JP7602352B2 - Antiviral interior materials - Google Patents

Description

The present invention relates to an antiviral interior material in which an antiviral treatment layer is provided on the surface of a base material.

For interior materials for homes and other buildings, products with antibacterial and antifungal properties have been commercially available in the past, but with the recent spread of COVID-19, there is a growing demand to impart antiviral properties to interior materials. Unlike bacteria and fungi (mold), viruses do not have cells and cannot grow on their own, but instead grow by invading human or animal cells. Furthermore, viruses are tens to hundreds of nanometers in size, which is about 1/100 to 1/1000 the size of bacteria and fungi. As such, viruses are completely different from bacteria and fungi, and therefore conventional antibacterial and antifungal agents are not necessarily effective in suppressing viruses as they are.

Previously, there have been interior decorative sheets with antiviral properties, the surface of which is coated with a resin containing a silver-based inorganic additive or a zinc-based inorganic additive (see, for example, Patent Document 1). The interior decorative sheet of Patent Document 1 is made by compounding an inorganic antibacterial agent, which is an inorganic compound (zeolite, apatite, zirconia, etc.) that has metal ions (silver ions, copper ions, zinc ions) incorporated therein, as a silver-based inorganic additive or a zinc-based inorganic additive, into a resin, and coating the surface of the interior decorative sheet with this.

In addition, as a product that claims to have antiviral properties, there is an antibacterial/antiviral polyvinyl chloride member with a layer containing a copper compound and a plasticizer on the surface (see, for example, Patent Document 2). The antibacterial/antiviral polyvinyl chloride member of Patent Document 2 has a layer containing a monovalent copper compound, which is an antibacterial/antiviral component, and a phthalate ester plasticizer, a phosphate ester plasticizer, or a trimellitic acid plasticizer formed on the surface of a base material formed of polyvinyl chloride, which is the main component.

JP 2015-80887 A JP 2019-44096 A

The commercial value of interior materials for homes and other buildings is greatly influenced not only by functionality but also by aesthetics and design. Therefore, when the surface of interior materials is treated with an antiviral agent, it is desirable that the aesthetics are not impaired, i.e., no discoloration or changes in color tone occur.

In this regard, the interior decorative sheet of Patent Document 1 is susceptible to discoloration of the metal ions (silver ions, copper ions, zinc ions) contained in the inorganic antibacterial agent when exposed to light, which may impair the aesthetics and design of the interior decorative sheet. In addition, according to the examples described in the specification, the interior decorative sheet of Patent Document 1 is said to have antiviral properties against influenza A virus (H1N1 type), but the results show that the antiviral properties were high when the amount of inorganic antibacterial agent was increased (Example 1), and that antiviral properties were not obtained when a small amount was added (Comparative Example 1). Note that if the amount of inorganic antibacterial agent is increased, the effect of the inorganic antibacterial agent becomes stronger, which may impair the aesthetics of the interior decorative sheet.

The antibacterial and antiviral vinyl chloride material in Patent Document 2 is said to be able to suppress discoloration caused by monovalent copper compounds used as antibacterial and antiviral ingredients by using a specific plasticizer, but no consideration has been given to antiviral agents other than copper compounds. Because the invention is specialized for monovalent copper compounds, it is expected that the discoloration suppression effect caused by other antiviral agents will not be observed.

The present invention was made in consideration of the above problems, and aims to provide an antiviral interior material that exhibits excellent antiviral properties at low cost and is suitable for use in homes and other applications where aesthetics and design are required.

The antiviral interior material according to the present invention for solving the above problems has the following characteristic configuration:
An antiviral interior material having an antiviral treatment layer on a surface of a base material,
the antiviral treatment layer contains an ionizing radiation curable resin as a matrix and an antiviral agent as an active ingredient,
The antiviral agent is
(1) 3-iodo-2-propynyl butylcarbamate;
(2) N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide);
(3) titanium oxide-containing zinc titanium complex compound; and (4) titanium oxide-containing copper titanium complex compound;
The object of the present invention is to include at least one selected from the group consisting of:

According to the antiviral interior material of this configuration, the antiviral treatment layer provided on the surface of the base material contains an ionizing radiation curable resin as a matrix and an antiviral agent as an active ingredient. The form of the antiviral agent in the antiviral treatment layer can be in various forms, such as a state in which the above-mentioned (1) to (4) antiviral agents are dispersed as fine particles as an active ingredient in the ionizing radiation curable resin matrix, a state in which the ionizing radiation curable resin and the antiviral agent are mixed at the molecular level, and a state in which the molecules of the antiviral agent are labeled on the side chains of the polymer that constitutes the ionizing radiation curable resin. The above-mentioned (1) to (4) antiviral agents exhibit antiviral properties against various viruses, regardless of the type of virus, whether or not it has an envelope, by themselves, but by coexisting with the ionizing radiation curable resin, the antiviral properties inherent to the antiviral agent are maximized due to the interaction between the antiviral agent and the ionizing radiation curable resin, or the antiviral properties of the antiviral agent are amplified in cooperation with the ionizing radiation curable resin, which is a unique property. As a result, even if a small amount of the antiviral agent is used, the antiviral agent exhibits excellent antiviral properties, and is low cost and low irritation to the skin is achieved. In addition, the above antiviral agents (1) and (2) are organic antiviral agents and do not contain metals, metal oxides, and metal salts that are easily discolored, so they do not discolor even when exposed to light. The above antiviral agents (3) and (4) are inorganic antiviral agents, but do not contain metals, metal oxides, and metal salts that are particularly prone to discoloration, and the metals contained are in the form of passivated oxides, complex oxides, or complex compounds, so they are less likely to discolor. Therefore, by using the above antiviral agents (1) to (4) in the antiviral treatment layer, it is possible to obtain an antiviral interior material suitable for applications such as housing where aesthetics and design are required.

In the antiviral interior material according to the present invention,
The total content of the antiviral agent per unit area of the antiviral treatment layer is preferably 0.1 to 16 g/ ^m2 .

According to the antiviral interior material having the above configuration, by setting the total content of the antiviral agent per unit area in the antiviral treatment layer to 0.1 to 16 g/ ^m2 , it is possible to provide an antiviral interior material that exhibits excellent antiviral properties while suppressing production costs.

In the antiviral interior material according to the present invention,
It is preferable that the antiviral treatment layer further contains hard fine particles.

According to the antiviral interior material of this configuration, the antiviral treatment layer contains hard microparticles, which improves abrasion resistance and provides an anti-slip effect when the antiviral interior material is a flooring material. In addition, by blending hard microparticles into the antiviral treatment layer, fine irregularities are formed on the surface of the antiviral interior material, and viruses are trapped in these irregularities, which are expected to be inactivated over time.

In the antiviral interior material according to the present invention,
The substrate preferably includes a resin molded body containing vinyl chloride resin as a main component.

The antiviral interior material of this configuration can provide an antiviral interior material with excellent antiviral properties at low cost in a wide range of fields, since resin molded bodies whose main component is polyvinyl chloride resin are used in a variety of situations and applications.

In the antiviral interior material according to the present invention,
The antiviral agent is preferably substantially free of silver, silver oxide, or silver salts.

According to the antiviral interior material of this configuration, the antiviral agent does not substantially contain silver, silver oxide, or silver salt, which are highly irritating to the skin and easily discolor, and metals contained other than silver are in the form of passivated oxides, composite oxides, or composite compounds, so it is possible to provide an antiviral interior material that is resistant to discoloration even when exposed to light or heat.

FIG. 1 is a schematic cross-sectional view of an antiviral interior material according to one embodiment of the present invention.

The antiviral interior material of the present invention will be described. However, the present invention is not limited to the configurations shown in the following embodiments, examples, and drawings.

<Anti-viral interior materials>
FIG. 1 is a schematic cross-sectional view of an antiviral interior material according to one embodiment of the present invention. Interior materials include floor materials (typically sheet-shaped or tile-shaped floor materials, excluding carpets), waist-wall sheets, wall sheets, ceiling sheets, etc. The antiviral interior material of the present invention is particularly suitable for use as floor materials and waist-wall sheets, since it is relatively thick and has excellent strength such as abrasion resistance. In FIG. 1, a resin floor material laid on the floor surface of a room in a house or the like is illustrated as an example of the interior material. Therefore, in the following description, the "antiviral interior material" may be referred to as the "antiviral floor material". In FIG. 1, the antiviral floor material is shown to be composed of multiple layers, but the thickness relationship of each layer is appropriately exaggerated or simplified for ease of explanation, and does not strictly reflect the size relationship (scale) of the thickness of each layer in an actual antiviral floor material.

As shown in FIG. 1, the antiviral flooring material 1 has a substrate 10 and an antiviral treatment layer 20 provided on the surface of the substrate 10.

[Substrate]
The substrate 10 is generally a resin molded body obtained by molding a thermoplastic resin with a mold or a rolling roll, but the substrate 10 used for the flooring material may be, for example, a floor sheet or a floor tile specified in JIS A 5705:2016. The floor sheet and the floor tile may have a single layer structure or a multi-layer structure. For example, according to JIS A 5705:2016, a single-layer vinyl floor sheet is an example of a single-layer floor sheet, and a multi-layer vinyl floor sheet, a foamed multi-layer vinyl floor sheet, and a cushion floor are examples of a multi-layer floor sheet. In addition, a single-layer vinyl floor tile and a composition vinyl floor tile are examples of a single-layer floor tile, and a multi-layer floor tile is an example of a multi-layer floor tile. FIG. 1 illustrates a resin molded sheet having a multi-layer structure as the substrate 10. A resin material mainly composed of vinyl chloride resin is preferably used for the resin molded portion of the resin molded sheet.

In this embodiment, the substrate 10 has, in order from the back side (laying surface side) to the front side (surface layer side), a foamed resin layer 11a, a shape stabilizing layer 12, an intermediate resin layer 11b, a decorative layer 13, and a surface layer 14. However, the surface layer 14 is of any configuration and may be provided as necessary. The foamed resin layer 11a and the intermediate resin layer 11b together constitute the resin layer 11. It is also possible that the resin layer 11 is made up of only the foamed resin layer 11a, and the intermediate resin layer 11b and the decorative layer 13 are integrated to form the decorative layer. The resin used in the resin layer 11 is preferably a thermoplastic resin. Examples of the thermoplastic resin include vinyl chloride resin, ethylene-vinyl acetate copolymer, vinyl acetate resin, olefin resin, acrylic resin, amide resin, ester resin, etc. These thermoplastic resins may be used alone or may be a mixture of multiple types (polymer blend). A preferred thermoplastic resin is vinyl chloride resin in terms of versatility, durability, and processability. In addition, it is possible to compound various additives such as fillers, plasticizers, flame retardants, stabilizers, antioxidants, lubricants, colorants, and foaming agents into the thermoplastic resin. The thickness of the substrate 10 is preferably 1 to 10 mm, and more preferably 1.5 to 6 mm. If the thickness of the substrate 10 is within the above range, it is easy to handle as an antiviral flooring material 1 while ensuring sufficient strength and durability.

The surface layer 14 is a layer for protecting the decorative layer 13 and for ensuring physical properties such as abrasion resistance. The surface layer 14 may be transparent or opaque, but in the case of a configuration having the decorative layer 13, it is preferable that the surface layer 14 is transparent so that the design of the decorative layer 13 on the back side of the surface layer 14 can be visually recognized. In addition, the surface layer 13 may not be provided. In this case, a pigment or the like may be added to the surface layer 14 to make it opaque and give the surface layer 14 the function of a decorative layer. Examples of materials for the surface layer 14 include polyvinyl chloride resin, silicone resin, and mixtures thereof. The surface layer 14 is preferably non-foamed, and the surface layer 14 and the antiviral treatment layer 20 are integrated to increase the strength of the flooring material. The thickness of the surface layer 14 is preferably 0.1 to 1 mm, more preferably 0.1 to 0.7 mm, and even more preferably 0.2 to 0.5 mm. If the thickness of the surface layer 14 is within the above range, the effect of abrasion resistance will last for a long time.

On the back surface of the substrate 10, multiple recesses 15 are formed by embossing. By providing multiple recesses 15, when the antiviral flooring 1 is adhered to the surface on which it is to be laid, the adhesive penetrates into the recesses 15, improving the adhesion between the antiviral flooring 1 and the surface on which it is to be laid. Note that the multiple recesses 15 are not essential and may be provided as needed. For example, when the antiviral flooring 1 is used as a carpet, it is desirable to increase the contact area between the antiviral flooring 1 and the surface on which it is to be laid to prevent slippage, so it may be better not to provide multiple recesses 15.

[Anti-viral treatment layer]
The antiviral treatment layer 20 is a layer for protecting the surface layer 14 from scratches and dirt and for exerting antiviral performance. The antiviral treatment layer 20 may be transparent or opaque, but is preferably transparent like the surface layer 14 so that the design of the decorative layer 13 can be visually recognized. The antiviral treatment layer 20 contains an ionizing radiation curable resin and an antiviral agent. The ionizing radiation curable resin is a matrix (base material) in the antiviral treatment layer 20, and the antiviral agent is an active ingredient. The antiviral agent can exist in various states, such as a state in which fine particles of the antiviral agent are dispersed in the ionizing radiation curable resin, a state in which the ionizing radiation curable resin and the antiviral agent are mixed at the molecular level, and a state in which molecules of the antiviral agent are labeled on the side chains of the polymer constituting the ionizing radiation curable resin. The thickness of the antiviral treatment layer 20 is preferably thinner than that of the surface layer 14, specifically, preferably 5 to 150 μm, more preferably 10 to 70 μm, and even more preferably 15 to 30 μm. If the thickness of the antiviral treatment layer 20 is within the above range, it will exhibit sufficient durability even when laid on a floor surface and stepped on with the soles of shoes, and the antiviral effect will last for a long period of time.

[Ionizing radiation curable resin]
Ionizing radiation curable resin is a general term for resins that are cured (polymerized) by exposure to ionizing radiation such as ultraviolet rays, X-rays, gamma rays, charged particle beams, and neutron beams. In the present invention, it is preferable to use an ultraviolet curable resin having reactivity to ultraviolet light as the electron radiation curable resin, since this resin has excellent processability and workability.

For the synthesis (polymerization) of ultraviolet curable resin, ultraviolet curable monomers or oligomers that are cured by irradiation with ultraviolet light are used. Examples of ultraviolet curable monomers or oligomers include monomers or oligomers having polymerizable unsaturated bond groups such as (meth)acrylate groups and (meth)acryloyloxy groups or epoxy groups in the molecule. Specific examples of ultraviolet curable monomers include styrene-based monomers such as α-methylstyrene, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane (meth)acrylate, and polyol compounds having two or more thiol groups in the molecule. Specific examples of ultraviolet curable oligomers include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate and other acrylates, unsaturated polyesters, and epoxies. These ultraviolet curable monomers or oligomers may be used alone or in a mixture of two or more. Of the above UV-curable monomers or oligomers, monomers or oligomers having a (meth)acrylate group in the molecule are preferred, and in particular, urethane (meth)acrylate is more preferred as the oligomer. The molecular weight of the UV-curable monomer or oligomer is not particularly limited, but is preferably about 200 to 10,000.

UV-curable monomers or oligomers begin to polymerize when irradiated with UV light, and a photopolymerization initiator is generally used as the initiator. Examples of photopolymerization initiators include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, benzyl dimethyl ketal, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and other thioxanthate compounds.

[Antiviral Agents]
Antiviral agents effective in the present invention include the following four compounds:
(1) 3-iodo-2-propynyl butylcarbamate (2) N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide)
(3) Titanium oxide-containing zinc-titanium complex compound (4) Titanium oxide-containing copper-titanium complex compound

(1) 3-iodo-2-propynyl butylcarbamate is an organic antiviral agent and has the following chemical structure (1).

(2) N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) is an organic antiviral agent and has the following chemical structural formula (2).

(3) The titanium oxide-containing zinc titanium complex compound is an inorganic antiviral agent, and can be in various forms, such as a form in which titanium oxide fine particles are dispersed in an amorphous or crystalline zinc titanium complex compound, a form in which titanium oxide is incorporated into the crystal lattice of a crystalline zinc titanium complex compound, a form in which titanium oxide is introduced into the micropores of a porous zinc titanium complex compound, and a form in which titanium oxide is intercalated between the layers of a layered zinc titanium complex compound.

(4) The titanium oxide-containing copper-titanium complex compound is an inorganic antiviral agent, and can be in various forms, such as a form in which titanium oxide fine particles are dispersed in an amorphous or crystalline copper-titanium complex compound, a form in which titanium oxide is incorporated into the crystal lattice of a crystalline copper-titanium complex compound, a form in which titanium oxide is introduced into the micropores of a porous copper-titanium complex compound, and a form in which titanium oxide is intercalated between the layers of a layered copper-titanium complex compound.

The above antiviral agents (1) to (4) were found by the present inventors after extensive research among the many available antiviral agents, as being particularly suitable for interior materials. The available antiviral agents include those that have been used conventionally as antibacterial agents or antifungal agents. The above antiviral agents (1) to (4) not only exhibit antiviral properties against various viruses, regardless of the type of virus, whether or not it has an envelope, but also exhibit unique properties in which the antiviral properties inherent to the antiviral agent are maximized by the interaction between the antiviral agent and the above ionizing radiation curable resin (ultraviolet ray curable resin), or the antiviral properties of the antiviral agent are amplified in cooperation with the above ionizing radiation curable resin. Therefore, if the above antiviral agents (1) to (4) are used together with the ionizing radiation curable resin as the antiviral treatment layer 20, excellent antiviral properties can be achieved even in small amounts, and as a result, it is possible to manufacture antiviral interior materials with low irritation to the skin at low cost. The amount of the antiviral agent used, as the content in the antiviral treatment layer 20, is 0.1 to 8 mass% for the antiviral agent (1) above, preferably 2 to 5 mass%, 0.1 to 5 mass% for the antiviral agent (2) above, preferably 0.2 to 1.5 mass%, more preferably 0.3 to 0.8 mass%, 1 to 15 mass% for the antiviral agent (3) above, preferably 5 to 10 mass%, and 0.1 to 5 mass% for the antiviral agent (4) above, preferably 0.2 to 1.5 mass%, more preferably 0.3 to 0.8 mass%.

The above antiviral agents (1) or (2) are organic antiviral agents that do not substantially contain metals, metal oxides, or metal salts that are prone to discoloration, and therefore do not discolor even when exposed to light. The above antiviral agents (3) or (4) are inorganic antiviral agents, but do not substantially contain metals (e.g., silver), metal oxides (e.g., silver oxide), or metal salts (e.g., silver salts such as silver nitrate, silver chloride, and silver phosphate) that are highly irritating to the skin and prone to discoloration, and the metals that are contained are in the form of passivated oxides, complex oxides, or complex compounds, making them less likely to discolor. Here, "substantially free" means that unavoidable trace amounts of contamination are permitted, but significant amounts of contamination are excluded. For example, when the antiviral agents (1) to (4) above are synthesized using a catalyst containing silver, trace amounts of silver derived from the catalyst may be mixed into the antiviral agent as a contaminant, but since this is an unavoidable trace amount, the agent is treated as being substantially free of silver, silver oxide, and silver salts.

Therefore, by using the above antiviral agents (1) to (4) in the antiviral treatment layer 20, it is possible to obtain an antiviral interior material that exhibits excellent antiviral properties while being suitable for applications such as housing where aesthetics and design are required.

In addition, when the antiviral agent is blended in the antiviral treatment layer 20, the above antiviral agents (1) to (4) may be blended alone or in combination of two or more. In particular, from the viewpoint of immediate antiviral effect, it is preferable to blend one of the organic antiviral agents (1) and (2), and more preferably to blend one of the inorganic antiviral agents (3) and (4) in addition from the viewpoint of immediate antiviral effect. The antiviral agent (3) has deodorizing properties in addition to antiviral properties, so that an antiviral interior material with deodorizing function can be obtained. In addition, only one of the inorganic antiviral agents (3) and (4) may be blended, and the antiviral effect can be exerted over a long period of time. By combining the organic (1) or (2) with the inorganic (3) or (4), a blend having an antiviral effect that is both immediate and long-lasting can be obtained. On the other hand, when it is necessary to reduce the total amount of chemicals used, it is also possible to use the antiviral agents (1) to (4) alone and achieve the desired effect. In this way, the present invention makes it possible to select from organic and inorganic antiviral agents that exhibit excellent antiviral properties and are highly suitable for the aesthetics and design required of flooring materials, in accordance with the properties and uses of the target flooring material.

[Other ingredients]
The antiviral treatment layer 20 may further contain hard microparticles as other components. By incorporating hard microparticles into the antiviral treatment layer 20, the abrasion resistance is improved, and in the case where the antiviral interior material 1 is a floor material as in this embodiment, a non-slip effect is also obtained. In addition, by blending hard microparticles into the antiviral treatment layer 20, fine irregularities are formed on the surface of the antiviral interior material 1, and the virus is trapped in the irregularities, and the effect of inactivating the virus as it is over time can be expected. The size of the hard microparticles is preferably 0.1 to 50 μm as an average particle size, and more preferably 10 to 30 μm. If the average particle size of the hard microparticles is within the above range, the abrasion resistance and non-slip effect of the antiviral interior material 1 can be improved without inhibiting the efficacy of the antiviral agent contained in the antiviral treatment layer 20. The particle size (average particle size) of the hard microparticles can be measured, for example, by a laser diffraction type particle size distribution measuring device. As the type of hard fine particles, either inorganic fine particles or organic fine particles can be used, and there is no particular limitation as long as the appearance is colorless or white so as not to impair the aesthetics and design of the interior material, and the fine particles do not discolor or are difficult to discolor due to light or heat, but as inorganic fine particles, alumina, titanium oxide, silica, silicon oxide, zirconium oxide, etc. are preferred, and as organic fine particles, crystalline cellulose, acrylic beads, etc. are preferred. As the shape of the hard fine particles, either spherical or irregular shape can be used, but when it is desired to make the surface unevenness gentle, spherical shapes are preferred, and when it is desired to form severe unevenness for the purpose of improving anti-slip properties, etc., irregular shapes are preferred.

Other ingredients include solvents, leveling agents, fillers, dispersants, plasticizers, surfactants, antioxidants, thixotropic agents, pigments, fragrances, etc.

[Interaction]
As described above, the antiviral treatment layer 20 in the antiviral interior material 1 of the present invention has an antiviral agent present as an active ingredient in a dispersed state in the ionizing radiation cured resin matrix. Although the mechanism of the antiviral treatment layer 20 in such a state has not been fully elucidated, a phenomenon has been observed that is unexpected from previous knowledge, that is, the antiviral agent shows extremely excellent antiviral properties even when used in a small amount. Regarding this phenomenon, the inventors have come to the hypothesis that the presence of some kind of interaction between the antiviral agent contained in the antiviral treatment layer 20 and the ionizing radiation cured resin maximizes the antiviral properties inherent to the antiviral agent, or that the antiviral properties of the antiviral agent are amplified in cooperation with the ionizing radiation cured resin. Based on this unpredictable phenomenon and the hypothesis of the present inventors, the inventors have intensively studied the formulation of antiviral agents that can cause the antiviral treatment layer 20 to exhibit effective antiviral properties. As a result, it has been revealed that by setting the total content of the above antiviral agents (1) to (4) per unit area in the antiviral treatment layer 20 to 0.1 to 16 g/m ² and the content per unit area of each antiviral agent to 0.02 to 4 g/m ² , excellent antiviral properties are exhibited against various viruses, regardless of the type of virus that has an envelope or not. In particular, the content of the antiviral agent (1) is preferably 0.02 to 1.53 g/m ² , more preferably 0.40 to 0.98 g/m ^2. The content of the antiviral agent (2) is preferably 0.02 to 0.98 g/m ² , more preferably 0.06 to 0.16 g/m ² . The antiviral agent (3) is preferably 0.20 to 2.70 g/ ^m2 , more preferably 0.98 to 1.88 g/ ^m2 . The antiviral agent (4) is preferably 0.02 to 0.98 g/ ^m2 , more preferably 0.06 to 0.16 g/ ^m2 . If the content of the antiviral agent per unit area is less than the lower limit, the antiviral treatment layer 20 cannot exhibit effective antiviral properties. On the other hand, even if the content of the antiviral agent per unit area exceeds the upper limit, the antiviral properties of the antiviral treatment layer 20 are not significantly improved, which is uneconomical. When the antiviral agent (3), which is an inorganic antiviral agent, is used, the lower limit of the content of the antiviral agent per unit area in the antiviral treatment layer 20 can be set to 1.50 g/m2 or ^more by slightly increasing the lower limit, thereby allowing the antiviral agent to exhibit deodorizing properties in addition to antiviral properties. The antiviral property test using the antiviral interior material 1 of the present invention will be specifically described in the examples described later.

<Method of manufacturing antiviral interior material>
The following describes a method for producing the antiviral interior material 1 of the present invention. The antiviral interior material 1 is completed by first producing the base material 10 by forming, in order from the bottom, the foamed resin layer 11a, the shape stabilizing layer 12, the intermediate resin layer 11b, the decorative layer 13, and the surface layer 14, and then forming the antiviral treatment layer 20 on the base material 10.

For example, a foaming resin material such as a foaming agent-containing vinyl chloride paste, which is the raw material for the foamed resin layer 11a, is applied to the development surface of a development film or the like, a shape stabilizing layer 12 such as a glass sheet is placed on top of that, and then a vinyl chloride paste, which is the raw material for the intermediate resin layer 11b, is applied on top of that to form a pre-gelled laminate. This laminate is then heated at 140-150°C to form a pre-gelled laminate, which is the source of the foamed resin layer 11a, the shape stabilizing layer 12, and the intermediate resin layer 11b. The decorative layer 13 is formed by attaching a transfer sheet to the surface of the pre-gelled laminate and transferring a design. Alternatively, the decorative layer 13 may be formed using a printed sheet on which a design is printed.

Next, a surface layer forming material containing vinyl chloride resin, alkoxysilane, a sol-gel reaction accelerating catalyst, etc. is applied to the surface of the pregelled laminate to form a film, and when this is heated at 160 to 200°C, both the pregelled laminate and the surface layer forming material gel, completing the substrate 10 with each layer laminated. If necessary, embossing may be performed from the surface layer 14 side of the substrate 10 to form a surface embossment.

Next, an antiviral treatment layer forming material is prepared by mixing an ultraviolet-curable monomer or oligomer, a photopolymerization initiator, an antiviral agent, and the like. The organic antiviral agents (1) and (2) have superior dispersibility and are easier to mix than the inorganic antiviral agents (3) and (4). The prepared antiviral treatment layer forming material is applied to the surface of the substrate 10 to form a film. The amount of application of the antiviral treatment layer forming material is appropriately adjusted depending on the content of the antiviral agent in the antiviral treatment layer 20 to be formed later, but can be, for example, 20 to 40 g/ ^m2 .

Then, when the applied antiviral treatment layer-forming material is irradiated with ultraviolet light, the antiviral treatment layer-forming material hardens, forming an antiviral treatment layer 20 on the substrate 10, and the antiviral interior material 1 of the present invention is obtained.

To confirm the virus suppression effect of the antiviral interior material of the present invention, an antiviral confirmation test was conducted on the non-enveloped feline calicivirus and the enveloped influenza A virus (H1N1 type). Incidentally, coronaviruses, like influenza viruses, are classified as enveloped viruses. The antiviral confirmation test was conducted in accordance with the film adhesion method defined by the Society of International Association of Antibacterial Products (SIAA). The procedure for the film adhesion method conducted in this example is as follows.

<Film adhesion method>
(1) An antiviral interior material (specimen) is treated (applied) with a phage liquid containing a virus.
(2) The test specimen coated with the phage liquid is covered with a film and left to stand for a predetermined period of time (24 hours in this embodiment).
(3) After a predetermined time has elapsed, the specimen is washed with a washing solution, and the virus-containing solution is recovered.
(4) The virus-containing liquid is infected into a host bacterium to evaluate the virus infectivity, and the number of viruses contained in the virus-containing liquid is measured.

Example 1
The substrate used was a foamed multilayer vinyl floor sheet (product name "Hospirium NW", manufactured by Toli Industries, Inc.). In detail, Hospirium NW has a coating of ultraviolet-curable resin formed as the outermost layer, but in this example, the laminate before this coating was formed was used as the substrate. An antiviral treatment layer was formed to a thickness of 20 μm on the surface of the substrate, thereby obtaining the antiviral interior material of Example 1. The composition of the antiviral treatment layer contained 100 parts by weight of a urethane acrylate ultraviolet-curable resin as the ultraviolet-curable resin, and 5.0 parts by weight of 3-iodo-2-propynyl butylcarbamate (product name "POLYPHASE AF3", manufactured by Troy Industries, Inc.) as the antiviral agent.

Example 2
In Example 1, the amount of the antiviral agent in the antiviral treatment layer of the antiviral interior material was 2.0 parts by weight, but the other components were the same as in Example 1, and an antiviral interior material of Example 2 was obtained by the same procedure as in Example 1.

Example 3
In Example 1, the antiviral treatment layer of the antiviral interior material contained 1.0 part by weight of N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) (product name "Slamoni D100", manufactured by Osaka Gas Chemicals Co., Ltd.) as the antiviral agent, and the rest of the composition was the same as in Example 1. An antiviral interior material of Example 3 was obtained by the same procedure as in Example 1.

Example 4
In Example 3, the amount of the antiviral agent in the antiviral treatment layer of the antiviral interior material was 0.5 parts by weight, but the other components were the same as in Example 3, and an antiviral interior material of Example 4 was obtained by the same procedure as in Example 3.

Example 5
In Example 1, the antiviral treatment layer of the antiviral interior material contained 5.0 parts by weight of a titanium oxide-containing zinc titanium composite compound (product name "Seventhol N-PC90", manufactured by Osaka Gas Chemicals Co., Ltd.) as the antiviral agent. The other components were the same as in Example 1, and the antiviral interior material of Example 5 was obtained by the same procedure as in Example 1.

Example 6
In Example 1, the antiviral interior material of Example 6 was obtained by the same procedure as in Example 1, except that the antiviral agent contained in the antiviral treatment layer of the antiviral interior material contained 0.5 parts by weight of a titanium oxide-containing copper titanium composite compound (product name "HPS POWDER AC-20", manufactured by DIC Corporation) was used as the antiviral agent.

Comparative Example 1
The same substrate as in Example 1 was used, and the same urethane acrylate ultraviolet-curable resin as in Example 1 was applied to the surface of the substrate, and this was cured to form a UV-resistant film with a thickness of 20 μm, thereby obtaining an interior material (control) of Comparative Example 1. That is, the interior material of Comparative Example 1 is the antiviral interior material of Example 1 except that the antiviral agent has been removed from the antiviral treatment layer.

<Evaluation of antiviral activity based on virus reduction rate>
To evaluate antiviral properties, the antiviral interior materials (specimens) of Examples 1 to 6 and the interior material (control) of Comparative Example 1 were subjected to a water resistance treatment or a light resistance treatment, and an antiviral property confirmation test was carried out using the above-mentioned film adhesion method. Then, for the antiviral interior materials (specimens) of Examples 1 to 6 and the interior material (control) of Comparative Example 1, the virus counts (n ₀ ) immediately after (0 hours) and after 24 hours (n ₂₄ ) were measured, and the virus reduction rate was calculated according to the following formula (I).
Virus reduction rate (%) = (1 - _n24 / _n0 ) x 100 ... (I)
When the virus reduction rate is 95% or more, it is recognized that there is an antiviral effect. The evaluation of antiviral properties (virus reduction rate) is shown in Table 1 below.

Regarding the antiviral effect against feline calicivirus, the antiviral interior material of Example 6, which was treated with water resistance, had a virus reduction rate of 99% or more, demonstrating an extremely excellent antiviral effect. A certain level of antiviral effect was also observed for the antiviral interior material of Example 2. For the antiviral interior materials of Examples 1 to 6, which were treated with light resistance, all had a virus reduction rate of 99% or more, demonstrating an extremely excellent antiviral effect.

Regarding the antiviral effect against influenza A virus, all of the antiviral interior materials of Examples 1 to 6 achieved a virus reduction rate of 99% or more, regardless of whether they were treated to be water-resistant or light-resistant, demonstrating an extremely excellent antiviral effect. A high virus reduction rate was also achieved for Comparative Example 1 (control), which did not contain an antiviral agent, but looking at the virus count after 24 hours, the virus count was lower in Examples 1 to 6 than in Comparative Example 1, particularly in the water-resistant treated material. From this, it is believed that a certain degree of virus proliferation suppression effect can be expected against influenza A virus, provided that the environment (conditions) are appropriate.

When the above antiviral effects against feline calicivirus or influenza A virus were examined, the titanium oxide-containing copper titanium complex compound incorporated in the antiviral interior material of Example 6 in particular exhibited an extremely excellent antiviral effect overall, and it can be said that it is highly practical as an antiviral agent to be applied to interior materials. In addition, the 3-iodo-2-propynyl butylcarbamate incorporated in the antiviral interior materials of Examples 1 and 2 also exhibited an overall excellent antiviral effect that was comparable to that of Example 6, particularly in Example 2, in which the amount of antiviral agent incorporated was optimized, and it can also be said that it is highly practical. In addition, the N,N'-hexamethylene bis(4-carbamoyl-1-decylpyridinium bromide) incorporated in the antiviral interior materials of Examples 3 and 4 and the titanium oxide-containing zinc titanium complex compound incorporated in the antiviral interior material of Example 5 also exhibited an overall antiviral effect that was superior to that of Comparative Example 1, and were sufficiently practical.

The antiviral interior material of the present invention can be used as resin flooring (sheet-like flooring, tile-like flooring), wainscoting sheets, wall sheets, ceiling sheets, etc. The antiviral interior material of the present invention can be used in a variety of situations, including general housing, schools, offices, commercial facilities, public facilities, and businesses.

1. Antiviral interior materials (antiviral flooring materials)
10 Substrate (resin molded sheet)
20 Antiviral treatment layer

Claims (3)

An antiviral interior material having an antiviral treatment layer on a surface of a base material,
The substrate is a floor sheet or floor tile as defined in JIS A 5705:2016,
the antiviral treatment layer contains an ionizing radiation curable resin as a matrix and an antiviral agent as an active ingredient,
The antiviral agent comprises N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide);
The content of the antiviral agent per unit area of the antiviral treatment layer is 0.06 to 0.16 g/ ^m2 ,
The content of the antiviral agent in the antiviral treatment layer is 0.2 to 1.5% by mass,
The antiviral agent is an antiviral interior material that is substantially free of silver, silver oxide, and silver salts . The antiviral interior material according to claim 1 , wherein the antiviral treatment layer further contains hard fine particles. The antiviral interior material according to claim 1 or 2 , wherein the base material comprises a resin molded body containing a polyvinyl chloride resin.

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