Antiviral interior materials

Abstract

To provide an antiviral interior material which can exhibit excellent antiviral property at low cost, and is suitable for applications of a housing requiring aesthetic property and designability.SOLUTION: An antiviral interior material 1 having an antiviral treatment layer 20 provided on a surface of a base material 10, in which the antiviral treatment layer 20 contains an ionizing radiation-curable resin as a matrix and an antiviral agent as an active ingredient, and the antiviral agent contains at least one selected from the group consisting of (1) 3-iodo-2-propynyl butyl carbamate, (2) N,N'-hexamethylene bis(4-carbamoyl-1-decylpyridinium bromide), (3) a titanium oxide-containing titanium zinc composite compound, and (4) a titanium oxide-containing titanium copper composite compound.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an antiviral interior material having an antiviral treatment layer provided on the surface of a base material. [Background technology]

[0002] For interior materials for houses and the like, products with antibacterial and antifungal properties have been commercially available up until now, but with the recent spread of COVID-19, there is an increasing demand for interior materials with antiviral properties. Unlike bacteria and fungi (mold), viruses do not have cells and cannot grow alone, but invade human or animal cells and grow. In addition, viruses are about tens to hundreds of nanometers in size, which is about 1 / 100 to 1 / 1000 of 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.

[0003] Conventionally, there have been interior decorative sheets having 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 in a resin, and coating the surface of the interior decorative sheet with this.

[0004] Additionally, as a product that claims to have antiviral properties, there is an antibacterial and antiviral polyvinyl chloride member having a layer containing a copper compound and a plasticizer on its surface (see, for example, Patent Document 2). The antibacterial and antiviral polyvinyl chloride member of Patent Document 2 has a layer containing a monovalent copper compound, which is an antibacterial and 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. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-80887 A [Patent Document 2] JP 2019-44096 A Summary of the Invention [Problem to be solved by the invention]

[0006] The commercial value of interior materials for homes, etc. 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 desired that the aesthetics are not impaired, i.e., no discoloration or change in color tone occurs.

[0007] In this regard, the interior decorative sheet of Patent Document 1 is prone 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.

[0008] 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.

[0009] The present invention has been made in consideration of the above problems, and has an object to provide an antiviral interior material that can exhibit excellent antiviral properties at low cost and is suitable for applications such as housing where aesthetics and design are required. [Means for solving the problem]

[0010] 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 dioxide-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:

[0011] 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 antiviral agent may exist in various forms in the antiviral treatment layer, such as a state in which the above-mentioned antiviral agents (1) to (4) are dispersed as fine particles as an active ingredient in the ionizing radiation curable resin as a 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 constituting the ionizing radiation curable resin. The above-mentioned antiviral agents (1) to (4) exhibit antiviral properties against various viruses by themselves, regardless of the type of virus due to the presence or absence of an envelope, but when coexisting with an 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 the amount of the antiviral agent used is small, the antiviral agent exhibits excellent antiviral properties, and low cost and low irritation to the skin are achieved. In addition, the above-mentioned (1) and (2) antiviral agents 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-mentioned (3) and (4) antiviral agents are inorganic antiviral agents, but do not contain metals, metal oxides, and metal salts that are particularly easily discolored, and the metals contained are in the form of passivated oxides, complex oxides, or complex compounds, so they are not easily discolored. Therefore, by using the above-mentioned (1) to (4) antiviral agents in the antiviral treatment layer, an antiviral interior material suitable for applications such as housing where aesthetics and design are required can be obtained.

[0012] 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 0.1 to 16 g / m 2 It is preferable that:

[0013] According to the antiviral interior material of this configuration, the total content per unit area of ​​the antiviral agent in the antiviral treatment layer is 0.1 to 16 g / m 2 This makes it possible to obtain an antiviral interior material that exhibits excellent antiviral properties while suppressing production costs.

[0014] In the antiviral interior material according to the present invention, It is preferable that the antiviral treatment layer further contains hard fine particles.

[0015] 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 floor 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 the effect of trapping viruses in the irregularities and inactivating them over time can be expected.

[0016] 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.

[0017] According to the antiviral interior material of the present configuration, since resin molded articles whose main component is polyvinyl chloride resin are used in a variety of situations and applications, it is possible to provide an antiviral interior material that is low-cost and has excellent antiviral properties for use in a wide range of fields.

[0018] In the antiviral interior material according to the present invention, The antiviral agent is preferably substantially free of silver, silver oxide, or silver salts.

[0019] 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 prone to discoloration, 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. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic cross-sectional view of an antiviral interior material according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The antiviral interior material according to the present invention will be described below. However, the present invention is not limited to the embodiments, examples, and configurations shown in the drawings described below.

[0022] <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, and the like. 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 magnitude relationship (scale) of the thickness of each layer in an actual antiviral floor material.

[0023] 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.

[0024] [Base material] 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 floor tile may be 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.

[0025] The substrate 10 in this embodiment 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 has an arbitrary 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, and the like. 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 also possible to blend 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 the antiviral flooring material 1, while sufficient strength and durability can be ensured.

[0026] 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 as a decorative layer. Examples of the material of the surface layer 14 include vinyl 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 as a 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 is sustained for a long period of time.

[0027] A plurality of recesses 15 are formed on the back surface of the substrate 10 by embossing. If such a plurality of recesses 15 is provided, when the antiviral flooring material 1 is adhered to a surface to be laid with an adhesive, the adhesive penetrates into the recesses 15, improving the adhesion between the antiviral flooring material 1 and the surface to be laid. Note that the plurality of recesses 15 is not an essential component and may be provided as necessary. For example, when the antiviral flooring material 1 is used as a carpet, it is desirable to increase the contact area between the antiviral flooring material 1 and the surface to be laid to prevent slippage, so it may be better not to provide a plurality of recesses 15.

[0028] [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.

[0029] [Ionizing radiation curable resin] An ionizing radiation curable resin is a general term for resins that are cured (polymerized) by irradiation with ionizing radiation such as ultraviolet rays, X-rays, gamma rays, charged particle beams, and neutron beams. Ionizing radiation curable resins are synthesized by radical polymerization accompanied by irradiation with ionizing radiation. In the present invention, it is preferable to use an ultraviolet curable resin that is reactive to ultraviolet rays as the electron radiation curable resin, since it has excellent processability and workability.

[0030] For the synthesis (polymerization) of the ultraviolet curable resin, an ultraviolet curable monomer or oligomer that is cured by irradiation with ultraviolet light is used. Examples of the ultraviolet curable monomer or oligomer include a monomer or oligomer having a polymerizable unsaturated bond group such as a (meth)acrylate group or a (meth)acryloyloxy group or an epoxy group in the molecule. Specific examples of the ultraviolet curable monomer 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 the ultraviolet curable oligomer include acrylates such as urethane (meth)acrylate, polyester (meth)acrylate, and epoxy (meth)acrylate, unsaturated polyester, and epoxy. These ultraviolet curable monomers or oligomers may be used alone or in a mixture of two or more. Among the above ultraviolet curable monomers or oligomers, monomers or oligomers having a (meth)acrylate group in the molecule are preferred, and in particular, as the oligomer, urethane (meth)acrylate is more preferred. The molecular weight of the ultraviolet curable monomer or oligomer is not particularly limited, but is preferably about 200 to 10,000.

[0031] The ultraviolet-curable monomer or oligomer starts to polymerize by irradiation with ultraviolet light, and a photopolymerization initiator is generally used as the initiator. Examples of the photopolymerization initiator 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.

[0032] [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) Zinc-titanium complex compound containing titanium dioxide (4) Titanium oxide-containing copper-titanium complex compound

[0033] (1) 3-iodo-2-propynyl butylcarbamate is an organic antiviral agent and has the following chemical structural formula (1).

[0034] [ka]

[0035] (2) N,N'-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) is an organic antiviral agent and has the following chemical structural formula (2).

[0036] [ka]

[0037] (3) The titanium oxide-containing zinc titanium composite compound is an inorganic antiviral agent and may be in various forms, for example, a form in which titanium oxide fine particles are dispersed in an amorphous or crystalline zinc titanium composite compound, a form in which titanium oxide is incorporated into the crystal lattice of a crystalline zinc titanium composite compound, a form in which titanium oxide is introduced into the micropores of a porous zinc titanium composite compound, or a form in which titanium oxide is intercalated between the layers of a layered zinc titanium composite compound.

[0038] (4) The titanium oxide-containing copper-titanium composite compound is an inorganic antiviral agent and can be in various forms, for example, a form in which titanium oxide fine particles are dispersed in an amorphous or crystalline copper-titanium composite compound, a form in which titanium oxide is incorporated into the crystal lattice of a crystalline copper-titanium composite compound, a form in which titanium oxide is introduced into the micropores of a porous copper-titanium composite compound, or a form in which titanium oxide is intercalated between the layers of a layered copper-titanium composite compound.

[0039] The above antiviral agents (1) to (4) were found by the present inventors after extensive research among 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 the virus 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 ionizing radiation curable resin (ultraviolet ray curable resin), or the antiviral properties of the antiviral agent are amplified in cooperation with the ionizing radiation curable resin. Therefore, by using the above antiviral agents (1) to (4) 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 an antiviral interior material 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 %, preferably 2 to 5 mass %, for the antiviral agent (1) above, 0.1 to 5 mass %, preferably 0.2 to 1.5 mass %, and more preferably 0.3 to 0.8 mass %, for the antiviral agent (2) above, 1 to 15 mass %, preferably 5 to 10 mass %, for the antiviral agent (3) above, and 0.1 to 5 mass %, preferably 0.2 to 1.5 mass %, and more preferably 0.3 to 0.8 mass %, for the antiviral agent (4) above.

[0040] In addition, the above antiviral agent (1) or (2) is an organic antiviral agent and does not substantially contain metals, metal oxides, and metal salts that are easily discolored, so it does not discolor even when exposed to light. The above antiviral agent (3) or (4) is an inorganic antiviral agent, but does not substantially contain metals (e.g., silver), metal oxides (e.g., silver oxide), and metal salts (e.g., silver salts such as silver nitrate, silver chloride, and silver phosphate) that are highly irritating to the skin and easily discolor, and the metals contained are in the form of passivated oxides, complex oxides, or complex compounds, so they are not easily discolored. Here, "substantially free" means that a trace amount of contamination that is unavoidable is allowed, but a significant amount of contamination is excluded. For example, when the above antiviral agents (1) to (4) are synthesized using a catalyst containing silver, a trace amount of silver derived from the catalyst may be mixed into the antiviral agent as a contaminant, but since this is a trace amount that is unavoidable, it is treated as being substantially free of silver, silver oxide, and silver salt.

[0041] Therefore, by using the antiviral agents (1) to (4) described above in the antiviral treatment layer 20, it is possible to obtain an antiviral interior material that exhibits excellent antiviral properties and is suitable for applications such as housing where aesthetics and design are required.

[0042] 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 further blend one of the inorganic antiviral agents (3) and (4). The antiviral agent (3) has deodorizing properties in addition to antiviral properties, so that an antiviral interior material having deodorizing functions can be obtained. Also, 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 sustained can be obtained. On the other hand, when it is necessary to suppress the total amount of chemicals used, it is also possible to achieve the effect by using the antiviral agents (1) to (4) alone. 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 for flooring materials, in accordance with the properties and uses of the target flooring material.

[0043] [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 the present 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 effect of trapping viruses in the irregularities and inactivating them as time passes 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.

[0044] Examples of other components include solvents, leveling agents, fillers, dispersants, plasticizers, surfactants, antioxidants, thixotropic agents, pigments, and fragrances.

[0045] [Interaction] As described above, the antiviral treatment layer 20 in the antiviral interior material 1 of the present invention is present in a state in which the antiviral agent is dispersed as an active ingredient 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 that was unexpected from previous knowledge was observed, that is, even if the amount of the antiviral agent used is small, the antiviral treatment layer 20 exhibits extremely excellent antiviral properties. Regarding this phenomenon, the inventors have come to the hypothesis that the existence 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 the antiviral properties of the antiviral agent are amplified in cooperation with the ionizing radiation cured resin. Based on this unpredictable phenomenon and the inventors' hypothesis, the blending of antiviral agents that can cause the antiviral treatment layer 20 to exhibit effective antiviral properties was earnestly studied, and it was found that the total content of the above antiviral agents (1) to (4) per unit area in the antiviral treatment layer 20 is 0.1 to 16 g / m 2 The content of each antiviral agent per unit area is 0.02 to 4 g / m 2 By doing so, it became clear that the antiviral agent (1) exhibited excellent antiviral properties against various viruses, regardless of the type of virus, whether it was enveloped or not. In particular, the antiviral agent (1) exhibited excellent antiviral properties against various viruses, regardless of the type of virus, regardless of the presence or absence of an envelope, at a concentration of 0.02 to 1.53 g / m 2 is preferable, and 0.40 to 0.98 g / m 2 The antiviral agent (2) is more preferably in an amount of 0.02 to 0.98 g / m 2 is preferably 0.06 to 0.16 g / m 2 The antiviral agent (3) is more preferably in an amount of 0.20 to 2.70 g / m 2 is preferably 0.98 to 1.88 g / m 2 The antiviral agent (4) is more preferably in an amount of 0.02 to 0.98 g / m 2 is preferably 0.06 to 0.16 g / m 2is more preferable. 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 do not improve significantly, which is uneconomical. When using the inorganic antiviral agent (3), the lower limit of the content of the antiviral agent per unit area in the antiviral treatment layer 20 is slightly increased to 1.50 g / m. 2 By setting the above, it is possible 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.

[0046] <Manufacturing method for antiviral interior materials> 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 a base material 10 by forming, from the bottom up, a foamed resin layer 11a, a shape stabilizing layer 12, an intermediate resin layer 11b, a decorative layer 13, and a surface layer 14 in that order, and then forming an antiviral treatment layer 20 on the base material 10.

[0047] For example, a foaming resin material such as a foaming agent-containing vinyl chloride paste, which is the raw material of 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 thereon, and a vinyl chloride paste, which is the raw material of the intermediate resin layer 11b, is further applied thereon to form a pre-gelled laminate. Next, this laminate is heated at 140 to 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.

[0048] 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 in which each layer is laminated. If necessary, embossing may be performed from the surface layer 14 side of the substrate 10 to form a surface embossment.

[0049] 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 the antiviral treatment layer-forming material applied is appropriately adjusted depending on the content of the antiviral agent in the antiviral treatment layer 20 to be formed later, but may be, for example, 20 to 40 g / m. 2 It can be said that:

[0050] When the applied antiviral treatment layer-forming material is irradiated with ultraviolet light, the antiviral treatment layer-forming material hardens, forming the antiviral treatment layer 20 on the substrate 10, thereby obtaining the antiviral interior material 1 of the present invention. EXAMPLES

[0051] In order to confirm the virus suppression effect of the antiviral interior material according to 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 are classified as enveloped viruses, just like influenza viruses. The antiviral confirmation test was conducted in accordance with the film adhesion method stipulated by the Society of International Association of Antibacterial Products (SIAA). The procedure of the film adhesion method conducted in this example is as follows.

[0052] <Film adhesion method> (1) Treat (paint) the antiviral interior material (specimen) with a phage liquid containing the 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 the specified time has elapsed, the test specimen is washed with a washing solution and the virus-containing solution is recovered. (4) The virus-containing solution is infected into the host bacteria to evaluate the virus infectivity, and the number of viruses contained in the virus-containing solution is also measured.

[0053] 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 on the surface of the substrate with a thickness of 20 μm to obtain 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.

[0054] Example 2 In Example 1, the amount of the antiviral agent in the antiviral treatment layer of the antiviral interior material was changed to 2.0 parts by weight, and the other components were the same as in Example 1. An antiviral interior material of Example 2 was obtained by the same procedure as in Example 1.

[0055] 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, but the rest of the composition was the same as in Example 1, and an antiviral interior material of Example 3 was obtained by the same procedure as in Example 1.

[0056] 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, and the other components were the same as in Example 3. An antiviral interior material of Example 4 was obtained by the same procedure as in Example 3.

[0057] 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 rest of the composition was the same as in Example 1, and the antiviral interior material of Example 5 was obtained by the same procedure as in Example 1.

[0058] Example 6 In Example 1, 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) as the antiviral agent. The other components were the same as in Example 1, and the antiviral interior material of Example 6 was obtained by the same procedure as in Example 1.

[0059] 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-curable 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.

[0060] <Evaluation of antiviral activity based on virus reduction rate> In evaluating the 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 by 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 immediately (0 hours) (n0) and after 24 hours (n 24 ) was measured, and the virus reduction rate was calculated according to the following formula (I). Viral reduction rate (%) = (1 - n 24 / n0) × 100 (I) If the virus reduction rate is 95% or more, it is recognized as having an antiviral effect. The evaluation of antiviral properties (virus reduction rate) is shown in Table 1 below.

[0061] [Table 1]

[0062] Regarding the antiviral effect against feline calicivirus, the antiviral interior material of Example 6, which was treated for water resistance, showed a virus reduction rate of 99% or more, demonstrating a very excellent antiviral effect. A certain level of antiviral effect was also observed for the antiviral interior material of Example 2. Among the antiviral interior materials treated for light resistance, all of the antiviral interior materials of Examples 1 to 6 showed a virus reduction rate of 99% or more, demonstrating a very excellent antiviral effect.

[0063] 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, and an extremely excellent antiviral effect was observed. A high virus reduction rate was also achieved for Comparative Example 1 (control) which did not contain an antiviral agent, but when 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 materials. From this, it is considered that a certain degree of virus proliferation suppression effect can be expected against influenza A virus under appropriate environment (conditions).

[0064] When the above antiviral effects against feline calicivirus or influenza A virus are examined, the titanium oxide-containing copper titanium complex compound blended in the antiviral interior material of Example 6 has an extremely excellent antiviral effect overall, and it can be said that it is highly practical as an antiviral agent applied to interior materials. In addition, with respect to 3-iodo-2-propynyl butylcarbamate blended in the antiviral interior materials of Examples 1 and 2, Example 2, in which the blending amount of the antiviral agent is optimized, has an overall excellent antiviral effect that is comparable to that of Example 6, and it can also be said that it is highly practical. In addition, the N,N'-hexamethylene bis(4-carbamoyl-1-decylpyridinium bromide) blended in the antiviral interior materials of Examples 3 and 4 and the titanium oxide-containing zinc titanium complex compound blended in the antiviral interior material of Example 5 also have a comprehensive antiviral effect superior to that of Comparative Example 1, and are sufficiently practical. [Industrial Applicability]

[0065] The antiviral interior material of the present invention can be used as a resin floor material (sheet-like floor material, tile-like floor material), a waist wall sheet, a wall sheet, a ceiling sheet, etc. Furthermore, the antiviral interior material of the present invention can be used in various situations such as for general housing, schools, offices, commercial facilities, public facilities, and businesses. [Explanation of symbols]

[0066] 1. Antiviral interior materials (antiviral flooring materials) 10 Base material (resin molded sheet) 20 Antiviral Treatment Layer

Claims

1. 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 / m 2 ; 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.

2. The antiviral interior material according to claim 1 , wherein the antiviral treatment layer further contains hard fine particles.

3. The antiviral interior material according to claim 1 or 2, wherein the base material comprises a resin molded body containing a polyvinyl chloride resin.

Images