7725809B2 - Antiviral products - Google Patents

Description

The present invention relates to an antiviral article and an antiviral resin composition.

From a hygiene perspective, antibacterial treatment has traditionally been performed by applying an antibacterial composition to the surfaces of objects that people touch, such as interior materials for buildings and vehicles, office equipment, and touch panels.

Antibacterial compositions or antibacterial articles have been proposed in, for example, Patent Documents 1 to 3.
However, for viruses such as influenza viruses, merely having antibacterial properties is not sufficient. That is, the antibacterial compositions or articles disclosed in Patent Documents 1 to 3 sometimes fail to provide satisfactory antiviral properties.

On the other hand, Patent Documents 4 and 5 propose compositions or articles with antiviral properties.

Japanese Unexamined Patent Publication No. 63-265958 Patent No. 3551201 Patent No. 4840048 Patent No. 6145758 Patent No. 6229429

The antiviral resin composition of Patent Document 4 contains cuprous oxide particles, etc. As a result, it is not possible to prevent the color (reddish-brown) derived from the color of cuprous oxide.

The antiviral decorative sheet for interior use of Patent Document 5 is obtained by compounding a silver-based inorganic additive or a zinc-based inorganic additive in the coating resin on the outermost surface of the decorative sheet.
Of the additives disclosed in Patent Document 5, the latter zinc-based inorganic additive has a problem of biotoxicity.
On the other hand, among the additives disclosed in Patent Document 5, the former silver-based inorganic additive is expensive but does not have the problem of biotoxicity. However, the former silver-based inorganic additive has the problem of discoloring to brown when exposed to light (visible light, ultraviolet light). In particular, when the amount of the silver-based inorganic additive added is increased to exhibit antiviral properties, the problem of discoloration due to light becomes significant.

The objective of the present invention is to provide antiviral articles and antiviral resin compositions that can suppress color problems such as discoloration due to light.

In order to solve the above problems, the present invention provides the following [1] and [2].
[1] An antiviral article having a cured material layer, wherein the cured material layer contains a cured material of a curable resin composition and particles of an imidazole-based compound.
[2] An antiviral resin composition comprising a curable resin composition and particles of an imidazole-based compound.

The present invention provides antiviral articles and antiviral resin compositions that can suppress color problems such as discoloration due to light.

FIG. 1 is a cross-sectional view showing one embodiment of the antiviral article of the present invention. FIG. 1 is a cross-sectional view showing another embodiment of the antiviral article of the present invention. FIG. 1 is a cross-sectional view showing another embodiment of the antiviral article of the present invention.

[Antiviral products]
The antiviral article of the present invention is an article having a cured material layer, and the cured material layer contains a cured material of a curable resin composition and particles of an imidazole-based compound.

Generally, anything that has "antiviral properties" also has "antibacterial properties." Therefore, the antiviral article of the present invention and the antiviral resin composition of the present invention described below can be used not only for antiviral purposes, but also for antibacterial purposes. Furthermore, because mold is a type of fungus, the antiviral article of the present invention and the antiviral resin composition of the present invention described below can also be used for antifungal purposes.

1(A) to 1(E), 2(A) to 2(D), and 3 are cross-sectional views showing representative embodiments of an antiviral article 100 of the present invention.
The antiviral article 100 in FIGS. 1(A) to 1(E), 2(A) to 2(D), and 3 has a cured material layer 10 containing a cured material 11 of a curable resin composition and particles 12 of an imidazole-based compound.

The antiviral article 100 in FIGS. 1(A) to 1(E) is formed of a single layer of a cured material layer 10.
The cured material layer 10 in Fig. 1(A) contains imidazole compound particles 12 throughout the cured material layer 10 in both the thickness direction (Z-axis direction in the figure) and in-plane directions (directions within the XY plane in the figure). The cured material layer 10 in Fig. 1(B) contains imidazole compound particles 12 on the surface side (upper side in the figure) of the cured material layer 10. The cured material layer 10 in Fig. 1(C) contains imidazole compound particles 12 on the surface side (upper side in the figure) and back side (lower side in the figure) of the cured material layer 10. The cured material layer 10 in Fig. 1(D) contains imidazole compound particles 12 in a partial region in the in-plane direction on the surface side (upper side in the figure) of the cured material layer 10. The cured material layer 10 in FIG. 1(E) contains particles 12 of an imidazole-based compound in a portion of the surface side (upper side of the figure) of the cured material layer 10 and in a portion of the back side (lower side of the figure) of the cured material layer 10.
1(A) to 1(E), there are no particular limitations on the location of the imidazole compound particles 12 within the cured material layer 10. However, from the viewpoint of enhancing antiviral properties, it is preferable that the imidazole compound particles 12 are present on the surface that comes into contact with people.

An antiviral article 100 consisting of a single layer of cured material layer 10, as shown in Figures 1(A) to (E), can be obtained, for example, by forming a laminate in which the cured material layer 10 is formed on a releasable substrate, and then peeling off the releasable substrate from the laminate.

The antiviral article 100 in FIGS. 2(A) to 2(D) has a cured material layer 10 on a substrate 20.
The antiviral article 100 in Fig. 2(A) has a cured material layer 10 over the entire surface of one side of the substrate 20. The antiviral article 100 in Fig. 2(B) has a cured material layer 10 over the entire surfaces of both sides of the substrate 20. The antiviral article 100 in Fig. 2(C) has a cured material layer 10 in a partial region of one side of the substrate 20 (the + side in the Z axis direction in the figure). The antiviral article 100 in Fig. 2(D) has a cured material layer 10 in a partial region of one side of the substrate 20 (the + side in the Z axis direction in the figure) and in a partial region of the other side of the substrate 20 (the - side in the Z axis direction in the figure).
2(A) to 2(D), the cured material layer 10 may be formed on the entire surface of the substrate 20, or may be formed on a part of the surface of the substrate 20. Furthermore, as shown in Figs. 2(A) to 2(D), the cured material layer 10 may be formed on only one surface of the substrate 20, or may be formed on both surfaces of the substrate 20.

The antiviral article 100 in Figure 3 has a cured material layer 10 on a three-dimensional substrate 20. The three-dimensional substrate 20 in Figure 3 is a door handle, and Figure 3 shows a cross-sectional view of the door handle.

<Cured Product of Curable Resin Composition>
The cured material layer contains a cured material of a curable resin composition. In this specification, the "cured material of a curable resin composition" may be abbreviated as "cured material."
The cured product of the curable resin composition mainly serves as a binder resin. By including this cured product, the antiviral article has good scratch resistance and can more easily maintain its antiviral properties over a long period of time.

Cured products of curable resin compositions include cured products of thermosetting resin compositions and cured products of ionizing radiation-curable resin compositions, of which cured products of ionizing radiation-curable resin compositions are preferred from the standpoints of scratch resistance and production efficiency.

The thermosetting resin composition is a composition that contains at least a thermosetting resin and is a resin composition that is cured by heating.
Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc. In addition to these thermosetting resins, a curing agent, a curing catalyst, etc. are added to the thermosetting resin composition as needed.

Typical examples of ionizing radiation-curable resin compositions include electron beam-curable resin compositions and ultraviolet light-curable resin compositions. Of these, electron beam-curable resin compositions are preferred because they do not require a polymerization initiator, have less odor, and are less prone to discoloration. Furthermore, when the cured product layer contains an ultraviolet light absorber, as described below, electron beam-curable resin compositions are preferred because they tend to increase the crosslink density of the cured product layer and improve scratch resistance and contamination resistance.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound").
The ionizing radiation-curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. Further examples of the ionizing radiation-curable functional group include an epoxy group and an oxetanyl group.
In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group, and the term "(meth)acrylate" refers to an acrylate or a methacrylate.
Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and typically includes ultraviolet (UV) rays or electron beams (EB), but also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.
Specifically, the ionizing radiation curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") that have been conventionally used as ionizing radiation curable resins.

The ionizing radiation-curable compound is preferably a compound having two or more ethylenically unsaturated bond groups, and more preferably a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. Both monomers and oligomers can be used as the polyfunctional (meth)acrylate compound.

Among the polyfunctional (meth)acrylate compounds, examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate.
Examples of trifunctional or higher functional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate.
Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

Urethane (meth)acrylates can be obtained, for example, by reacting polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates.

Preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting a trifunctional or higher aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with (meth)acrylic acid; (meth)acrylates obtained by reacting a difunctional or higher aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with a polybasic acid and (meth)acrylic acid; and (meth)acrylates obtained by reacting a difunctional or higher aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with a phenol and (meth)acrylic acid.

The above ionizing radiation curable resins can be used alone or in combination of two or more.

When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like.
The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, and the like.

The content of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass, based on the total amount of binder resin.

<Imidazole Compound Particles>
The cured material layer contains particles of an imidazole-based compound.
Metal-based antiviral agents such as cuprous oxide particles and silver-based inorganic additives have color problems, such as being colored from the beginning or discoloring due to the influence of light, etc. On the other hand, imidazole-based compound particles do not cause the above-mentioned color problem.
In addition, in the present invention, the imidazole-based compound is present in the form of particles in the cured material layer. In other words, the imidazole-based compound is present in the form of particles without dissolving in the ink for the cured material layer (antiviral resin composition). Therefore, in the process of forming the cured material layer, the particles of the imidazole-based compound are more likely to float up, making it possible to easily unevenly distribute the particles of the imidazole-based compound on one surface side of the cured material layer. Furthermore, by unevenly distributing the particles of the imidazole-based compound on one surface side of the cured material layer, it is possible to reduce the amount of imidazole-based compound added necessary to obtain a predetermined antiviral property, and therefore it is possible to easily prevent a decrease in the scratch resistance of the cured material layer.
Typically, the imidazole compound is dissolved in the ink (antiviral resin composition) for the cured material layer before use. The reason for this is to uniformly diffuse the imidazole compound within the cured material layer, allowing the effect of the imidazole compound to be exerted throughout the cured material layer. Therefore, when using an imidazole compound in a typical manner, the imidazole compound does not exist in a particulate state within the cured material layer. In other words, the present invention differs from cured material layers containing general-purpose imidazole compounds in that the imidazole compound remains in a particulate state.

To facilitate uneven distribution of imidazole compound particles on the surface of the cured material layer, it is preferable to select a curable resin composition that satisfies the relationship "specific gravity of imidazole compound particles < specific gravity of curable resin composition." Furthermore, using an imidazole compound with a high degree of polarity is preferable, as it facilitates uneven distribution of imidazole compound particles on the surface of the cured material layer. Furthermore, when the solvent contained in the ink for the cured material layer evaporates, it can facilitate floating of the imidazole compound particles to the surface of the cured material layer, making it easier to unevenly distribute the imidazole compound particles near the surface of the cured material layer.

Imidazole compounds are compounds that contain an imidazole skeleton as a molecular structural unit. In the present invention, various imidazole compounds that maintain their particle form in the ink for the cured product layer (antiviral resin composition) and in the cured product layer can be used. Such imidazole compounds are preferably those that are poorly soluble in water and organic solvents, such as methyl benzimidazol-2-ylcarbamate (also known as carbendazim) and polymerized imidazole compounds.
However, care must be taken because even methyl benzimidazol-2-ylcarbamate (also known as carbendazim) and polymerized imidazole compounds may dissolve in certain solvents. For example, for methyl benzimidazol-2-ylcarbamate (also known as carbendazim), it is preferable to use methyl ethyl ketone, ethyl acetate, or the like as a solvent.

The shape of the particles of the imidazole compound is not particularly limited, and examples include spheres, ellipsoids, polyhedrons, scales, etc.

The average particle size of the particles of the imidazole compound is preferably 0.1 to 10.0 μm, more preferably 0.5 to 8.0 μm, and even more preferably 1.0 to 7.0 μm.
By setting the average particle size to 0.1 μm or more, the ink for the cured product layer can be more easily stabilized, while by setting the average particle size to 10.0 μm or less, it is possible to easily prevent poor appearance, reduced scratch resistance and stain resistance, and whitening of the coating film due to protrusion of the imidazole compound particles from the surface of the cured product layer.

When the average particle size of the particles of the imidazole compound is defined as D and the thickness of the cured material layer is defined as T, D/T is preferably 1.0 or less, more preferably 0.7 or less, and even more preferably 0.5 or less.
By setting D/T to 1.0 or less, it is possible to easily suppress poor appearance, reduced scratch resistance and stain resistance, and whitening of the coating film caused by particles of the imidazole compound protruding from the surface of the cured layer.
The lower limit of D/T is not particularly limited, but is usually 0.01 or more, preferably 0.05 or more.

In this specification, the average particle size refers to the mass average value d50 measured in particle size distribution measurement using laser diffraction method.

The content of the imidazole compound particles is preferably 0.5 to 20.0 parts by mass, more preferably 1.0 to 13.0 parts by mass, and even more preferably 3.0 to 10.0 parts by mass, per 100 parts by mass of the cured product.
By setting the content of the imidazole compound particles to 0.5 parts by mass or more, it is possible to easily improve the antiviral properties.
By setting the content of the imidazole compound particles to 20.0 parts by mass or less, it is possible to suppress deterioration in coating film properties such as coating film strength, scratch resistance, etc. Furthermore, by setting the content of the imidazole compound particles to 20.0 parts by mass or less, it is possible to easily suppress deterioration in contamination resistance and whitening of the coating film due to the imidazole compound particles protruding from the surface of the cured product layer.

It is preferable that the cured material layer is substantially free of silver and silver ions. This is because silver-based antiviral agents containing silver or silver ions cause discoloration to brown when exposed to light. "Substantially free" means that the content of silver and silver ions relative to the total solid content of the cured material layer is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less.
Furthermore, it is preferable that the cured material layer is substantially free of metals and metal ions, since metals and metal ions other than silver or silver ions can also cause color. "Substantially free" means that the content of metals and metal ions is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less, relative to the total solid content of the cured material layer.

<Additives>
The cured product layer may contain additives such as antioxidants, light stabilizers, and ultraviolet absorbers.

Antioxidants
Examples of the antioxidant include phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants.
The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.5 to 3.0 parts by mass, per 100 parts by mass of the cured product.

<Light stabilizer>
Examples of light stabilizers include aromatic compounds, amine compounds, organic acid compounds, catechin compounds, and hindered amine compounds, of which hindered amine compounds are preferred. Hindered amine compounds have a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.
The content of the light stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8.0 parts by mass, and even more preferably 1.0 to 5.0 parts by mass, per 100 parts by mass of the cured product. It is preferable that the light stabilizer contains a hindered amine compound in the above range.

<Ultraviolet absorber>
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, and triazine-based ultraviolet absorbers are preferred. One or more types of ultraviolet absorbers can be used.

Among the triazine-based ultraviolet absorbers, more preferred are hydroxyphenyltriazine-based ultraviolet absorbers in which three organic groups selected from hydroxyphenyl groups, alkoxyphenyl groups, and organic groups containing these groups are linked to a triazine ring, and even more preferred are hydroxyphenyltriazine-based ultraviolet absorbers represented by the following general formula (A): Because the hydroxyphenyltriazine-based ultraviolet absorber has a branched structure, it is expected that it will be less likely to bleed out from the cured product layer, and will provide excellent weather resistance over a longer period of time.
Furthermore, ultraviolet absorbers having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, or an allyl group, are preferred because they are more likely to suppress bleeding out.

In general formula (A), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by —C(═O)OR ¹⁵ , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a monovalent organic group, and n ₁₁ and n ₁₂ are each independently an integer of 1 to 5.

Examples of the divalent organic group for ^R11 include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group, and from the viewpoint of weather resistance, an alkylene group is preferred, and the number of carbon atoms therein is preferably from 1 to 20, more preferably from 1 to 12, still more preferably from 1 to 8, and particularly preferably from 1 to 4. The alkylene group and alkenylene group may be linear, branched, or cyclic, and is preferably linear or branched.
Examples of alkylene groups having 1 to 20 carbon atoms include methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 2,2-propylene, and other various propylene groups (hereinafter, "various" refers to linear, branched, and isomeric forms thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecylene groups, and various icosylene groups.

Examples of the monovalent organic group of R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group, among which aromatic hydrocarbon groups such as an aryl group and an arylalkyl group are preferred, and an aryl group is preferred. Among these, a phenyl group is preferred as the monovalent organic group of R ¹³ and R ¹⁴ .
The aryl group preferably has from 6 to 20 carbon atoms, more preferably from 6 to 12 carbon atoms, and even more preferably from 6 to 10 carbon atoms, such as a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups. The arylalkyl group preferably has from 7 to 20 carbon atoms, more preferably from 7 to 12 carbon atoms, and even more preferably from 7 to 10 carbon atoms, such as a benzyl group, a phenethyl group, various phenylpropyl groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, and various hexylbenzyl groups.

Examples of the monovalent organic group for R ¹⁵ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group, and an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred. That is, R ¹² is preferably an alkyl ester group or an alkenyl ester group, and more preferably an alkyl ester group.
The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 6 to 12 carbon atoms, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various icosyl groups.
The alkenyl group is preferably an alkenyl group having from 2 to 20 carbon atoms, more preferably from 3 to 16 carbon atoms, and even more preferably from 6 to 12 carbon atoms, such as a vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups, and various icosenyl groups.

More specifically, the hydroxyphenyltriazine compound represented by general formula (A) is preferably a hydroxyphenyltriazine compound in which R ¹¹ is an alkylene group having 1 to 20 carbon atoms, R ¹² and R ¹⁵ are alkyl ester groups which are alkyl groups having 1 to 20 carbon atoms, R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms, and n ₁₁ and n ₁₂ are 1, and more preferably a hydroxyphenyltriazine compound in which R ¹¹ is an alkylene group having 1 to 12 carbon atoms, R ¹² and R ¹⁵ are alkyl ester groups which are alkyl groups having 2 to 16 carbon atoms, R ¹³ and R ¹⁴ are aryl groups having 6 to 12 carbon atoms, and n ₁₁ and n ₁₂ are 1, and more preferably a hydroxyphenyltriazine compound in which R ¹¹ is an alkylene group having 1 to 8 carbon atoms, R ¹² is R ¹⁵ and an alkyl ester group which is an alkyl group having 6 to 12 carbon atoms, and R ¹³ and R Hydroxyphenyltriazine compounds in which ^{R 14} is an aryl group having from 6 to 10 carbon atoms, and n ₁₁ and n ₁₂ are 1 are more preferred, and hydroxyphenyltriazine compounds in which R ¹¹ is an alkylene group having from 1 to 4 carbon atoms, R ¹² and R ¹⁵ are ester groups which are alkyl groups having 8 carbon atoms, R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1 are particularly preferred.

The content of the UV absorber is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, and even more preferably 1.0 to 4.0 parts by mass per 100 parts by mass of the cured product.

The cured product layer may contain an extender pigment, which is used, for example, to adjust the design of the antiviral article.
Examples of extender pigments include inorganic particles such as silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, and organic particles such as polyethylene, urethane resin, polycarbonate, and polyamide (nylon).
The shape of the extender pigment is not particularly limited, but is preferably polyhedral, spherical, scaly, etc. The average particle size of the extender pigment is usually about 1 to 10 μm, preferably 3 to 8 μm.

If necessary, the cured material layer may contain a colorant to be colored to a desired hue, brightness, and saturation. The colorant may be appropriately selected from the same colorants as those used in the colored layer and design layer described below. By coloring the cured material layer with a colorant to an appropriate color (hue, brightness, and saturation), the design appearance can be improved, and discoloration of the cured material layer caused by light, etc. can be made less noticeable by coloring. This, combined with the discoloration-reducing effect of the benzimidazole compound particles, can further improve the discoloration-reducing effect of the cured material layer.

<Thickness>
The thickness of the cured product layer can be, for example, from 1.0 μm to 10,000 μm (1 cm) in view of the balance between processing characteristics and scratch resistance.
When the antiviral article is constructed from a single layer of the cured material layer, it is preferable that the thickness of the cured material layer be made relatively large.
On the other hand, in the case of a form in which a cured product layer is formed on a substrate by coating (applying), it is preferable that the thickness of the cured product layer is thin, taking into consideration that the substrate is responsible for self-supporting properties and durability to external forces, that the antiviral effect saturates at a certain thickness or more, and that an increase in the thickness of the cured product layer causes disadvantages such as a decrease in post-processing suitability and a rise in material costs, etc. Specifically, from the viewpoint of a balance between processing properties and scratch resistance, the thickness of the cured product layer is preferably 1.5 μm or more and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and even more preferably 3 μm or more and 15 μm or less.

<Formation method>
The cured material layer can be formed, for example, by applying, drying, and curing an ink for the cured material layer, which contains materials constituting the cured material layer (such as a curable resin composition and particles of an imidazole-based compound), a solvent added as necessary, and the like, onto a substrate. The cured material layer can also be formed by applying, drying, and curing the ink for the cured material layer onto a substrate having releasability to form a cured material layer, and then transferring the cured material layer to another substrate, etc.
As described above, by applying an ink for the cured material layer, which contains materials constituting the cured material layer (such as a curable resin composition and particles of an imidazole-based compound) and a solvent, to a substrate, followed by drying and curing, to form a cured material layer, the particles of the imidazole-based compound can be made to easily rise to the surface of the cured material layer when the solvent evaporates, and the particles of the imidazole-based compound can be made to easily be unevenly distributed near the surface of the cured material layer.

<Layer structure>
The antiviral article of the present invention may be a single layer of the cured product layer, or may have layers other than the cured product layer.
An antiviral article consisting of a single layer of a cured material layer can be obtained, for example, by producing a laminate by forming a cured material layer on a substrate having releasability, and then peeling off the substrate having releasability from the laminate.
Examples of layers other than the cured product layer that the antiviral article has include a substrate, a primer layer, a decorative layer, a transparent resin layer, and an adhesive layer. Examples of layer configurations of antiviral articles include the following (1) to (12). In the following (1) to (12), "/" indicates the interface between each layer.
Examples of layers other than the cured product layer that the antiviral article may have include functional layers such as a magnetic layer for magnetic recording, a conductive layer that functions as a circuit, a copper wire for current, or an electromagnetic wave shielding layer, a gas barrier layer that suppresses the transmission of gases such as water vapor and oxygen, a light reflective layer that reflects visible light with a high reflectance, and an antireflection layer that suppresses reflection of visible light. These functional layers can be formed in any of the following laminate structures (1) to (12) depending on the function of each layer.

(1) Cured product layer (2) Substrate/cured product layer (3) Substrate/primer layer/cured product layer (4) Substrate/decorative layer/cured product layer (5) Substrate/transparent resin layer/cured product layer (6) Substrate/adhesive layer/transparent resin layer/cured product layer (7) Substrate/adhesive layer/decorative layer/transparent resin layer/cured product layer (8) Substrate/decorative layer/adhesive layer/transparent resin layer/cured product layer (9) Substrate/transparent resin layer/primer layer/cured product layer (10) Substrate/adhesive layer/transparent resin layer/primer layer/cured product layer (11) Substrate/adhesive layer/decorative layer/transparent resin layer/primer layer/cured product layer (12) Substrate/decorative layer/adhesive layer/transparent resin layer/primer layer/cured product layer

From the standpoint of ease of handling, it is preferable for the antiviral article to have a cured material layer on a substrate.

《Base material》
The form of the substrate is not particularly limited, and may include flat forms such as films, sheets, and plates, as well as three-dimensional forms such as polyhedrons, polygonal prisms, cylinders, spheres, and spheroids.
Although films, sheets, and plates are often referred to as films, sheets, and plates in the order of relatively thinnest thickness, no distinction is made between these three in this specification unless otherwise specified.

Materials constituting the substrate include resins, metals, non-metallic inorganic materials, fibrous materials, and wood-based materials, and can be selected appropriately depending on the application.

The substrate may be a single layer, or may be a laminate of two or more layers made of the above materials. When the substrate is a laminate of two or more layers, it is preferable that two or more layers of different materials are laminated so that the properties of the materials in each layer complement each other. Examples of substrates made of two or more layers are A to J below. Note that "/" indicates the interface between each layer.
(A) Resin/wood-based material (B) Resin/metal (C) Resin/fibrous material (D) Resin/non-metallic inorganic material (E) Resin 1/Resin 2
(F) Metal/wood-based materials (G) Metal/non-metallic inorganic materials (H) Metal/fibrous materials (I) Metal 1/Metal 2
(J) Non-metallic inorganic materials/fibrous materials

In E above, Resin 1 and Resin 2 represent different types of resins (for example, Resin 1 is an olefin resin and Resin 2 is an acrylic resin). In H above, Metal 1 and Metal 2 represent different types of metals (for example, Metal 1 is copper and Metal 2 is chromium).

Furthermore, when the substrate is a laminate such as those described above in A to J, layers (such as adhesive layers) may be present between the constituent layers of the laminate to strengthen the adhesive strength.

Resins used as the base material include various synthetic resins and natural resins. Synthetic resins that can be used include thermoplastic resins and curable resins.

Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins typified by nylon 6 or nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers (ABS); polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins.
Examples of the curable resin include the thermosetting resins and ionizing radiation curable resins exemplified for the cured material layer.
Natural resins include natural rubber, pine resin, and amber.

Metals that can be used as substrates include, for example, aluminum or aluminum-containing alloys such as duralumin, iron or iron-containing alloys such as carbon steel and stainless steel, copper or copper-containing alloys such as brass and bronze, gold, silver, chromium, nickel, cobalt, tin, titanium, etc. Metal substrates that have been plated with these metals can also be used.

Non-metallic inorganic materials used as substrates include, for example, non-ceramic ceramic materials such as cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as porcelain, earthenware, glass, and enamel; and natural stones such as limestone (including marble), granite, and andesite.

Examples of fibrous materials used as substrates include tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, parchment paper, glassine paper, wallpaper backing paper, paperboard and gypsum board base paper, and other papers; woven or nonwoven fabrics made of fibers such as polyester resin fiber, acrylic resin fiber, protein-based or cellulose-based natural fibers such as silk, cotton, and hemp; glass fiber; and carbon fiber. These papers may further contain resins such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin (impregnated after papermaking or inserted during papermaking) to increase the strength between the fibers of the paper substrate or between other layers of the paper and prevent fluffing. Examples of resin-added papers include inter-fiber reinforced paper and resin-impregnated paper.
Furthermore, an example of a substrate in which a resin layer is laminated onto a fibrous material layer is wallpaper base paper, which is often used in the building materials field and has a resin layer such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer laminated on the surface of wallpaper backing paper.

The shape and dimensions of the substrate are not particularly limited and may be appropriately selected depending on the intended use, desired performance properties and processability.
When the substrate is a flat film, sheet, or plate, the thickness is a typical dimension in the design of the article. There are no particular restrictions on the thickness, but it is generally set to about 10 μm or more and 10 cm or less from the viewpoints of manufacturing processability, mechanical strength, ease of use and handling, and economic efficiency. In the case of a film or sheet form, a thickness of about 20 μm or more and 300 μm or less is usually selected, and in the case of a plate form, a thickness of about 1 mm or more and 2 cm or less is usually selected.

To improve adhesion between the substrate and other layers constituting the antiviral article or between the antiviral article and a member to be laminated thereto, one or both surfaces of the substrate can be subjected to a surface treatment such as a physical surface treatment by an oxidation method or a roughening method, or a chemical surface treatment.
Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc., and examples of roughening methods include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but generally, corona discharge treatment is preferably used in terms of the effect of the surface treatment, operability, etc.

<Primer layer>
The antiviral article preferably has a primer layer in contact with the substrate-side surface of the cured material layer. The primer layer improves adhesion between the substrate and the cured material layer, making it easier to ensure long-term interlayer adhesion when exposed to ultraviolet light (so-called weather-resistant adhesion) and improve scratch resistance.
Examples of cases in which antiviral articles are exposed to ultraviolet light include cases in which the antiviral article is installed, constructed, or used in places where sunlight containing ultraviolet light shines in, such as near a window; inside a kitchen, refrigerator, or cupboard where a sterilizing mercury lamp is installed; or outdoors where the antiviral article is exposed to direct sunlight.

The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.
Preferred examples of binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. These can be used alone or in combination. Furthermore, the binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the resin and crosslinking and curing the resin. Among these, a polyol-based resin such as an acrylic polyol resin and crosslinking and curing it with an isocyanate-based curing agent is preferred, and an acrylic polyol resin and crosslinking and curing it with an isocyanate-based curing agent is more preferred.

The primer layer preferably contains an ultraviolet absorber and/or a light stabilizer to further improve weather resistance. General-purpose ultraviolet absorbers and light stabilizers can be used.

The thickness of the primer layer is preferably 0.01 μm or more and 10 μm or less, more preferably 0.7 μm or more and 8 μm or less, and even more preferably 1.0 μm or more and 6 μm or less.

The antiviral article may have a back primer layer on the side of the substrate opposite the cured product layer for the purpose of improving adhesion to an adherend, etc.
The antiviral article may also have a pressure-sensitive adhesive layer on the side of the substrate opposite the cured layer for the purpose of bonding to an adherend. It is preferable to form a peelable separator on the surface of the pressure-sensitive adhesive layer opposite the substrate.

《Transparent resin layer》
The antiviral article may have a transparent resin layer between the substrate and the cured product layer from the viewpoint of increasing strength, etc. In particular, when the substrate is a resin substrate, it is preferable that the antiviral article have a transparent resin layer.
When the antiviral article has a primer layer, the transparent resin layer is preferably located between the substrate and the primer layer. When the antiviral article has a decorative layer, the transparent resin layer is preferably located between the decorative layer and the cured product layer from the viewpoint of protecting the decorative layer.

Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, etc. Among these, polyolefin resins are preferred from the viewpoint of processability. Furthermore, two or more of these exemplified resins may be laminated or mixed and used.
From the viewpoint of processability, the content of the polyolefin resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, of the total resin components of the transparent resin layer.

Examples of polyolefin resins for the transparent resin layer include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, etc. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferred, with polypropylene being more preferred.

The transparent resin layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a colorant.
The thickness of the transparent resin layer is preferably from 20 μm to 150 μm, more preferably from 40 μm to 120 μm, and even more preferably from 60 μm to 100 μm, from the viewpoint of a balance between scratch resistance, processability, and weather resistance.

Decorative Layer
From the viewpoint of improving the design, the antiviral article preferably has a decorative layer at any location on the antiviral article.
From the viewpoint of improving the weather resistance of the decorative layer, the decorative layer is preferably formed on a side closer to the substrate. For example, when the antiviral article has a primer layer, the decorative layer is preferably located between the substrate and the primer layer. Furthermore, when the antiviral article has a transparent resin layer, the decorative layer is preferably located between the substrate and the transparent resin layer.

The decorative layer may be formed over the entire surface of the antiviral article, or only on a portion of it. In cases where the decorative layer covers the outer surface of the cured material layer, it is preferable to form the decorative layer only on a partial area so as not to inhibit the expression of antiviral properties.

Examples of the decorative layer include a colored layer formed by applying ink in a solid manner, a patterned layer formed by printing ink as a pattern, and a thin metal film.
Examples of patterns (designs) that can be expressed by the decorative layer include wood grain patterns such as tree rings and vessel grooves on the surface of a wooden board; stone grain patterns on the surface of stone slabs such as marble and granite; fabric grain patterns on the surface of fabric; leather grain patterns on the surface of leather; tile patterns including grooves; brickwork patterns including grooves; sand grain patterns; pear-skin patterns; patterns consisting of an arrangement of multiple concave and convex stripes extending in parallel directions (so-called ``line-like concave and convex patterns'' or ``ray-carved patterns''); and abstract patterns such as geometric patterns, letters, figures, polka dots, and floral designs.

The ink used for the colored layer and the design layer is a mixture of a binder resin with an appropriate amount of a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc.
The binder resin for the colored layer and the design layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. Furthermore, various types of resins can be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound.

The colorant is not particularly limited, and examples thereof include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complexes, phthalocyanine blue, and azomethine azo black; metal pigments consisting of flaky flakes of aluminum, brass, or the like; and pearlescent pigments consisting of flaky flakes of titanium dioxide-coated mica, basic lead carbonate, or the like.
The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the resin constituting the colored layer and the pattern layer.

The color layer and the design layer may contain additives such as ultraviolet absorbers, light stabilizers, and colorants.
The thickness of the colored layer and the patterned layer may be selected appropriately depending on the desired pattern, but from the viewpoint of concealing the base color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

Examples of metal thin films include thin films of simple metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt, and thin films of alloys containing two or more of the above metal elements. Examples of alloys include brass, bronze, and stainless steel.
The metal thin film can have a thickness of about 0.1 μm to 1 μm.

《Adhesive layer》
The antiviral article may have an adhesive layer.

For example, when the antiviral article has a transparent resin layer, it is preferable to form an adhesive layer between the substrate and the transparent resin layer in order to improve the adhesion between the two layers.
When a decorative layer is further provided between the substrate and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited. Specifically, the decorative layer, adhesive layer, and transparent resin layer may be provided in this order from the side closest to the substrate, or the adhesive layer, decorative layer, and transparent resin layer may be provided in this order from the side closest to the substrate layer.
Furthermore, as described above, when the substrate is a laminate of two or more layers, an adhesive layer may be provided between the layers constituting the substrate.

The adhesive layer can be made of, for example, an adhesive such as a urethane adhesive, an acrylic adhesive, an epoxy adhesive, a rubber adhesive, etc. Among these adhesives, a urethane adhesive is preferred in terms of adhesive strength.
Examples of urethane adhesives include adhesives that utilize two-component curing urethane resins containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.

The thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

The decorative layer, adhesive layer, and primer layer described above can be formed by applying a coating liquid containing the composition that will form each layer using a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, and then drying and curing as necessary.

<Excipient processing>
The antiviral article may be given a desired uneven shape (also called an uneven pattern) by a shaping treatment such as embossing.
When embossing is performed, for example, the antiviral article can be heated to preferably from 80° C. to 260° C., more preferably from 85° C. to 200° C., and even more preferably from 100° C. to 180° C., and then an embossing plate can be pressed against the antiviral article. The area where the embossing plate is pressed is preferably the cured product layer side of the antiviral article.

<Application>
The antiviral article of the present invention can be used for various purposes, including the following (1) to (12):
(1) Surface materials for interior walls, floors, ceilings, etc. of buildings such as houses, offices, stores, hospitals, and clinics.
(2) Surface materials for exterior parts such as exterior walls, roofs, eaves ceilings, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics.
(3) Surface materials (interior or exterior parts) of building fixtures such as windows, window frames, doors, and door frames; surface materials of fixture accessories (handles, etc.); surface materials of building fixture jigs.
(4) Surface materials for construction components such as handrails, waist walls, moldings, thresholds, lintels, and top boards.
(5) Surface materials for outdoor (exterior) parts such as fences, gates, drying rack pillars and handrails.
(6) Surface materials for furniture such as chests of drawers, desks, chairs, cupboards, kitchen sinks, etc.; surface materials for furniture accessories (handles, etc.); surface materials for furniture fixtures.
(7) Surface materials for the housings of various home appliances such as television receivers, radio receivers, refrigerators, microwave ovens, washing machines, electric fans, and air conditioners; surface materials for accessories of home appliances (handles, switches, touch panels, etc.); surface materials for fixtures of home appliances.
(8) Surface materials for office equipment such as various computing devices such as electronic copiers, facsimiles, printers, and personal computers; surface materials for the housings of various office equipment such as ATM devices at financial institutions such as banks and post offices; surface materials for accessories of various office equipment (keyboards, touch panels, etc.); surface materials for jigs of various office equipment.
(9) Surface materials for the interior or exterior parts (walls, floors, ceilings, handrails, supports, control panels, levers, handles, steering wheels, and other control equipment) of vehicles such as automobiles, railway cars, ships, and aircraft.
(10) Partitions in various buildings; shielding plates or curtains to prevent droplet infection of viruses at counters of stores, offices, government offices, etc., accounting settlement locations, etc.; face protection equipment such as protective masks (face guards) and protective glasses (goggles); or surface materials thereof.
(11) Business forms such as slips; bankbooks; cards such as cash cards, credit cards, and point cards of financial institutions; or the surface materials thereof.
(12) Glass, resin, etc. bottles; metal cans; resin soft packaging materials such as resin retort containers; packaging materials such as various tubes; or surface materials thereof.

[Antiviral resin composition]
The antiviral resin composition of the present invention contains a curable resin composition and particles of an imidazole compound.

The embodiments of the "curable resin composition" and "particles of imidazole-based compound" in the antiviral resin composition of the present invention are the same as the embodiments of the "curable resin composition" and "particles of imidazole-based compound" in the antiviral article of the present invention described above.

The antiviral resin composition of the present invention may contain an antioxidant, a light stabilizer, an ultraviolet absorber, and the like, as necessary.
The embodiments of the "antioxidant,""lightstabilizer," and "ultraviolet absorber" in the antiviral resin composition of the present invention are the same as the embodiments of the "antioxidant,""lightstabilizer," and "ultraviolet absorber" in the antiviral article of the present invention described above.

<Solvent>
The antiviral resin composition of the present invention preferably contains a solvent. When the antiviral resin composition contains a solvent, the imidazole compound particles can be more likely to float to the surface of the cured material layer when the solvent volatilizes, making it easier to unevenly distribute the imidazole compound particles near the surface of the cured material layer.

Examples of the solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), glycol ethers (propylene glycol monomethyl ether acetate, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and mixtures thereof may also be used.
Among these, for example, methyl ethyl ketone and ethyl acetate are preferred from the viewpoint of maintaining the shape of the particles of the imidazole compound.

The solvent content is preferably 10 to 60% by mass, and more preferably 30 to 50% by mass, of the total amount of the antiviral resin composition (ink for the cured product layer).

Next, the present invention will be explained in more detail using examples, but the present invention is not limited to these examples in any way.

1. Evaluation The following evaluations were carried out on the inks for cured layers (antiviral resin compositions) of the Examples and Comparative Examples, and the antiviral articles of the Examples and Comparative Examples. The evaluations were carried out in an atmosphere with a temperature of 23°C ± 5°C and a humidity of 40 to 65% RH.

1-1. Discoloration of the ink for cured material layer (antiviral resin composition) In a room shielded from external light, 30 g of the ink for cured material layer (antiviral resin composition) of each of the Examples and Comparative Examples was placed in a glass bottle (manufactured by AS ONE Corporation, product number: Labolan screw cap bottle, 50 ml) and the lid was closed to prepare a sample for evaluation. At this stage, the color of the ink for cured material layer (antiviral resin composition) in each sample was white and did not differ from the color of a composition containing no antiviral agent (a composition obtained by removing the antiviral agent from the ink for cured material layer (antiviral resin composition) of each of the Examples and Comparative Examples).
The sample was then placed on a desk and left indoors under fluorescent lighting for 24 hours, after which the color of the ink for the cured layer (antiviral resin composition) in the sample was visually evaluated. The brightness of the fluorescent lighting on the desk was in the range of 500 to 1,000 lux. The results are shown in Table 1.

1-2. Discoloration of antiviral article The L ^* a ^* b ^* values of the antiviral articles of the examples and comparative examples were measured immediately after production. The measurement device used was a spectrophotometer ("Spectrolino" (model number), manufactured by GretagMacbeth).
Next, the antiviral articles of the Examples and Comparative Examples were subjected to an accelerated weather resistance test using a metal halide lamp (MWOM) for four cycles (96 hours), in which one cycle consisted of irradiating with ultraviolet light for 20 hours under the irradiation conditions described below, followed by condensation for four hours under the condensation conditions described below. The L ^* a ^* b ^* values after the accelerated weather resistance test were then measured.
The color difference (ΔE ^* ab) was calculated from the measured value immediately after production and the measured value after the accelerated weathering test. The results are shown in Table 2.
The color difference (ΔE ^* ab) can be calculated using the following formula, where the measured values immediately after production are L ^*1 , a ^*1 , and b ^* 1, and the measured values after the accelerated weather resistance test are L ^*2 , a ^*2 , and b ^*2 .
ΔE ^* ab = [(L ^*2 - L ^*1 ) ² + (a ^*2 - ^{a *1} ) ² + (b ^* 2 - a ^*2 ) ² ] ^1/2

<Test equipment>
Product name "Daipla Metal Weather" manufactured by Daipla Wintes
<Irradiation conditions>
Illuminance: 65 mW/cm ² , Black panel temperature: 63°C, Humidity inside chamber: 50% RH, Time: 20 hours <Condensation conditions>
Illuminance: 0 mW/cm ² , Humidity inside the tank: 98% RH, Time: 4 hours

2. Preparation of ink for cured layer (antiviral resin composition) and production of antiviral article [Example 1]
The following components were mixed and stirred to prepare ink a for the cured product layer (antiviral resin composition a) of Example 1.

<Ink a for cured layer (antiviral resin composition a)>
100 parts by mass of ionizing radiation curable resin composition (trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000)
Imidazole compound particles: 5 parts by mass (methyl benzimidazol-2-ylcarbamate, average particle size: 5.8 μm)
Ultraviolet absorber: 2 parts by mass (hydroxyphenyltriazine, TUNUVIN 479, manufactured by BASF)
Extender pigment (irregular silica) 16 parts by weight (average particle size: 10 μm)
Solvent: 50 parts by mass (ethyl acetate)

Next, a decorative layer ink containing a two-component curing acrylic-urethane resin and a colorant was applied by gravure printing to one side of a substrate (a titanium oxide-containing polypropylene resin sheet having a thickness of 60 μm) that had been subjected to a corona discharge treatment on both sides, and then dried to form a wood grain pattern decorative layer having a thickness of 3 μm.
Next, a 3 μm thick adhesive layer made of a urethane resin adhesive was formed on the decorative layer, and then a polypropylene resin was hot-melt extruded onto the adhesive layer using a T-die extruder to form an 80 μm thick transparent resin layer.
Next, the surface of the transparent resin layer was subjected to a corona discharge treatment, and then a primer layer ink having the following composition was applied onto the transparent resin layer by gravure printing and dried to form a primer layer having a thickness of 2 μm.
Next, the ink a for cured layer (antiviral resin composition a) was applied onto the primer layer by roll coating to form an uncured cured layer, which was then dried at 60°C for 1 minute and then irradiated with an electron beam (acceleration voltage: 175 kV, 5 Mrad (50 kGy)) to crosslink and cure the curable resin composition (ionizing radiation-curable resin composition), forming a cured layer with a thickness of 15 µm, and the antiviral article of Example 1 was obtained.

<Ink for primer layer>
100 parts by weight of a mixture of urethane-acrylic copolymer and acrylic polyol 5 parts by weight of hexamethylene diisocyanate

[Comparative Example 1]
Ink b for a cured product layer (antiviral resin composition b) of Comparative Example 1 was prepared by removing "5 parts by mass of imidazole compound particles" from ink a for a cured product layer (antiviral resin composition a) and adding "3 parts by mass of an antiviral agent obtained by supporting silver ions on glass (product number "PG711" manufactured by Koa Glass Co., Ltd., average particle size 3 μm)" instead.

Next, an antiviral article of Comparative Example 1 was obtained in the same manner as in Example 1, except that ink a for the cured product layer (antiviral resin composition a) was changed to ink b for the cured product layer (antiviral resin composition b).

As shown in Table 1, it can be confirmed that the ink for the cured layer (antiviral resin composition) and antiviral article of the example can suppress discoloration.

100: Antiviral article 10: Cured material layer 11: Cured material of curable resin composition 12: Particles of imidazole compound 20: Substrate

Claims (5)

An article having a cured material layer,
the cured material layer contains a cured material of a curable resin composition and particles of methyl benzimidazol-2-ylcarbamate,
wherein D is an average particle size of the methyl benzimidazol-2-ylcarbamate particles and T is a thickness of the cured material layer, and D/T is 0.01 or more and 1.0 or less;
An antiviral article in which the cured material layer is substantially free of silver and silver ions (excluding those in which the cured material layer contains an azole derivative other than the methyl benzimidazol-2-ylcarbamate). The antiviral article according to claim 1, comprising 0.5 to 20.0 parts by mass of the methyl benzimidazol-2-yl carbamate particles per 100 parts by mass of the cured product. The antiviral article according to claim 1 or 2, comprising the cured material layer on a substrate. The antiviral article according to any one of claims 1 to 3, wherein the average particle size of the methyl benzimidazol-2-ylcarbamate particles is 0.1 to 10.0 μm. The antiviral article according to any one of claims 1 to 4, wherein the thickness of the cured layer is 1.5 μm or more and 30 μm or less.