JP2022026339A - Antiviral article and antiviral resin composition - Google Patents

Abstract

To provide an antiviral article with suppressed discoloration due to light.SOLUTION: An antiviral article 100 has a cured product layer 10. The cured product layer 10 contains a cured product 11 of a curable resin composition and an antiviral agent 12 in which silver ions are carried on or contained in apatite or glass. The antiviral agent 12 is contained in an amount of more than 1 pt.mass based on 100 pts.mass of the cured product 11. It is preferable that the antiviral article 100 has a foamed resin layer 30, a non-foamed resin layer 40, a decorative layer 50, and a primer layer 60 between a substrate 20 and the cured product layer 10.SELECTED DRAWING: Figure 4

Description

The present invention relates to antiviral articles and antiviral resin compositions.

Conventionally, from the viewpoint of hygiene, an antibacterial composition is applied to the surface of building interior materials such as wallpaper, vehicle interior materials, OA equipment, touch panels, and other objects that people touch. Processing was being carried out.

For example, Patent Documents 1 to 3 have been proposed with respect to an antibacterial composition or an antibacterial article.
However, it is not enough to have antibacterial properties against viruses such as influenza virus. That is, the compositions or articles having antibacterial properties of Patent Documents 1 to 3 may not be able to satisfy the antiviral properties.

On the other hand, patent documents 4 to 5 have been proposed as compositions or articles having antiviral properties.

Japanese Unexamined Patent Publication No. 63-265598 Japanese Patent No. 3551201 Japanese Patent No. 4840048 Japanese Patent No. 6145758 Japanese Patent No. 6229429

The antiviral resin composition of Patent Document 4 contains cuprous oxide particles and the like. Therefore, the tint derived from the color of cuprous oxide (reddish brown) could not be prevented.

The interior decorative sheet having antiviral properties of Patent Document 5 is formed by blending a silver-based inorganic additive or a zinc-based inorganic additive in a coating resin on the outermost surface of the decorative sheet.
Of the additives in Patent Document 5, the latter zinc-based inorganic additive has a problem of biotoxicity.
On the other hand, among the additives of Patent Document 5, the former silver-based inorganic additive is expensive, but has no problem of biotoxicity. However, when the amount of the silver-based inorganic additive added is increased in order to exhibit antiviral properties, there is a problem that the color changes to brown due to light (visible light, ultraviolet rays). Patent Document 5 does not examine the problem of discoloration due to an increase in the amount of the silver-based inorganic additive added.

An object of the present invention is to suppress discoloration of a silver-based antiviral article and an antiviral resin composition due to light.

In order to solve the above problems, the present invention provides the following [1] to [2].
[1] An article having a cured product layer, wherein the cured product layer contains a cured product of a curable resin composition and an antiviral agent obtained by carrying or containing silver ions in apatite or glass. An antiviral article containing more than 1 part by mass of the antiviral agent with respect to 100 parts by mass of the cured product.
[2] The curable resin composition and an antiviral agent comprising or containing silver ions in apatite or glass are contained, and 1 mass of the antiviral agent is added to 100 parts by mass of the curable resin composition. An antiviral resin composition containing a portion.

According to the present invention, it is possible to provide an antiviral article and an antiviral resin composition that suppresses discoloration due to light (visible light, ultraviolet rays) of a silver-based antiviral agent.

It is sectional drawing which shows one Embodiment of the antiviral article of this invention. It is sectional drawing which shows the other embodiment of the antiviral article of this invention. It is sectional drawing which shows the other embodiment of the antiviral article of this invention. It is sectional drawing which shows one Embodiment of the antiviral article for the wallpaper of this invention.

[Antiviral article]
The antiviral article of the present invention is an article having a cured product layer, wherein the cured product layer carries or contains silver ions in a cured product of a curable resin composition and apatite or glass. It contains a virus agent and contains more than 1 part by mass of the antiviral agent with respect to 100 parts by mass of the cured product.

Generally, if it has "antiviral property", it has "antibacterial property". Therefore, the antiviral article of the present invention and the antiviral resin composition of the present invention described later can be applied not only to antiviral use but also to antibacterial use. Since mold is a kind of fungus, the antiviral article of the present invention and the antiviral resin composition of the present invention described later can also be applied to antifungal uses.

1 (A) to (E), FIGS. 2 (A) to 2 (D), FIGS. 3 and 4, are cross-sectional views showing a typical embodiment of the antiviral article 100 of the present invention.
In the antiviral articles 100 of FIGS. 1 (A) to 1 (E), FIGS. 2 (A) to 2 (D), FIGS. 3 and 4, silver ions are added to the cured product 11 and apatite or glass of the curable resin composition. It has a cured product layer 10 containing an antiviral agent 12 that is carried or contained.

The antiviral article 100 of FIGS. 1A to 1E is formed of a single layer of the cured product layer 10.
The cured product layer 10 of FIG. 1 (A) contains the antiviral agent 12 in the entire cured product layer 10. In the cured product layer 10 of FIG. 1 (B), the antiviral agent 12 is applied to the cured product layer in both the thickness direction (Z-axis direction in the figure) and the in-plane direction (each direction in the XY plane in the figure). It is included on the surface side (upper side of the figure) of 10. The cured product layer 10 of FIG. 1C contains the antiviral agent 12 on the front surface side (upper side of the figure) and the back surface side (lower side of the figure) of the cured product layer 10. The cured product layer 10 of FIG. 1 (D) contains the antiviral agent 12 in a part of the region in the in-plane direction on the surface side (upper side of the figure) of the cured product layer 10. In the cured product layer 10 of FIG. 1 (E), the antiviral agent 12 is applied to a part of the surface side (upper side of the figure) of the cured product layer 10 and the back surface side (lower side of the figure) of the cured product layer 10. Included in some areas.
As shown in FIGS. 1A to 1E, the location of the antiviral agent 12 in the cured product layer 10 is not particularly limited. However, from the viewpoint of enhancing the antiviral property, it is preferable that the antiviral agent 12 is present on the surface on the side touched by a person.

The antiviral article 100 composed of a single layer of the cured product layer 10 as shown in FIGS. 1 (A) to 1 (E) is laminated by forming the cured product layer 10 on a substrate having releasability, for example. After producing the body, it can be obtained by peeling the base material having releasability from the laminated body.

The antiviral article 100 of FIGS. 2A to 2D has a cured product layer 10 on the base material 20.
The antiviral article 100 of FIG. 2A has a cured product layer 10 on the entire surface of one side of the base material 20. The antiviral article 100 of FIG. 2B has a cured product layer 10 on both sides of the base material 20. The antiviral article 100 of FIG. 2C has a cured product layer 10 in a part of a region on one side (Z-axis direction + side in the figure) of the base material 20. The antiviral article 100 of FIG. 2D has a part of a region on one side of the base material 20 (Z-axis direction + side in the figure) and the other side of the base material 20 (Z in the figure). The cured product layer 10 is provided in a part of the region (axially-side).
As shown in FIGS. 2A to 2D, the cured product layer 10 may be formed on the entire surface of the base material 20 or may be formed on a part of the base material 20. Further, as shown in FIGS. 2A to 2D, the cured product layer 10 may be formed on only one surface of the base material 20 or may be formed on both sides of the base material 20. good.

The antiviral article 100 of FIG. 3 has a cured product layer 10 on a three-dimensional base material 20. The three-dimensional base material 20 in FIG. 3 is a handle for a door, and FIG. 3 illustrates a plan view thereof.

The antiviral article 100 in FIG. 4 is an antiviral article 100 for wallpaper. That is, the antiviral article 100 of FIG. 4 functions as the wallpaper 200.
As shown in FIG. 4, the antiviral article 100 for wallpaper preferably has the base material 20, the foamed resin layer 30, and the cured product layer 10 in this order. The antiviral article 100 for wallpaper in FIG. 4 has a non-foamed resin layer 40, a decorative layer 50, and a primer layer 60 in this order between the foamed resin layer 30 and the cured product layer 10.

<Curing product of curable resin composition>
The cured product layer contains a cured product of the curable resin composition. In the present specification, the "cured product of a curable resin composition" may be abbreviated as "cured product".
The cured product of the curable resin composition mainly has a role as a binder resin. By including the cured product, the scratch resistance of the antiviral article is improved, and the antiviral property can be easily maintained for a long period of time.

Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionized radiation curable resin composition, and among them, an ionized radiation curable resin from the viewpoint of scratch resistance and production efficiency. A cured product of the composition is preferred.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. In addition to these thermosetting resins, a curing agent, a curing catalyst, and the like are added to the thermosetting resin composition, if necessary.

Typical examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet curable resin composition. Among these, a polymerization initiator is not required, so that the resin composition has less odor and is colored. An electron beam curable resin composition is preferable from the viewpoint of difficulty. Further, when the cured product layer contains an ultraviolet absorber described later, the electron beam curable resin composition tends to have a higher crosslink density of the cured product layer, and it is easier to improve scratch resistance and stain resistance. preferable.

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 is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group is preferable. Further, examples of the ionizing radiation curable functional group include an epoxy group and an oxetanyl group.
In addition, in this specification, a (meth) acryloyl group means an acryloyl group or a metachloroyl group. Further, in the present specification, (meth) acrylate means acrylate or methacrylate.
Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but other than that, Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
Specifically, the ionizing radiation curable compound is appropriately selected from polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") conventionally used as ionizing radiation curable resins. Can be used.

The ionizing radiation curable compound is more preferably a compound having two or more ethylenically unsaturated bonding groups, and more preferably a polyfunctional (meth) acrylate compound having two or more ethylenically unsaturated bonding groups. As the polyfunctional (meth) acrylate compound, either a monomer or an oligomer can be used.

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

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

The preferred epoxy (meth) acrylate is a (meth) acrylate obtained by reacting a trifunctional or higher aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like with a (meth) acrylic acid, and a bifunctional or higher functional epoxy resin. (Meta) acrylate obtained by reacting aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with polybasic acid and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resin, alicyclic. It is a (meth) acrylate obtained by reacting a group epoxy resin, an aliphatic epoxy resin or the like with phenols and (meth) acrylic acid.

The ionizing radiation curable compound preferably contains a silicone (meth) acrylate. By containing silicone (meth) acrylate as the ionizing radiation curable compound, the stain resistance of the cured product layer can be improved.

Examples of the silicone (meth) acrylate include silicone oils made of polysiloxane, or modified silicone oils in which a (meth) acrylic group is introduced at one or both ends.
The content of the silicone (meth) acrylate is preferably 1 to 7 parts by mass, more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable compound other than the silicone (meth) acrylate.

The ionizing radiation curable resin may be used alone or in combination of two or more.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable resin composition preferably contains an additive such as a photopolymerization initiator or a photopolymerization accelerator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones and the like.
Further, the photopolymerization accelerator can reduce the polymerization inhibition due to air at the time of curing and accelerate the curing rate. For example, from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more selected species can be mentioned.

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, and further preferably 90% by mass or more with respect to the total amount of the binder resin. It is preferably 100% by mass, most preferably 100% by mass.

<Antiviral agent that carries or contains silver ions on apatite or glass>
The cured product layer contains an antiviral agent comprising or containing silver ions on apatite or glass. In the present specification, "an antiviral agent obtained by supporting or containing silver ions in apatite or glass" may be abbreviated as "antiviral agent".

Apatite or glass serves as a carrier for silver ions.
Examples of the carrier other than apatite or glass include zeolite, zirconium phosphate, titanium phosphate and the like. However, these antiviral agents using materials other than apatite or glass as a carrier for silver ions cannot suppress discoloration due to light when the amount added is increased in order to exhibit antiviral properties.
The principle that an antiviral agent that carries or contains silver ions on apatite or glass can suppress discoloration is unknown, but it is said that the carrier apatite or glass suppresses the alteration of silver ions by some action. Conceivable. In particular, apatite is preferable to glass in that it can further suppress discoloration of the cured product layer.

Examples of the glass include soda glass, borosilicate glass, lead glass, aluminosilicate glass, borate glass and phosphoric acid glass.
Apatite is a general term for minerals having a composition represented by the following general formula. Apatite is preferably porous.
M ₁₀ (ZO ₄ ) ₃ X ₂

In the above formula, M represents Ca, Ba, Mg, Na, K, Fe, Al and the like, Z represents P, S, Si and As and the like, and X represents F, Cl, O and OH and the like. show. Typical examples corresponding to the above formula include fluorine apatite "Ca ₁₀ (PO ₄ ) ₆ F ₂ " and hydroxyapatite "Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ".

As a method for supporting or containing silver ions in apatite or glass, various known forms are appropriately used in consideration of various conditions such as the type of curable resin composition, each form thereof, processing conditions, and required antiviral performance. You can select it. Here, "containing silver ions" means holding silver ions or a substance capable of generating silver ions in a carrier such as glass or apatite in some form. Further, the "substance capable of generating silver ions" means a substance that generates silver ions due to an external factor, a time-dependent factor, or the like, for example, a substance that generates silver ions by dissolving in water or the like. do.
Specific supporting or containing forms include a method of supporting by physical adsorption or chemical adsorption; a method of supporting by an ion exchange reaction; a method of supporting by a binder; a method of containing a silver compound by driving it into an apatite or glass; , A method of supporting or containing a thin layer of a silver compound on the surface of apatite by a thin film forming method such as a dissolution-precipitation reaction or spatter; and the like.

The content of the antiviral agent needs to be more than 1 part by mass with respect to 100 parts by mass of the cured product.
When the content of the antiviral agent is 1 part by mass or less, it is difficult to improve the antiviral property.
The content of the antiviral agent is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, and 11 by mass with respect to 100 parts by mass of the cured product. It is more preferably more than parts by mass.

If the content of the antiviral agent is too large, the color may be slightly discolored by light. Further, if the content of the antiviral agent is too large, it is possible to suppress deterioration of the physical properties of the coating film such as the strength and scratch resistance of the coating film. In addition, if the content of the antiviral agent is too large, the antiviral agent tends to protrude from the surface of the cured product layer, resulting in a decrease in stain resistance, whitening of the coating film, and members of the coating device (coating roll, doctor blade, etc.). ) May occur.
Therefore, the content of the antiviral agent is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 35 parts by mass or less with respect to 100 parts by mass of the cured product. preferable.

The amount of silver ions in the antiviral agent is preferably 0.1 to 30.0 parts by mass, more preferably 0.5 to 25.0 parts by mass with respect to 100 parts by mass of apatite. It is more preferably 0.0 to 20.0 parts by mass. Here, the "amount of silver ions" means both the carried silver ions and the contained silver ions.
By setting the amount of silver ions to 0.1 parts by mass or more, it is possible to easily improve the antiviral property. Further, by setting the amount of silver ions to 30.0 parts by mass or less, discoloration due to light can be more easily suppressed.

The antiviral agent is preferably in the form of particles.
The shape of the particles of the antiviral agent may be a sphere, an ellipsoid, a polyhedron, a scaly shape, or the like, and is not particularly limited, but a spherical surface is preferable.

The average particle size of the antiviral agent is preferably 0.5 to 7.0 μm, more preferably 1.0 to 5.0 μm, and even more preferably 1.5 to 3.0 μm.
By setting the average particle size to 0.5 μm or more, the stability of the ink for the cured product layer can be easily obtained. Further, by setting the average particle size to 7.0 μm or less, it is easy to suppress poor appearance, deterioration of scratch resistance and stain resistance, and whitening of the coating film due to the antiviral agent protruding from the surface of the cured product layer. Further, it is possible to easily suppress the wear of the members of the coating device (coating roll, doctor blade, etc.).

When the average particle size of the antiviral agent is defined as D and the thickness of the cured product layer is defined as T, the D / T is preferably 4.0 or less, and more preferably 2.5 or less.
By setting the D / T to 4.0 or less, it is possible to easily suppress deterioration of stain resistance and whitening of the coating film due to the antiviral agent protruding from the surface of the cured product layer, and further, a member of the coating device. Wear of (coating rolls, doctor blades, etc.) can be easily suppressed.
The lower limit of D / T is not particularly limited, but is usually 0.10 or more, preferably 0.25 or more.

In the present specification, the average particle size of the antiviral agent and the silica particles described later means those measured as the mass average value d50 in the particle size distribution measurement by the laser light diffraction method.

It should be noted that an antiviral agent supporting silver ions using a carrier other than apatite or glass is difficult to suppress discoloration. Therefore, it is preferable that the cured product layer does not substantially contain other antiviral agents (antiviral agents supporting silver ions having a carrier other than apatite or glass). The term "substantially free" means that the content of the other antiviral agent is 0.1% by mass or less, preferably 0.01% by mass or less, based on the total solid content of the cured product layer. More preferably, it is 0.001% by mass or less. Further, it is more preferable that the cured product layer does not substantially contain an antiviral agent supporting silver ions having a carrier other than apatite.

<Silica particles>
The cured product layer preferably further contains silica particles.
The cured product layer can be formed by a cured product layer ink containing a material constituting the cured product layer such as a curable resin composition and an antiviral agent. The inclusion of silica particles in the cured product layer makes it easier to prevent the antiviral agent from settling in the ink, increasing the stability of the ink and improving the coating suitability, which in turn makes the cured product layer antiviral. It is possible to easily express sex. In addition, the silica particles can easily impart design.

The particle shape of the silica particles includes a sphere, an ellipsoid, a polyhedron, a scaly shape, and the like, and is not particularly limited, but a spherical shape is preferable.
The average particle size of the silica particles is preferably 0.03 to 8.0 μm, more preferably 0.5 to 5.0 μm, and even more preferably 2.5 to 4.5 μm. By setting the average particle size of the silica particles in the above range, the effects of the silica particles described above can be easily obtained, and further, it is possible to easily suppress the protrusion of the silica particles from the cured product layer.

The content of the silica particles is preferably 0.5 to 15.0 parts by mass, more preferably 5.0 to 13.0 parts by mass with respect to 100 parts by mass of the cured product. By setting the content of the silica particles in the above range, the effects of the silica particles described above can be easily obtained, and further, it is possible to easily suppress the protrusion of the silica particles from the cured product layer.

<Antioxidant>
The cured product layer may contain an antioxidant.
Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like. Among these, phosphorus-based antioxidants are preferable in that they can further suppress discoloration of antiviral resin compositions and the like due to light.

<< Phosphorus-based antioxidants >>
Examples of the phosphorus-based antioxidant include a compound having a phosphorous acid structure represented by the following formula (1), a compound having a phosphonic acid structure represented by the following formula (2), and a phosphinic acid structure represented by the following formula (3). Examples thereof include a compound having a phosphine oxide structure represented by the following formula (4). Among these, a compound having a phosphorous acid structure represented by the following formula (1) is preferable.
As the phosphorus-based antioxidant, one kind or two or more kinds can be used.

Examples of the compound having a phosphorous acid structure represented by the formula (1) include compounds represented by the following general formulas (1-1) to (1-3). Among the general formulas (1-1) to (1-3), the general formulas (1-1) and (1-2) tend to have good solubility in the cured product layer ink. Is preferable. By improving the solubility of the phosphorus-based antioxidant in the ink for the cured product layer, the phosphorus-based antioxidant is diffused throughout the cured product layer, which is preferable in that discoloration can be more easily suppressed.

In the general formula (1-1), R ¹¹ , R ¹² and R ¹³ are hydrocarbons which may independently contain a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hetero atom, respectively. Groups are shown, which may have substituents. Further, two selected from R ¹¹ , R ¹² and R ¹³ may be combined to form a ring.

From the viewpoint of further suppressing discoloration, it is preferable that at least one of R ¹¹ , R ¹² and R ¹³ is a linear alkyl group. The linear alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 15 carbon atoms, and even more preferably 8 to 10 carbon atoms. When at least one of R ¹¹ , R ¹² and R ¹³ is a linear alkyl group, the remaining R ¹¹ , R ¹² and R ¹³ are preferably phenyl groups.
Further, from the viewpoint of enhancing solubility and further suppressing discoloration, it is preferable that R ¹¹ , R ¹² and R ¹³ do not bind to each other (two selected from R ¹¹ , R ¹² and R ¹³ are bonded and ringed. It is preferable not to form).

Specific examples of the phosphorus-based antioxidant of the general formula (1-1) are shown in the following formulas (1-1-1) to (1-1-3).

In the general formula (1-2), R ²³ is a hydrocarbon group which may contain a hetero atom and may further have a substituent. Further, R ²¹ , R ²² , R ²⁴ and R ²⁵ are hydrocarbon groups which may independently contain a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hetero atom, respectively. Further, it may have a substituent. Further, R ²¹ and R ²² may be combined to form a ring. Further, R ²⁴ and R ²⁵ may be combined to form a ring.

From the viewpoint of further suppressing discoloration, it is preferable that at least one of R ²¹ , R ²² , R ²² and R ²⁴ is a linear alkyl group, and it is more preferable that all of them are linear alkyl groups. The linear alkyl group preferably has 6 to 18 carbon atoms, more preferably 12 to 15 carbon atoms. Further, from the viewpoint of enhancing solubility and further suppressing discoloration, it is preferable that R ²¹ , R ²² , R ²⁴ and R ²⁵ do not bind to each other (R ²¹ , R ²² , R ²⁴ and R ²⁵ bind to each other). It is preferable not to form a ring).

Specific examples of the phosphorus-based antioxidant of the general formula (1-2) are shown below. In the following general formula (1-2-1), R independently represents a linear alkyl group having 12 to 15 carbon atoms.

In the general formula (1-3), R ³² is a hydrocarbon group which may contain a hetero atom and may further have a substituent. Each of R ³¹ and R ³³ is a hydrocarbon group which may independently contain a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hetero atom, and further has a substituent. May be good.

The phosphorus-based antioxidant may or may not have a polymerizable ethylenic double bond with the curable resin composition, but is preferably not. Since the phosphorus-based antioxidant does not have a polymerizable ethylenic double bond with the curable resin composition, the degree of freedom of movement of the phosphorus-based antioxidant in the cured product layer is increased, and the degree of freedom of movement of the phosphorus-based antioxidant in the cured product layer is increased. It is considered that the phosphorus-based antioxidant is diffused throughout and the discoloration can be easily suppressed.

The molecular weight of the phosphorus-based antioxidant is preferably 1500 or less, more preferably 1300 or less, still more preferably 1200 or less, from the viewpoint of facilitating good solubility in the cured product layer ink. The lower limit of the molecular weight of the phosphorus-based antioxidant is not particularly limited, but is usually 270 or more, preferably 300 or more, and more preferably 330 or more.

The content of the phosphorus-based antioxidant is preferably 10 to 200 parts by mass, more preferably 15 to 100 parts by mass, and 20 to 70 parts by mass with respect to 100 parts by mass of the antiviral agent. Is even more preferable.
By setting the content of the phosphorus-based antioxidant to 10 parts by mass or more, discoloration can be easily suppressed. Further, by setting the content of the phosphorus-based antioxidant to 200 parts by mass or less, it is easy to suppress that the crosslink density of the cured product of the curable resin composition is lowered and the scratch resistance of the cured product layer is lowered. can.

<Light stabilizer>
The cured product layer may further contain a light stabilizer. By including a light stabilizer, discoloration can be more easily suppressed. The light stabilizer is superior in suppressing discoloration in the state of the cured product layer rather than in the state of the composition.
Examples of the light stabilizer include hindered amine compounds. The hindered amine compound has a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

Examples of the hindered amine compound include NH type hindered amine compound, NR type hindered amine compound and NOR type dardamine compound.
Among these hindered amine compounds, NH-type hindered amine compounds and NR-type hindered amine compounds are preferable, and NR-type hindered amine compounds are more preferable, from the viewpoint of making it easier to suppress discoloration. That is, the cured product layer preferably contains one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds, and preferably contains one or more hindered amine compounds selected from NR-type hindered amine compounds. Is more preferable.

The NH-type hindered amine compound is a hydrogen atom bonded to a nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton that remains as a hydrogen atom.
Specific examples of the NH-type hindered amine compound include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

The NR-type hindered amine compound refers to a compound in which a hydrogen atom bonded to a nitrogen atom is replaced with an alkyl group in the 2,2,6,6-tetramethylpiperidine skeleton. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 (the alkyl group is a methyl group).
Specific examples of the NR-type hindered amine compound include 2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylpropanediate bis [1,2, 2,6,6-Pentamethyl-4-piperidinyl], bissebacate (1,2,2,6,6-pentamethyl-4-piperidinyl), 1-methyl sebacate 10- (1,2,2,6,, 6-Pentamethyl-4-piperidyl), 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate and the like.

The NOR-type hindered amine compound refers to a compound in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is replaced with OR ¹ or OCOR ² . In addition, R ¹ and R ² are an alkyl group and / or a cycloalkyl group, preferably an alkyl group having 5 to 12 carbon atoms and / or a cycloalkyl group.

The hindered amine compound preferably has a base dissociation constant (pkb) of 8.5 or less, more preferably 7.0 or less, and even more preferably 6.0 or less. When the pkb of the hindered amine compound is 8.5 or less, discoloration can be more easily suppressed.
The lower limit of pkb of the hindered amine compound is not particularly limited, but is preferably 4.0 or more, and more preferably 4.5 or more.

The hindered amine compound may or may not have an ethylenic double bond polymerizable with the curable resin composition.

The molecular weight of the hindered amine compound is preferably 1000 or less, more preferably 800 or less, still more preferably 700 or less, from the viewpoint of facilitating good solubility in the cured product layer ink. The lower limit of the molecular weight of the hindered amine compound is not particularly limited, but is usually 200 or more, preferably 215 or more, and more preferably 230 or more.

The content of the light stabilizer is preferably 20 to 1000 parts by mass, more preferably 30 to 500 parts by mass, and further preferably 50 to 200 parts by mass with respect to 100 parts by mass of the antiviral agent. preferable. The light stabilizer preferably contains a hindered amine compound in the above range.
By setting the content of the light stabilizer to 20 parts by mass or more, discoloration can be easily suppressed. Further, by setting the content of the light stabilizer to 1000 parts by mass or less, it is possible to easily suppress the decrease in the cross-linking density of the cured product of the curable resin composition and the decrease in the scratch resistance of the cured product layer.

<UV absorber>
The cured product layer may further contain an ultraviolet absorber from the viewpoint of weather resistance.
Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and the like, and a triazine-based ultraviolet absorber is preferable. As the ultraviolet absorber, one kind or two or more kinds can be used.

Further, among the triazine-based ultraviolet absorbers, the hydroxyphenyltriazine-based ultraviolet absorber in which at least one organic group selected from a hydroxyphenyl group, an alkoxyphenyl group and an organic group containing these groups is linked to the triazine ring is one. More preferably, a hydroxyphenyltriazine-based ultraviolet absorber represented by the following general formula (A) is further preferable. Since the hydroxyphenyltriazine-based ultraviolet absorber has a branched structure, it is expected that it will be difficult to bleed out from the cured product layer, and excellent weather resistance will be obtained over a longer period of time.
Further, an ultraviolet absorber having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group and an allyl group is preferable because it is easy to suppress bleed-out.

In the general formula (A), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by −C (= O) OR ¹⁵ , and R ¹³ , R ¹⁴ and R ¹⁵ are independent of each other. It is a monovalent organic group, and n ₁₁ and n ₁₂ are independently integers of 1 to 5.

Examples of the divalent organic group of R ¹¹ include an aliphatic hydrocarbon group such as an alkylene group and an alkaneylene group, and an alkylene group is preferable from the viewpoint of weather resistance, and the carbon number thereof is preferably 1 or more and 20 or less. 1 or more and 12 or less are more preferable, 1 or more and 8 or less are further preferable, and 1 or more and 4 or less are particularly preferable. The alkylene group and the alkenylene group may be linear, branched or cyclic, but linear or branched are preferable.
Examples of the alkylene group having 1 or more and 20 or less carbon atoms include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,3-propylene, a 1,2-propylene and a 2,2-propylene group. Various propylene groups (hereinafter, "various" means linear, branched, and those containing isomers 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 nonadecilene groups, various icosilene groups. The group is mentioned.

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, an arylalkyl group and the like, and an aromatic hydrocarbon group such as an aryl group and an arylalkyl group can be used. Aryl groups are preferred. Of these, a phenyl group is preferable as the monovalent organic group of R ¹³ and R ¹⁴ .
The aryl group preferably has 6 or more and 20 or less carbon atoms, more preferably 6 or more and 12 or less carbon atoms, and more preferably 6 or more and 10 or less carbon atoms, for example, a phenyl group, various methylphenyl groups, and various ethylphenyl groups. Groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and the like can be mentioned. The arylalkyl group preferably has 7 or more and 20 or less carbon atoms, more preferably 7 or more and 12 or less carbon atoms, and more preferably 7 or more and 10 or less carbon atoms, for example, a benzyl group, a phenethyl group, and various phenylpropyl groups. Groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, various hexylbenzyl groups and the like can be mentioned.

^Examples of the monovalent organic group of R15 include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group is preferable. Is more preferable. That is, as R ¹² , an alkyl ester group and an alkenyl ester group are preferable, and an alkyl ester group is more preferable.
The alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 2 or more and 16 or less, and further preferably 6 or more and 12 or less, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, and various types. Pentyl group, 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 nonadesyl groups and various icosyl groups.
As the alkenyl group, an alkenyl group having preferably 2 or more and 20 or less carbon atoms, more preferably 3 or more and 16 or less, still more preferably 6 or more and 12 or less, for example, 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 nonadesenyl groups. Examples include groups and various icosenyl groups.

More specifically, as the hydroxyphenyltriazine compound represented by the general formula (A), R ¹¹ is an alkylene group having 1 or more carbon atoms and 20 or less carbon atoms, and R ¹² and R ¹⁵ are alkyl groups having 1 or more carbon atoms and 20 or less carbon atoms. It is an alkyl ester group as a group, R ¹³ and R ¹⁴ are aryl groups having 6 or more carbon atoms and 20 or less carbon atoms, and a hydroxyphenyltriazine compound having n ₁₁ and n ₁₂ of 1 is preferable, and R ¹¹ has 1 or more carbon atoms and 12 carbon atoms. The following alkylene groups, R ¹² and R ¹⁵ are alkyl ester groups having 2 or more and 16 or less carbon atoms, and R ¹³ and R ¹⁴ are aryl groups having 6 or more and 12 or less carbon atoms, and n ₁₁ And a hydroxyphenyltriazine compound having n ₁₂ of 1 is more preferable, R ¹¹ is an alkylene group having 1 or more and 8 or less carbon atoms, and R ¹² is an alkyl ester group having R ¹⁵ and 6 or more and 12 or less carbon atoms. R ¹³ and R ¹⁴ are aryl groups having 6 or more and 10 or less carbon atoms, hydroxyphenyltriazine compounds having n ₁₁ and n ₁₂ of 1 are more preferable, and R ¹¹ is an alkylene group having 1 or more and 4 or less 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 hydroxyphenyl triazine compounds having n ₁₁ and n ₁₂ of 1 are particularly preferable.

The content of the ultraviolet absorber is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, and 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the cured product. Is even more preferable.

Further, if necessary, the cured product layer may contain a colorant and be colored to a desired hue, lightness, and saturation. The colorant may be appropriately selected from those of the same color as the colorants used for the color layer and the pattern layer described later. By coloring the cured product layer to an appropriate color (hue, lightness, and saturation) with a colorant, the appearance of the design can be improved, and discoloration caused by light or the like of the cured product layer can be made less noticeable by coloring. It is also possible to further improve the discoloration reducing effect of the cured product layer.

<Thickness>
The thickness of the cured product layer can be, for example, 1.0 μm or more and 10000 μm (1 cm) or less from the viewpoint of the balance between processing characteristics and scratch resistance.
When the antiviral article is composed of a single layer of a cured product layer, the thickness of the cured product layer is preferably thick.
On the other hand, in the case of coating (coating) a cured product layer on the base material, the base material is responsible for self-supporting property and durability against external force, and if the antiviral property is thicker than a certain level, that is the case. Considering that the effect is saturated and that as the thickness of the cured product layer becomes thicker, disadvantages such as a decrease in post-processing suitability and an increase in material cost occur, it is preferable that the thickness of the cured product layer is a thin film. Specifically, the thickness of the cured product layer is preferably 1.0 μm or more and 20 μm or less, more preferably 1.5 μm or more and 15 μm or less, and further preferably 2.0 μm or more and 10 μm or less.

<Formation method>
For the cured product layer, for example, an ink for the cured product layer containing a material constituting the cured product layer (curable resin composition, antiviral agent, etc.), a solvent to be added as necessary, etc. is applied onto the substrate. It can be formed by drying and curing. An ink for a cured product layer is applied, dried, and cured on a base material having releasability to form a cured product layer, and the cured product layer is transferred to another substrate or the like to form a cured product layer. It can also be formed.

<Laminate structure>
The antiviral article of the present invention may be a single layer of a cured product layer, or may have a layer other than the cured product layer.
An antiviral article composed of a single layer of a cured product layer is, for example, a group having a mold releasable property from a laminated body obtained by forming a cured product layer on a substrate having a releasable property. It can be obtained by peeling off the material.
Examples of the layer other than the cured product layer of the antiviral article include a base material, a decorative layer, a primer layer, a film layer, an adhesive layer and the like. When the antiviral article is used for wallpaper, the layers other than the cured product layer include a foamed resin layer and a non-foamed layer in addition to the above-mentioned examples (base material, decorative layer, primer layer, film layer, adhesive layer). A resin layer can be mentioned.

Examples of the laminated structure of the antiviral article include the following (1) to (23). In the following (1) to (23), "/" indicates the interface of each layer. Of the following (1) to (23), (13) to (23) are suitable for wallpaper. In the laminated structure of (13) to (23), the non-foamed resin layer may be additionally provided on one side or both sides of the foamed resin layer.
Further, examples of the layer other than the cured product layer of the antiviral article include a functional layer. As the functional layer, a magnetic material layer for magnetic recording use; a conductor layer that functions as a circuit, a copper wire for current, or an electromagnetic wave shielding layer; a gas barrier layer for suppressing the permeation of gas such as water vapor and oxygen; visible light. Examples include a light reflecting layer that reflects with high reflectance; an antireflection layer for suppressing reflection of visible light; and the like. These functional layers can be formed at any of the following laminated configurations (1) to (23) depending on the function of each layer.

(1) Hardened material layer (2) Base material / Hardened material layer (3) Base material / Primer layer / Hardened material layer (4) Base material / Decorative layer / Hardened material layer (5) Base material / Decorative layer / Primer layer / Hardened material layer (6) Base material / Adhesive layer / Film layer / Hardened material layer (7) Base material / Adhesive layer / Decorative layer / Film layer / Hardened material layer (8) Base material / Decorative layer / Adhesive Layer / Film layer / Hardened material layer (9) Base material / Film layer / Primer layer / Hardened material layer (10) Base material / Adhesive layer / Film layer / Primer layer / Hardened material layer (11) Base material / Adhesive Layer / decorative layer / film layer / primer layer / cured product layer (12) base material / decorative layer / adhesive layer / film layer / primer layer / cured product layer (13) base material / foamed resin layer / cured product layer ( 14) Base material / Foamed resin layer / Primer layer / Hardened material layer (15) Base material / Foamed resin layer / Decorative layer / Hardened material layer (16) Base material / Foamed resin layer / Decorative layer / Primer layer / Hardened material layer (17) Base material / Foamed resin layer / Adhesive layer / Film layer / Hardened material layer (18) Base material / Foamed resin layer / Adhesive layer / Decorative layer / Film layer / Hardened material layer (19) Base material / Foam Resin layer / decorative layer / adhesive layer / film layer / cured product layer (20) base material / foamed resin layer / film layer / primer layer / cured product layer (21) base material / foamed resin layer / adhesive layer / film Layer / Primer layer / Hardened material layer (22) Base material / Foamed resin layer / Adhesive layer / Decorative layer / Film layer / Primer layer / Hardened material layer (23) Base material / Foamed resin layer / Decorative layer / Adhesive layer / Film layer / Primer layer / Hardened material layer

From the viewpoint of handleability, the antiviral article preferably has a structure having a cured product layer on the substrate.

"Base material"
The form of the base material may be a flat plate such as a film, a sheet or a plate, or a three-dimensional shape such as a polyhedron, a polygonal prism, a cylinder, a spherical surface or a spheroidal surface, and is not particularly limited.
In addition, films, sheets and boards are often referred to as films, sheets and boards in order from the one having a relatively thin thickness, but in the present specification, these three are not distinguished unless otherwise specified. ..

Examples of the constituent material of the base material include resin, metal, non-metal inorganic material, fibrous material, wood-based material and the like, which can be appropriately selected depending on the intended use.

The base material may be a single layer, or may be a laminated layer of two or more layers made of the above materials. When the base material is a laminate of two or more layers, it is preferable that two or more layers of different materials are laminated to complement each other's various performances of the materials of each layer. Examples of the base material formed by laminating two or more layers include the following A to J. In addition, "/" indicates the interface of each layer.
(A) Resin / wood-based material (B) resin / metal (C) resin / fibrous material (D) resin / non-metal inorganic material (E) resin 1 / resin 2
(F) Metal / Wood-based material (G) Metal / Non-metal Inorganic material (H) Metal / Fibrous material (I) Metal 1 / Metal 2
(J) Non-metal inorganic material / fibrous material

In the above E, the resin 1 and the resin 2 represent different types of resins (for example, the resin 1 is an olefin resin and the resin 2 is an acrylic resin). Further, in the above H, the metal 1 and the metal 2 represent different kinds of metals (for example, the metal 1 is copper and the metal 2 is chromium).

Further, when the base material is a laminated body such as A to J, a layer (adhesive layer or the like) for strengthening the adhesive force may be provided between the layers of each constituent layer of the laminated body. ..

Examples of the resin used as the base material include those made of various synthetic resins or natural resins. As the synthetic resin, a thermoplastic resin and a curable resin can be used.

Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomer, and various olefin-based thermoplastic elastomers, vinyl chloride-based resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers, and polyethylene. Telephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester resin such as polyester-based thermoplastic elastomer, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, poly ( Acrylic resin such as butyl acrylate, methyl (meth) butyl acrylate-(meth) butyl acrylate copolymer, polyamide resin typified by nylon 6 or nylon 66, cellulose triacetate, cellophane, celluloid and the like. Stylized resin, polystyrene, acrylonitrile-styrene copolymer, styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, poly Examples thereof include allylate resin and polyimide resin.
Examples of the curable resin include the thermosetting resin and the ionizing radiation curable resin exemplified in the cured product layer.
Examples of the natural resin include natural rubber, pine fat, amber and the like.

Metals used as a base material include, for example, alloys containing aluminum such as aluminum or duralumin, alloys containing iron such as iron or carbon steel and stainless steel, alloys containing copper such as copper or brass and bronze, gold and silver. , Chromium, nickel, cobalt, tin, titanium and the like. Further, as the metal base material, those obtained by plating or the like with these metals can also be used.

Examples of non-metal inorganic materials used as a base material include non-ceramic ceramic materials such as cement, ALC (lightweight cellular concrete), gypsum, calcium silicate, and wood piece cement, and ceramic materials such as ceramics, earthenware, glass, and amber. Examples include ceramic materials, natural stones such as limestone (including marble), granite, and Anshan rock.

Fibrous materials used as base materials include, for example, thin leaf paper, kraft paper, high-quality paper, Japanese paper, titanium paper, linter paper, sulfate paper, paraffin paper, parchment paper, glassin paper, wallpaper backing paper, board paper and gypsum board. Examples thereof include woven fabrics or non-woven fabrics made of paper such as base paper, polyester resin fibers, acrylic resin fibers, protein-based or cellulose-based natural fibers such as silk, cotton and linen, glass fibers, carbon fibers and the like. In these papers, acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin are used to increase the interfiber strength between the fibers of the paper base material or between other layers and the paper, to prevent fluffing, and to prevent fluffing. It may be the one to which the resin such as the above is added (impregnated with resin after making or filled in at the time of making). Examples of the paper to which the resin is added include inter-paper reinforced paper and resin-impregnated paper.
Further, as an example of a base material in which a resin layer is laminated on a fibrous material layer, a resin layer such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer is formed on the surface of a backing paper for wallpaper, which is often used in the field of building materials. Examples include the original wallpaper of laminated wallpaper.

The shape and dimensions of the base material are not particularly limited and may be appropriately selected depending on the intended use, desired performance and processing suitability.
When the base material is a flat plate of a film, a sheet or a plate, the thickness is a typical design dimension of the article. The thickness is not particularly limited, but is generally set to about 10 μm or more and 10 cm or less from the viewpoint of manufacturing processability, mechanical strength, usability, and economy. In the case of a film or sheet form, a film having a size of 20 μm or more and 300 μm or less is usually selected, and in the case of a plate form, a film having a size of 1 mm or more and 2 cm or less is usually selected.

When the anti-virus article is used as a wallpaper, examples of the base material include backing paper, flame-retardant paper, synthetic resin sheet, woven fabric, non-woven fabric and knitted fabric alone, or a composite thereof.
Further, a flame retardant, an inorganic agent, a dry paper strength enhancer, a wet paper strength enhancer, a colorant, a sizing agent, a fixing agent and the like may be appropriately added to the substrate, if necessary.
The thickness of the base material as the wallpaper is not particularly limited, but the basis weight is usually in the range of about 50 to 300 g / m ² , preferably in the range of 60 to 160 g / m ² .

In order to improve the adhesion of the base material to other layers constituting the antiviral article or the adhesion of the member to be laminated with the antiviral article, the base material is subjected to an oxidation method or unevenness on one or both sides of the base material. A physical surface treatment such as a law or a surface treatment such as a chemical surface treatment can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected depending on the type of the base material, but in general, the corona discharge treatment method is preferably used from the viewpoint of the effectiveness and operability of the surface treatment.

《Primer layer》
The antiviral article preferably has a primer layer in contact with the surface of the cured product layer on the substrate side. The primer layer improves the adhesion between the base material and the cured product layer, and makes it easy to secure long-term interlayer adhesion (so-called weather resistance) and scratch resistance when exposed to ultraviolet rays.
Examples of cases where antiviral articles are exposed to ultraviolet rays include places where sunlight including an ultraviolet spectrum such as near a window enters; inside a kitchen, refrigerator and cupboard where a mercury lamp for sterilization is installed; in direct sunlight. Examples include the installation, construction, or use of anti-virus articles outdoors where they are 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.
As the binder resin, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (carbonate bond to the polymer main chain). Urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the terminal and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic co-weight Resins such as a coalesced resin, a chlorinated propylene resin, a nitrocellulose resin (nitrated cotton), and a cellulose acetate resin are preferably mentioned, and these can be used alone or in combination of two or more. Further, the binder resin may be one obtained by cross-linking and curing these resins by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent. Among these, a polyol resin such as an acrylic polyol resin is preferably cross-linked and cured with an isocyanate-based curing agent, and a acrylic polyol resin is more preferably cross-linked and cured with an isocyanate-based curing agent.

The primer layer preferably contains an ultraviolet absorber and / or a light stabilizer in order to further improve weather resistance. As the ultraviolet absorber and the light stabilizer, general-purpose ones 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 further preferably 1.0 μm or more and 6 μm or less.

The antiviral article may have a back surface primer layer on the side opposite to the cured product layer of the base material for the purpose of improving the adhesiveness with the adherend.
Further, the antiviral article may have an adhesive layer on the side opposite to the cured product layer of the base material for the purpose of adhering it to the adherend. It is preferable to form a peelable separator on the surface of the pressure-sensitive adhesive layer opposite to the base material.

《Film layer》
The antiviral article may have a film layer between the base material and the cured product layer from the viewpoint of increasing the strength and the like.
When the antiviral article has a primer layer, the film layer is preferably located between the substrate and the primer layer. Further, when the antiviral article has a decorative layer, the film layer is preferably located between the decorative layer and the cured product layer from the viewpoint of protecting the decorative layer.

The film layer may be colored as long as it is transparent. When the film layer is formed on the surface of the decorative layer, it may be translucent within the visible range of the decorative layer.

The film layer is preferably in the form of a single layer or a plurality of layers, and at least one layer constituting the film layer is preferably a layer containing polyethylene and / or an ethylene copolymer.
When the film layer is a multi-layer, at least the layer arranged on the base material side (that is, the lowest layer arranged on the foamed resin layer side of the multi-layers) contains polyethylene and / or an ethylene copolymer. It is preferably a layer containing it. After laminating a film in which a layer containing polyethylene and / or an ethylene copolymer is arranged on the bottom layer, the resin layer is crosslinked with an electron beam to improve the melt tension of the resin layer, so that the gas generated from the foamed layer during foaming is improved. Permeation can be efficiently suppressed. Therefore, even if a resin (polypropylene or the like) having a relatively low melt tension is placed as the upper layer of the film layer, the stain resistance of the film layer itself can be maintained.
The polyethylene and / or ethylene copolymer used for the film layer is not particularly limited, and specific examples thereof include the same resins as those used for the foamed resin layer.

When the film layer has a layer containing polyethylene and / or an ethylene copolymer, among the above-mentioned polyethylene and ethylene polymers, polyethylene and ethylene-α, β are preferable from the viewpoint of further improving stain resistance. At least one of the unsaturated carboxylic acid ester copolymers, more preferably at least one of polyethylene and an ethylene-methacrylic acid copolymer (EMAA), particularly preferably an acid-modified polyethylene and an ethylene-methacrylic acid copolymer (EMAA). At least one of the above is mentioned.
Further, the layer containing the polyethylene and / or the ethylene copolymer may contain other resin components as long as the effects of the present invention are not impaired. The ratio of the polyethylene and / or ethylene copolymer to other resin components is, for example, the total amount of the polyethylene and / or ethylene copolymer and other resin components, for example, the polyethylene and / or ethylene copolymer. Is 50 to 100% by weight, preferably 60 to 100% by weight.
When the film layer is made into a plurality of layers, two or more layers containing polyethylene and / or an ethylene copolymer may be provided, and one resin layer other than the layer containing polyethylene and / or an ethylene copolymer is provided. More than one layer may be provided.

The MFR of the polyethylene and / or the ethylene copolymer used for the film layer is not particularly limited, but is usually 1 to 100 g / 10 minutes, preferably 5 to 30 g / from the viewpoint of further improving the extruded film forming property. 10 minutes can be mentioned.
When the film layer contains a resin layer other than the layer containing the polyethylene and / or the ethylene copolymer, the resin component of the resin layer is, for example, a polyolefin resin other than polyethylene and / or the ethylene copolymer. Examples thereof include methacrylic resin, polyvinyl alcohol resin, and fluororesin. Among these, polyolefin resins other than polyethylene and / or ethylene copolymers are preferable, and examples of such polyolefin resins include simple resins such as polypropylene, polybutene, polybutadiene, and polyisoprene.
The thickness of the film layer is not particularly limited, but may be, for example, about 3 to 25 μm, preferably about 5 to 20 μm. When the film layer is a plurality of layers, the thickness of each layer is preferably about 5 to 15 μm.

When the film layer is formed by extrusion film formation, particularly when the film layer is a multi-layer, extrusion film formation by a T-die extruder is suitable. For example, in the case of being composed of two layers, a multi-manifold type T-die capable of simultaneously forming two layers by simultaneously extruding the molten resin corresponding to the two layers can be used.
Further, the film layer may be formed by laminating a film-shaped product in advance to adjacent layers, and even when there are a plurality of film layers, a film layer composed of a plurality of layers may be formed in advance. It may be formed by molding and laminating it on an adjacent layer.
The surface of the film layer, which will be described later, may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, and heavy chromic acid treatment, if necessary. good. The surface treatment may be performed according to the conventional method of each treatment.
When the film layer contains polyethylene and / or an ethylene copolymer as a resin component, the polyethylene and / or ethylene in the film layer can be combined by irradiating an electron beam from the film layer side of the antiviral article. It is preferable that the polymer is crosslinked. By cross-linking by electron beam irradiation in this way, the heat resistance of the layer containing polyethylene and / or the ethylene copolymer is improved, and the finally obtained antiviral article is provided with excellent stain resistance and scratch resistance. It will be possible to prepare.

《Decorative layer》
From the viewpoint of improving the design, the antiviral article preferably has a decorative layer at any position on the antiviral article.
The location where the decorative layer is formed is preferably between the base material and the cured product layer from the viewpoint of enhancing the weather resistance of the decorative layer. When the antiviral article has either a foamed resin layer or a non-foamed resin layer, the portion where the decorative layer is formed is a foamed resin layer, a non-foamed resin layer, and a cured product from the viewpoint of visibility of the decorative layer. It is preferably between layers.

The decorative layer may be formed on the entire surface of the antiviral article or may be formed only on a part thereof. In the case where the outer surface of the cured product layer is covered with the decorative layer, it is preferable to form the decorative layer only in a part of the region in order not to inhibit the expression of antiviral property.

Examples of the decorative layer include a colored layer formed by solid coating with ink; a pattern layer formed by printing ink as a pattern; a metal thin film; and the like.
The patterns expressed by the decorative layer include wood grain patterns such as annual rings and conduit grooves on the surface of the wood board; stone grain patterns on the surface of stone boards such as marble and granite; cloth grain patterns on the surface of the fabric; leather grain patterns on the leather surface; Tile-pasted pattern including joint groove; Brick stack pattern including joint groove; Sand grain pattern; Pear-skin pattern; "Pattern" or "ray carved pattern"); Geometric patterns, letters, figures, polka dots, floral patterns and other abstract patterns; etc.

As the ink used for the coloring layer and the pattern layer, a binder resin is appropriately mixed with a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer and the like. Is used.
The binder resin for the coloring layer and the pattern layer is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-acetic acid. Examples thereof include resins such as vinyl copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. Further, various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.

The colorant is not particularly limited, and is, for example, an inorganic pigment such as carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, cobalt blue; , Isoindolinon yellow, nickel azo complex, phthalocyanine blue, azomethine azo black and other organic pigments or dyes; metal pigments consisting of scaly foil pieces such as aluminum and brass; titanium dioxide coated mica, scaly foil such as basic lead carbonate Pearl gloss (pearl) pigment consisting of one piece; and 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 30 parts by mass or more with respect to 100 parts by mass of the resin constituting the coloring layer and the pattern layer. 70 parts by mass or less is more preferable.

The coloring layer and the pattern layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a coloring agent.
The thickness of the colored layer and the pattern layer may be appropriately selected according to the desired pattern, but is preferably 0.5 μm or more and 20 μm or less from the viewpoint of concealing the ground color of the adherend and improving the design. It is more preferably 1 μm or more and 10 μm or less, and further preferably 2 μm or more and 5 μm or less.

Examples of the metal thin film include a thin film of a single metal element such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt; and a thin film of an alloy containing two or more of the metal elements. Examples of the alloy include brass, bronze, stainless steel and the like.
The film thickness of the metal thin film can be about 0.1 μm to 1 μm.

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

The position of the adhesive layer is not particularly limited, but for example, when the antiviral article has a foamed resin layer (or non-foamed resin layer B), the side opposite to the base material of the foamed resin layer (or non-foamed resin layer B). May have an adhesive layer. Further, when the antiviral article has a film layer, an adhesive layer may be provided between the base material and the film layer. Further, when the antiviral article has a decorative layer, an adhesive layer may be provided on the opposite side of the base material of the decorative layer. Further, as described above, when the base material is a laminated body having two or more layers, an adhesive layer may be provided between the layers constituting the base material.
The adhesive layer is mainly provided to improve the adhesive strength of each layer constituting the antiviral article.

Further, the adhesive layer may be partially provided in a pattern for the purpose of providing regions having different adhesive strengths (weak adhesive region and strong adhesive region) in the plane of the antiviral article. In this case, the portion where the adhesive layer is provided becomes the strong adhesive region, and the portion where the adhesive layer is not provided becomes the weak adhesive region.

The resin used for the adhesive layer can be set according to the type of the layer adjacent to the adhesive layer. For example, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene. -(Meta) acrylic acid copolymer (EMAA), acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd Examples thereof include based resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluororesins, silicone resins, fibrous derivatives, rubber resins and the like.

The thickness of the adhesive layer is not particularly limited, but is preferably about 0.1 to 10 μm.

《Effervescent resin layer》
The antiviral article may have a foamed resin layer. The foamed resin layer is preferably arranged between the base material and the cured product layer. When the antiviral article has a foamed resin layer, the design and the texture are improved, which is particularly suitable for wallpaper.

As the resin constituting the foamed resin layer, a thermoplastic resin is preferable. Examples of the thermoplastic resin include polyvinyl chloride-based resins, polyethylene-based, polypropylene-based, and polybutene-based polyolefin resins, ethylene-vinyl acetate copolymer resins, polystyrene-based resins, and acrylonitrile-butadiene-styrene-based copolymer resins ( Thermoplastics of ABS-based resin), acrylonitrile-styrene copolymer resin, nylon, polyacetal-based resin, acrylic resin, polycarbonate-based resin, polyester-based resin, polyvinyl acetate-based resin, polyvinyl alcohol-based resin, polyurethane-based resin, etc. Examples thereof include a resin alone and a copolymer, or a mixed resin thereof. Among them, polyvinyl chloride-based resin is preferable because it has film-forming property, flexibility, and processability at low temperature, and can be used as a relatively low-cost wallpaper. Also, from the viewpoint of environmental protection, polyolefin-based resin and ethylene are preferable. -Vinyl acetate-based copolymer resin and ethylene- (meth) acrylic acid copolymer resin are preferable.

The foamed resin layer can be formed, for example, by emulsifying the resin constituting the foamed layer and applying a composition for forming a foamed resin layer formed by adding a foaming agent or the like to the emulsion by a comma coater method or the like. can. Alternatively, the foamed resin layer is obtained by pelletizing a composition for forming a foamed resin layer containing a resin, a foaming agent, an inorganic filler to be added as needed, and the like by a method such as an extrusion film forming method or a calendar film forming method. Can be formed by. The timing for foaming the foamed resin layer is preferably after laminating all the layers constituting the antiviral article.

Examples of the foaming agent used for the foamed resin layer include inorganic foaming agents such as sodium hydrogencarbonate, sodium carbonate, ammonium hydrogencarbonate, ammonium carbonate and ammonium nitrite, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, and the like. Nitroso compounds such as N, N'-dinitrosopentamethylenetetramine, azo compounds such as azodicarboxylic amide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzene Sulfonyl hydrazide compounds such as sulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonylhydrazide, calcium azide, 4,4'-diphenyldisulfonylazide, p. -Azide compounds such as toluenesulfonylazide can be mentioned.

The amount of the foaming agent added may be appropriately determined depending on the required design, but is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin constituting the foamed resin layer. If necessary, a foaming aid that promotes the decomposition of the foaming agent can be used in combination to improve the foaming effect.

The foamed resin layer preferably contains an inorganic filler from the viewpoint of enhancing flame retardancy.
Examples of the inorganic filler include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, and water. Aluminum oxide, alumina, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite , Aluminum borate, silica balloon, glass flakes, glass balloon, silica, iron slag, copper, iron, iron oxide, carbon black, sentust, alnico magnet, magnetic powder such as various ferrites, cement, glass powder, diatomaceous earth, trioxide Examples thereof include antimony, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, myoban, and the like. Of these, calcium carbonate and titanium dioxide are preferable. In addition, these inorganic fillers may be used alone, or two or more kinds may be used together.

The content of the inorganic filler is preferably 30 to 150 parts by mass, more preferably 40 to 100 parts by mass with respect to 100 parts by mass of the resin constituting the foamed resin layer.
The average particle size of the inorganic filler is preferably 5 to 25 μm, more preferably 5 to 15 μm.

Various additives can be blended in the foamed resin layer according to the required physical characteristics. Examples of the additive include a fungicide, an insect repellent, a preservative, an antibacterial agent, a diluent, a deodorant, a light stabilizer, a plasticizer and the like.

The thickness of the foamed resin layer is preferably 50 to 300 μm in the film-forming state, and the thickness after foaming is preferably 500 to 1200 μm.

<Non-foaming resin layer>
When the antiviral article has a foamed resin layer, it may further have a non-foamed resin layer. The non-foaming resin layer can be formed, for example, between the foamed resin layer and the cured product layer and / or between the base material and the foamed resin layer.

<Non-foaming resin layer A>
For example, a non-foamed resin layer A (adhesive resin layer) may be provided on the back surface of the foamed resin layer (between the base material and the foamed resin layer) for the purpose of improving the adhesive force with the base material.

The resin component of the non-foaming resin layer A is not particularly limited, but an ethylene-vinyl acetate copolymer (EVA) is preferable. Known or commercially available EVA can be used. In particular, the ethylene-vinyl acetate copolymer preferably has a vinyl acetate component (VA component) of 10 to 46% by mass, more preferably 15 to 41% by mass, based on the total amount of the copolymer.
The thickness of the non-foaming resin layer A is not particularly limited, and examples thereof include about 5 to 50 μm.

<Non-foaming resin layer B>
The non-foaming resin layer B may be provided on the upper surface (the surface opposite to the base material) of the foamed resin layer. The non-foaming resin layer B is provided, for example, for the purpose of clarifying the design of the decorative layer and improving the scratch resistance of the foamed resin layer.

Examples of the resin component of the non-foaming resin layer B include polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluororesins and the like, and among these, polyolefin resins are preferable.
Examples of the polyolefin-based resin include a homopolymer of ethylene, a single resin such as polypropylene, polybutene, polybutadiene, and polyisoprene, a copolymer of ethylene and an α-olefin having 4 or more carbon atoms (linear low-density polyethylene, etc.), and the like. Ethylene (meth) acrylic acid-based copolymer resin such as ethylene-acrylic acid copolymer resin, ethylene-methyl acrylate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, etc. , Ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate copolymer resin saponified product, ionomer and the like. The thickness of the non-foaming resin layer B is not particularly limited, but may be, for example, about 5 to 10 μm.
In the present embodiment, it is preferable to have the non-foaming resin layer A, the foaming resin layer, and the non-foaming resin layer B in this order from the base material side.

<Excipient processing>
The antiviral article may be given a desired uneven shape (also referred to as an uneven pattern) by a shaping treatment such as embossing.
When embossing, for example, the antiviral article is heated to preferably 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 200 ° C. or lower, and further preferably 100 ° C. or higher and 180 ° C. or lower to obtain an antiviral article. Embossing can be performed by pressing the embossed plate. The portion where the embossed plate is pressed is preferably on the cured product layer side of the antiviral article. When the antiviral article has a foamed resin layer, it is preferable to foam the foamed resin layer and then perform shaping treatment.

<Use>
The antiviral article of the present invention can be used for various purposes. Specific uses include the following (1) to (12).
(1) Surface materials (for example, wallpaper) for interior parts such as walls, floors, and ceilings of buildings such as houses, offices, stores, hospitals, and clinics.
(2) Surface materials for exterior walls, roofs, eaves ceilings, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics.
(3) Surface materials for fittings (interior or exterior parts) such as windows, window frames, doors, door frames; surface materials for accessories (handles, etc.) of fittings; surface materials for jigs for fittings.
(4) Surface materials for handrails, waist walls, surrounding edges, thresholds, Kamoi, and Kasagi's building members.
(5) Surface material for outdoor (exterior) parts such as fences, gates, pillars of drying stands, and handrails.
(6) Surface materials for furniture such as chests of drawers, desks, chairs, cupboards, and kitchen sinks; surface materials for furniture accessories (handles, etc.); surface materials for furniture jigs.
(7) Surface materials for housings of various home appliances such as television receivers, radio receivers, refrigerators, microwave ovens, washing machines, fans, air conditioners, etc .; Accessories (handles, switches, touch panels, etc.) of home appliances Surface material; Surface material for home appliance jigs.
(8) Surface materials for OA equipment such as various computer equipment such as electronic copiers, facsimiles, printers, and personal computers; Surface materials for housings of various OA equipment for ATM equipment of financial institutions such as banks and post offices; Surface material for accessories (keyboard keyboard, touch panel, etc.) of OA equipment; Surface material for jigs of various OA equipment.
(9) Surface materials for interior or exterior parts (walls, floors, ceilings, handrails, columns, control panels, levers, handles, steering wheels, etc.) of vehicles such as automobiles and railroad vehicles, ships, and aircraft. ..
(10) Partitions of various buildings; Shielding plates or curtains to prevent virus droplet infection at stores, offices, windows of government offices, checkout locations, etc .; Protective surfaces (face guards), protective glasses (goggles) Face protectors such as; or these surface materials.
(11) Business forms such as slips; passbooks; cards such as cash cards, credit cards, and point cards of financial institutions; or their surface materials.
(12) Bottles of glass, resin, etc .; metal cans; resin flexible 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 an antiviral agent obtained by supporting or containing silver ions in apatite or glass, with respect to 100 parts by mass of the curable resin composition. , The antiviral agent is contained in an amount of more than 1 part by mass.

The embodiments of the "curable resin composition" and the "antiviral agent carrying or containing silver ions in apatite or glass" in the antiviral resin composition of the present invention are the above-mentioned antiviral properties of the present invention. It is the same as the embodiment of the "curable resin composition" and the "antiviral agent carrying or containing silver ions in apatite or glass" in the article.

The antiviral resin composition of the present invention may contain silica particles, an antioxidant, a light stabilizer, an ultraviolet absorber and the like, if necessary.
Embodiments of "silica particles", "antioxidants", "light stabilizers" and "ultraviolet absorbers" in the antiviral resin composition of the present invention are the "silica" in the antiviral article of the present invention described above. It is the same as the embodiment of "particle", "antioxidant", "light stabilizer" and "ultraviolet absorber".

<Solvent>
The antiviral resin composition of the present invention preferably contains a solvent.
The solvent may be, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.). Etc.), aromatic hydrocarbons (toluene, xylene, etc.), carbon halides (di 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 (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. It can be exemplified and may be a mixture thereof.

The content of the solvent is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total amount of the antiviral resin composition (ink for cured product layer).

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

1. 1. Evaluation The following evaluations were carried out for the antiviral articles of Examples and Comparative Examples. The atmosphere for evaluation was a temperature of 23 ° C. ± 5 ° C. and a humidity of 40 to 65% RH.

1-1. Discoloration of antiviral articles With respect to the antiviral articles of Examples and Comparative Examples, the L ^* a ^* b ^* values immediately after production were measured. A spectrocolorimeter (product number "CM-3700A" manufactured by Konica Minolta Co., Ltd.) was used as the measuring device.
Next, the antiviral articles of Examples and Comparative Examples were subjected to an accelerated weather resistance test under the following conditions using an ultraviolet autofade meter. Then, the L ^* a ^* b ^* value after the accelerated weather resistance test was measured.
Then, 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 1.
The color difference (ΔE ^* ab) is when the measured values immediately after production are L ^{* 1} , a ^{* 1} and b ^{* 1} , and the measured values after the accelerated weathering test are L ^{* 2} , a ^{* 2} and b ^{* 2} . , Can be calculated by the following formula.
ΔE ^* ab = [(L ^{* 2} -L ^{* 1} ) ² + (a ^{* 2} -a ^{* 1} ) ² + (b ^* 2-a ^{* 2} ) ² ] ^1/2

<Test equipment>
・ "Ultraviolet auto fade meter" from Suga Test Instruments Co., Ltd.
<Irradiation conditions>
-Illuminance: 500 W / m ² , black panel temperature: 63 ° C, time: 300 hours

2. 2. Preparation of antiviral article [Example 1]
Using a 3 type 3-layer multi-manifold T-die extruder, a film is extruded onto a fibrous sheet so that the thickness is 5 μm / 50 μm / 5 μm in the order of non-foamed resin layer A / foamed resin layer / non-foamed resin layer B. did. As a result, the laminate 1 composed of a base material (backing paper for wallpaper having a basis weight of 65 g / m2. Product name: NI-65A of Nippon Paper Industries, Ltd.) / non-foamed resin layer A / foamed resin layer / non-foamed resin layer B is formed. Obtained. At this stage, the foaming agent of the foamed resin layer is not foamed.
Next, on the non-foaming resin layer B, an ink for a pattern layer (an ink composition using an acrylic resin as a binder and an inorganic pigment as a colorant) is gravure-printed so that the coating amount is 3.0 g / m ² . A substrate / non-foaming resin layer A / foamed resin layer / non-foaming resin layer B / pattern layer was obtained.
Next, the following film layer and the following adhesive layer are co-extruded onto the pattern layer of the laminate B using a multi-manifold T-die extruder so that the adhesive layer is on the pattern layer side, and then on the surface. A load was applied using a roll having an uneven shape to obtain a laminate C composed of a base material / non-foaming resin layer A / foaming resin layer / non-foaming resin layer B / pattern layer / adhesive layer / film layer. ..
Next, an ink for a cured product layer having the following composition was applied onto the film layer of the laminate C by a gravure direct coater method so that the coating amount was 2.0 g / m ² .
After coating, an electron beam having an acceleration voltage of 175 kV and an irradiation dose of 30 kGy (3Mrad) was irradiated to cure the ionizing radiation curable resin composition to form a cured product layer (physical film thickness: 2 μm).
The sheet thus obtained is foamed with a foamed resin composition at 230 ° C. using a heating foaming furnace to form a foamed resin layer, and then between a cooling roll and a pressure roll on which an embossed mold is formed. Was embossed to obtain an antiviral article for wallpaper of Example 1, which had an uneven pattern on the surface.

<Non-foaming resin layer A>
-Ethylene-vinyl acetate copolymer (EVA) 100 parts by mass "Evaflex EV150 manufactured by Mitsui Dou Polychemical Co., Ltd."
<Effervescent resin layer composition>
-Ethylene methacrylic acid copolymer 90 parts by mass (Mitsui / Dow Polychemical Co., Ltd., trade name: Nuclel N1050H)
・ Petroleum-based resin softening modifier 10 parts by mass (Arakawa Chemical Industry Co., Ltd., trade name: Alcon R-100)
・ 4 parts by mass of foaming agent (Otsuka Chemical Co., Ltd., product name: Uniform AZ Ultra)
・ 40 parts by mass of calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name: Whiten H)
20 parts by mass of titanium oxide (DuPont, trade name: Typure R-108)
・ 5 parts by mass of light stabilizer (manufactured by Adeka Argus Chemical, trade name: O-1305)
・ Dispersant 3 parts by mass (manufactured by Daikyo Kasei Kogyo Co., Ltd., product name: MFX-50E)
1 part by mass of cross-linking agent (manufactured by JSR Corporation, trade name: Obstar JVA-702)
<Non-foaming resin layer B>
-Ethylene-methacrylic acid copolymer (EMAA) 100 parts by mass "Mitsui-Dau Polychemical Co., Ltd., trade name: Nuclel N1560"
<Adhesive layer>
-Acid-modified polyethylene "Modic M545 manufactured by Mitsubishi Chemical Corporation" (5 μm)
<Film layer>
-Polyethylene "HC170 (MFR: 10 g / 10 min) manufactured by Japan Polyethylene Corporation" (10 μm)

<Ink for cured product layer>
70 parts by mass of trifunctional urethane oligomer (KESchem, trade name: KUA-6I)
・ 30 parts by mass of bifunctional urethane oligomer (KESK, trade name: KUA-4I)
-Silicone methacrylate 3 parts by mass (JNC Corporation, trade name: Cyraplane FM-0711)
-Anti-virus agent that supports silver ions on apatite 6.5 parts by mass (manufactured by Shinto V-Cerax, trade name: antibacterial ceramics, silver ion loading amount 3% by mass, average particle diameter 0.8 μm)
・ Silica particles 8 parts by mass (average particle size about 3-4 μm)
-Weather resistant agent 1 part by mass (NR type hindered amine compound, ADEKA, trade name: ADEKA STAB LA-72)

[Comparative Example 1]
"Antiviral agent that carries silver ions on apatite" for cured material layer, "Antiviral agent that carries silver ions on zeolite (trade name" Zeomic AJ-10D "of Sinanen New Ceramics Co., Ltd.", An antiviral article for the wallpaper of Comparative Example 1 was obtained in the same manner as in Example 1 except that the average particle size was changed to 2.2 μm).

As shown in Table 1, it can be confirmed that the antiviral article for the wallpaper of the example can suppress discoloration.

100: Antiviral article 200: Wallpaper 10: Cured material layer 11: Cured material of curable resin composition 12: Antiviral agent carrying or containing silver ions on apatite or glass 20: Base material 30: Foamed resin Layer 40: Non-foamed resin layer 50: Decorative layer 60: Primer layer

Claims (7)

An article with a hardened layer
The cured product layer contains a cured product of a curable resin composition and an antiviral agent obtained by supporting or containing silver ions on apatite or glass.
An antiviral article containing more than 1 part by mass of the antiviral agent with respect to 100 parts by mass of the cured product. The antiviral article according to claim 1, wherein the cured product layer further contains silica particles. The antiviral article according to claim 1 or 2, wherein the cured product layer is provided on a substrate. The antiviral article according to claim 3, further comprising a foamed resin layer between the base material and the cured product layer. The antiviral article according to claim 4, wherein a non-foaming resin layer is provided between the foamed resin layer and the cured product layer. The antiviral article according to any one of claims 1 to 5, which is for wallpaper. The curable resin composition and an antiviral agent obtained by supporting or containing silver ions in apatite or glass are contained, and the antiviral agent is contained in an amount of more than 1 part by mass with respect to 100 parts by mass of the curable resin composition. , Antiviral resin composition.

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