Antiviral decorative sheet, antiviral adhesion processing sheet using the same, and antiviral decorative panel

Abstract

To provide an antiviral decorative sheet that exhibits excellent antiviral effects while maintaining surface performance of a surface protective layer.SOLUTION: A decorative sheet with a crosslinking and curing resin layer 7 on its top surface layer is characterized in: (1) the crosslinking and curing resin layer contains a cured product of a crosslinking and curing resin and an antiviral agent 9; (2) an average particle diameter of the antiviral agent is 1 μm and more and 5 μm or less, and the average particle diameter is 1 / 2 or less of a thickness of the crosslinking and curing resin layer; (3) the crosslinking and curing resin layer has an area occupied by the antiviral agent of 1% or more and 10% or less of 100% of the area of a cross section observed in the cross section in a thickness direction; and (4) when the thickness of the crosslinking and curing resin layer is divided into three equal parts and classified into a lower layer, a middle layer and an upper layer, the center point of the antiviral agent of 60% or more of the total antiviral agent, is located in the upper layer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an antiviral decorative sheet, and an antiviral adhesive-processed sheet and an antiviral decorative board using the same. [Background technology]

[0002] Conventionally, various decorative sheets have been used for the surface decoration of fittings, floors, walls, etc. used as interior materials for buildings. For example, decorative sheets composed of a laminate having, in order in the thickness direction, a base sheet, a transparent resin layer, and a surface protective layer are widely used, and it is known that, if necessary, a decorative layer is provided on the base sheet, a primer layer is provided between the transparent resin layer and the surface protective layer to improve adhesion, and an ionizing radiation curable resin is contained in the resin component of the surface protective layer to improve the scratch resistance of the surface protective layer.

[0003] As an example of imparting functionality to a decorative sheet, a decorative sheet having antiviral properties is known. For example, Patent Document 1 discloses a specific example, "a decorative sheet having a surface protective layer formed of a single layer or multiple layers on a base sheet, and an antiviral agent added to the outermost layer located on the outermost surface of the surface protective layer."

[0004] Patent Document 1 describes that the antiviral agent contains at least one of a carboxylic acid material, a sulfonic acid material, and a quaternary ammonium salt as an organic material, thereby exerting an antiviral effect against both enveloped and non-enveloped viruses (claim 7 and paragraphs

[0044] to

[0047] ). Furthermore, paragraphs

[0048] to

[0049] of Patent Document 1 describe the relationship between the average particle size of the antiviral agent and the thickness of the surface protection layer to which the antiviral agent is added, the amount of the antiviral agent to be added, etc.

[0005] However, in the antiviral decorative sheets of the prior art including Patent Document 1, it is not easy to achieve both the surface performance that the surface protective layer should have and the excellent antiviral effect by adding an antiviral agent, and there is room for improvement. Specifically, by adding an antiviral agent with a large particle size relative to the thickness of the surface protective layer, a protuberance due to the antiviral agent is formed on the outermost surface, making it easier to obtain the antiviral effect, but when the resin composition for forming the surface protective layer is applied by gravure printing with good production efficiency, there are problems such as streaky defects caused by the antiviral agent with a large particle size, reduced scratch resistance, and the antiviral agent falling off over time. On the other hand, by adding an antiviral agent with a small particle size relative to the thickness of the surface protective layer, a surface protective layer with good surface performance can be formed by gravure printing, but there is a problem that the antiviral agent is buried inside the surface protective layer and the distance from the outermost surface is large, making it difficult to obtain the antiviral effect.

[0006] Therefore, there is a demand for the development of an antiviral decorative sheet that exhibits excellent antiviral effects while maintaining the surface performance of the surface protective layer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2022-41101 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to provide an antiviral decorative sheet that exhibits excellent antiviral effect while maintaining the surface performance of a surface protective layer. It also aims to provide an antiviral adhesive-processed sheet and an antiviral decorative board using the decorative sheet. [Means for solving the problem]

[0009] As a result of intensive research, the present inventors have found that the above object can be achieved by incorporating an antiviral agent in a specific form in a surface protective layer, and have thus completed the present invention.

[0010] That is, the present invention relates to the following antiviral decorative sheet, and an antiviral adhesive-processed sheet and an antiviral decorative board using the same. 1. A decorative sheet having a cross-linked curable resin layer on the outermost layer, (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an antiviral agent, (2) the average particle size of the antiviral agent is 1 μm or more and 5 μm or less, and the average particle size is ½ or less of the thickness of the cross-linked cured resin layer; (3) When a cross-section of the cross-linked cured resin layer is observed in the thickness direction, the area occupied by the antiviral agent in a 100% area of ​​the cross-section is 1% or more and 10% or less, (4) When the thickness of the cross-linked cured resin layer is divided into three equal parts, a lower layer, a middle layer, and an upper layer, the center points of 60% or more of the antiviral agent are present in the upper layer. An antiviral decorative sheet characterized by: 2. The anti-viral decorative sheet according to item 1, wherein the cross-linked cured resin layer has a two-layer structure consisting of a first cross-linked cured resin layer and a second cross-linked cured resin layer in that order from the front surface to the back surface, and the first cross-linked cured resin layer contains the anti-viral agent. 3. The anti-viral decorative sheet according to item 1 or 2, wherein the cross-linking curable resin contains an ionizing radiation curable resin. 4. The anti-viral decorative sheet according to any one of items 1 to 3, wherein the cross-linked curable resin layer has a thickness of 5 μm or more and 35 μm or less. 5. The anti-viral decorative sheet according to any one of items 1 to 4, wherein the specific gravity of the anti-viral agent is smaller than the specific gravity of the curable resin. 6. The anti-viral decorative sheet according to any one of items 1 to 4, wherein the specific gravity of the anti-viral agent is greater than the specific gravity of the curable resin. 7. The antiviral decorative sheet according to any one of items 1 to 6, wherein the antiviral agent is at least one selected from the group consisting of benzimidazole antiviral agents, anionic antiviral agents, and ether antiviral agents. 8. The antiviral decorative sheet according to any one of items 1 to 7, wherein the antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative. 9. An antiviral decorative sheet according to item 8, wherein the antiviral agent contains all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the styrene polymer derivative. 10. The anti-viral decorative sheet according to any one of items 1 to 9, which is composed of a laminate having at least a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and the cross-linked cured resin layer in that order in the thickness direction. 11. An anti-viral adhesive processed sheet composed of a laminate having at least, in order in the thickness direction, an adhesive sheet and the anti-viral decorative sheet according to any one of items 1 to 9. 12. An anti-viral decorative board composed of a laminate having at least, in order in the thickness direction, a decorative board substrate and the anti-viral decorative sheet according to any one of items 1 to 9 above. 13. An anti-viral decorative board composed of a laminate having at least, in order in the thickness direction, a decorative board base material and the anti-viral adhesive sheet described in item 11 above. Effect of the Invention

[0011] The antiviral decorative sheet of the present invention contains an antiviral agent in a specific form in the crosslinked cured resin layer (surface protective layer) which is the outermost layer, and can exhibit excellent antiviral effects while maintaining the surface performance of the surface protective layer (any surface performance that a surface protective layer should originally have, such as scratch resistance, impact resistance, chemical resistance, etc.) In addition, the decorative sheet can be combined with an adhesive sheet to form an antiviral adhesive sheet, and the decorative sheet and the adhesive sheet can each be combined with a decorative board substrate to form an antiviral decorative board. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one example of the antiviral decorative sheet of the present invention (composed of a single cross-linked cured resin layer). [Diagram 2] FIG. 1 is a schematic cross-sectional view showing an example of the antiviral adhesive processed sheet of the present invention. [Diagram 3] FIG. 1 is a cross-sectional view showing a schematic diagram of an example of a constituent member of the antiviral decorative board of the present invention. [Figure 4] FIG. 1 is a schematic cross-sectional view showing one example of the antiviral decorative sheet of the present invention (having a two-layer structure of cross-linked curable resin layers). [Diagram 5] FIG. 1 is a schematic cross-sectional view illustrating the relationship between the thickness A of the cross-linked cured resin layer of the antiviral decorative sheet of the present invention and the position of the center point of the antiviral agent when the layer is divided into a lower layer c, a middle layer b, and an upper layer a. [Figure 6] FIG. 1 is a schematic cross-sectional view showing an example of a conventional antiviral decorative sheet (comparative example) (in which an antiviral agent with small particle diameters is embedded deep inside the surface protective layer). [Figure 7] FIG. 1 is a schematic cross-sectional view showing an example of a conventional antiviral decorative sheet (comparative example) (in which large particle size antiviral agents form excessive protuberances above the surface protective layer). [Figure 8] FIG. 1 is an example of a cross-sectional observation image in the thickness direction of a cross-linked curable resin layer, showing the presence of primary particles and amorphous or tuft-like aggregated particles of antiviral particles. [Figure 9]FIG. 1 is a schematic cross-sectional view showing an example of the antiviral pressure-sensitive adhesive sheet and antiviral decorative board of the present invention obtained using a transfer method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 1. Antiviral cosmetic sheet The antiviral decorative sheet of the present invention (hereinafter also referred to as "the decorative sheet of the present invention") is a decorative sheet having a cross-linked cured resin layer as the outermost layer, (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an antiviral agent, (2) the average particle size of the antiviral agent is 1 μm or more and 5 μm or less, and the average particle size is ½ or less of the thickness of the cross-linked cured resin layer; (3) When a cross-section of the cross-linked cured resin layer is observed in the thickness direction, the area occupied by the antiviral agent in a 100% area of ​​the cross-section is 1% or more and 10% or less, (4) When the thickness of the cross-linked cured resin layer is divided into three equal parts, a lower layer, a middle layer, and an upper layer, the center points of 60% or more of the antiviral agent are present in the upper layer. It is characterized by:

[0014] The decorative sheet of the present invention contains an antiviral agent in a specific form in the crosslinked cured resin layer (surface protective layer) which is the outermost layer, and can exhibit excellent antiviral effects while maintaining the surface performance of the surface protective layer (any surface performance that a surface protective layer should originally have, such as scratch resistance, impact resistance, chemical resistance, etc.) In addition, the decorative sheet can be combined with a pressure-sensitive adhesive sheet to form an antiviral adhesive sheet, and the decorative sheet and the pressure-sensitive adhesive sheet can each be combined with a decorative board substrate to form an antiviral decorative board.

[0015] The decorative sheet of the present invention has a cross-linked curable resin layer as the outermost layer, and as long as the cross-linked curable resin layer and the antiviral agent contained therein satisfy the predetermined requirements shown in (1) to (4) above, there are no limitations on its specific configuration (layer configuration).

[0016] In a specific embodiment, the decorative sheet of the present invention may be composed of a laminate having, in order in the thickness direction, at least, for example, a base sheet, a transparent thermoplastic resin layer, and a cross-linked cured resin layer. The decorative sheet of the present invention may also be composed of a laminate having, in order in the thickness direction, at least, for example, a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and a cross-linked cured resin layer. In the decorative sheet of the present invention, the outermost cross-linked cured resin layer plays the role of a so-called surface protective layer.

[0017] FIG. 1 is a schematic cross-sectional view showing an example of the decorative sheet of the present invention. In FIG. 1, a picture pattern layer 3, a transparent adhesive layer 4, a transparent thermoplastic resin layer 5, a primer layer 6, and a cross-linked cured resin layer 7 are laminated in this order on a base sheet 2, and a back primer layer 8 is further provided on the back surface of the base sheet 2. Furthermore, the cross-linked cured resin layer 7 is shown in a schematic manner in which an antiviral agent 9 is present, and the cross-linked cured resin layer and the antiviral agent of the decorative sheet of the present invention satisfy the predetermined requirements shown in (1) to (4) above. The antiviral agent 9 is not limited to primary particles, and may be aggregated particles (see FIG. 8, details will be described later) formed by aggregation of primary particles. Furthermore, as shown in FIG. 1 (II), the decorative sheet of the present invention may have an embossed uneven pattern.

[0018] The thickness of the cross-linked cured resin layer 7 is the thickness indicated by A in the figure, but the presence of the antiviral agent 9 on the front surface side of the cross-linked cured resin layer 7 may form a protuberance (convex portion) exceeding the thickness A within a range that does not impair the surface performance. Even when the outermost surface has a protuberance due to the antiviral agent 9, the thickness of the cross-linked cured resin layer 7 means the thickness A of the smooth portion excluding the protuberance on the outermost surface (this is the same in an embodiment having an embossed uneven pattern as in FIG. 1(II)). Here, FIG. 1 illustrates a slight protuberance due to the antiviral agent 9, but the antiviral agent 9 itself is not exposed, and is a protuberance as the cross-linked cured resin layer.

[0019] 1 shows an example of a single-layer crosslinked cured resin layer 7, but as shown in FIG. 4, the crosslinked cured resin layer 7 may have a two-layer structure of a first crosslinked cured resin layer 7-1 and a second crosslinked cured resin layer 7-2, and the first crosslinked cured resin layer 7-1 may contain an antiviral agent 9. Even when the crosslinked cured resin layer 7 has a two-layer structure, the thickness of the crosslinked cured resin layer 7 means the thickness A (the sum of the thicknesses of 7-1 and 7-2) shown in FIG. 4 (this also applies to an embodiment having an embossed uneven pattern on the outermost surface, although not shown).

[0020] Furthermore, the present invention also includes an invention (for example, an embodiment shown in Fig. 2) of an antiviral adhesive sheet (hereinafter also referred to as "adhesive sheet of the present invention") composed of a laminate having at least an adhesive sheet and a decorative sheet of the present invention in that order in the thickness direction. Note that Fig. 2 illustrates the configuration of an adhesive sheet 11 having an adhesive sheet 10 on the back surface of the decorative sheet 1 shown in Fig. 1, but the configuration of the decorative sheet 1 is not limited thereto.

[0021] Furthermore, the present invention also includes an invention (for example, an embodiment shown in FIG. 3) of an antiviral decorative board (hereinafter also referred to as "the decorative board of the present invention") composed of a laminate having at least the decorative board substrate and the decorative sheet of the present invention or the adhesive sheet of the present invention in order in the thickness direction. Note that FIG. 3 illustrates the configuration of a decorative board 13 having a decorative board substrate 12 on the back side of the decorative sheet 1 shown in FIG. 1. Also, the decorative board 13 may be configured to have a decorative board substrate 12 on the back side of the adhesive sheet 11 shown in FIG. 2.

[0022] Also, Fig. 9 is a cross-sectional schematic diagram showing an example of an antiviral adhesive sheet and an antiviral decorative board of the present invention obtained by using a transfer method. In Fig. 9 (I), a cross-linked curable resin layer 7 and an adhesive sheet 10 are formed in order on a release film 14. At this time, by using an antiviral agent 9 having a larger specific gravity than the cross-linked curable resin, the antiviral agent 9 is precipitated in the cross-linked curable resin layer 7 and easily unevenly distributed in the vicinity of the release film 14. Next, in Fig. 9 (II), the release film 14 is peeled off to obtain an antiviral adhesive sheet 11 of the present invention, which is laminated on a decorative board substrate 12 such as a building material, to produce an antiviral decorative board 13.

[0023] 6 and 7 are schematic cross-sectional views showing an example of a conventional decorative sheet (comparative example). The decorative sheet in Fig. 6 does not provide sufficient antiviral effect because the small particle antiviral agent 9 is embedded deep inside the cross-linked cured resin layer 7. The decorative sheet in Fig. 7 provides an antiviral effect easily because the large particle antiviral agent 9 excessively protrudes from the cross-linked cured resin layer 7, but the surface characteristics are impaired.

[0024] In this specification, the surface visible after application of the decorative sheet of the present invention, i.e., the direction in which the cross-linked cured resin layer (surface protective layer) is laminated as viewed from the base sheet, is referred to as the "upper" or "front surface", and the direction in which the back primer layer is laminated as viewed from the base sheet is referred to as the "lower" or "back surface". This relationship is the same in the case of the pressure-sensitive adhesive sheet of the present invention and the decorative board of the present invention. In addition, when referring to the "side of the cross-linked cured resin layer (surface protective layer)" in the laminate, it is also abbreviated to "the side of the cross-linked cured resin layer (surface protective layer)".

[0025] Hereinafter, each layer of the decorative sheet of the present invention will be described with reference to Fig. 1 and Fig. 4. However, the layer structure of the decorative sheet of the present invention is not limited to the embodiment of Fig. 1 and Fig. 4, and various layer structures can be adopted as a laminate as described above. In the following description, the lower and upper limits of numerical ranges expressed by "to" mean "not less than or equal to" (for example, if α~β, it is not less than α and not more than β).

[0026] Base Sheet The substrate sheet has a surface (front surface) on which a pattern layer and the like are laminated in order, and the outermost layer is a cross-linked cured resin layer (surface protection layer).

[0027] Examples of the base sheet include various resin films, paper, resin-impregnated paper, etc., and among resin films, those containing a thermoplastic resin as a resin component are preferred.Specific examples include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc.In the present invention, at least one of polyvinyl chloride and polyolefin (polyethylene, polypropylene, etc.) can be preferably used.

[0028] The substrate sheet may be colored. For example, a colorant (pigment or dye) can be added to the thermoplastic resin to color it. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black, iron oxide, etc., organic pigments such as phthalocyanine blue, etc., as well as various dyes can be used. One or more of these can be selected. The amount of the colorant added can be appropriately determined depending on the desired color tone, etc.

[0029] The base sheet may contain various additives, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbing agents, and light stabilizers, as necessary.

[0030] The thickness of the substrate sheet can be appropriately set depending on the application and method of use of the final product, but is generally preferably 50 to 250 μm.

[0031] If necessary, the surface (front surface) of the base sheet may be subjected to a corona discharge treatment in order to improve the adhesion of the ink forming the picture pattern layer. The method and conditions for the corona discharge treatment may be performed according to a known method. If necessary, the back surface of the base sheet may be subjected to a corona discharge treatment, a picture pattern layer (so-called back print) may be formed, or a back primer layer (described later), a backing layer (described later), etc. may be formed.

[0032] Pattern layer The picture pattern layer is an optional layer that imparts a desired pattern (design) to the decorative sheet of the present invention, and the type of pattern is not limited. Examples include wood grain patterns, leather patterns, stone patterns, sand patterns, tile patterns, brickwork patterns, fabric patterns, geometric figures, letters, symbols, abstract patterns, floral patterns, landscapes, characters, and the like.

[0033] The method for forming the picture pattern layer is not particularly limited, and for example, the picture pattern layer may be formed on the surface of the base sheet by a known printing method using an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) together with a binder resin in a solvent (or dispersion medium). From the viewpoint of reducing the VOC of the decorative sheet, an aqueous composition may also be used as the ink.

[0034] Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc oxide, red iron oxide, Prussian blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; and luminous pigments. These colorants can be used alone or in combination of two or more. These colorants can be used together with fillers such as silica, extender pigments such as organic beads, neutralizers, surfactants, and the like.

[0035] As the binder resin, in addition to the polyester-based urethane resin that has been hydrophilically treated, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative, alcohol adduct of styrene-maleic anhydride copolymer, cellulose-based resin, etc. can be used in combination. More specifically, for example, polyacrylamide-based resin, poly(meth)acrylic acid-based resin, polyethylene oxide-based resin, poly N-vinylpyrrolidone-based resin, water-soluble polyester-based resin, water-soluble polyamide-based resin, water-soluble amino-based resin, water-soluble phenol-based resin, other water-soluble synthetic resin, water-soluble natural polymer such as polynucleotide, polypeptide, polysaccharide, etc. can also be used. In addition, for example, natural rubber, synthetic rubber, polyvinyl acetate-based resin, (meth)acrylic resin, polyvinyl chloride-based resin, polyurethane-polyacrylic resin, etc., or modified products thereof, other resins can also be used. The above-mentioned binder resins can be used alone or in combination of two or more.

[0036] Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion mediums) can be used alone or in combination of two or more.

[0037] Examples of printing methods used to form the picture pattern layer include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. When forming a picture pattern layer that is solid over the entire surface, examples of coating methods include roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating. In addition, hand-drawing, ink-flowing, photography, transfer printing, laser beam drawing, electron beam drawing, partial deposition of metals, etching, and the like may be used, or may be used in combination with other forming methods.

[0038] The thickness of the picture pattern layer is not particularly limited and can be appropriately set depending on the product characteristics, but the layer thickness is about 0.1 to 15 μm.

[0039] transparent resin layer The transparent resin layer is a layer that can be provided arbitrarily, and is not particularly limited as long as it is transparent, and may be any of colorless transparent, colored transparent, translucent, etc. The material of the transparent resin layer is not limited, but it is preferably formed from a thermoplastic resin. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc. can be mentioned. In the present invention, at least one of polyvinyl chloride and polyolefin (polyethylene, polypropylene, etc.) can be preferably used. In this specification, when the transparent resin layer contains a thermoplastic resin, the transparent resin layer is particularly referred to as a "transparent thermoplastic resin layer".

[0040] The transparent resin layer may be colored as long as it has transparency.

[0041] In addition, the transparent resin layer may contain various additives such as a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer, as necessary, so long as it has transparency.

[0042] The thickness of the transparent resin layer is not limited, but is preferably 40 μm to 300 μm, more preferably 60 μm to 200 μm, and most preferably 60 μm to 100 μm. By setting the thickness of the transparent resin layer within the above range, a deep embossing can be formed, and the effect of suppressing the occurrence of scratches and scraping (removal of the pattern) due to wear of the pattern layer can be easily obtained.

[0043] transparent adhesive layer A transparent adhesive layer may be formed to enhance adhesion between the picture pattern layer and the transparent resin layer or the cross-linked cured resin layer (surface protective layer) described later. The transparent adhesive layer is not particularly limited as long as it is transparent, and may be colorless transparent, colored transparent, translucent, etc.

[0044] The adhesive is not particularly limited, and adhesives known in the field of decorative sheets can be used. Examples of adhesives known in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins, and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives can be used alone or in combination of two or more. Two-component curing polyurethane resins or polyester resins using isocyanate as a curing agent can also be used.

[0045] The thickness of the transparent adhesive layer is not particularly limited, but is about 0.1 to 30 μm, and preferably about 1 to 20 μm.

[0046] Primer layer A primer layer for the crosslinked cured resin layer (surface protective layer) may be provided on the transparent resin layer. This primer layer not only acts to increase the adhesion between the transparent resin layer and the crosslinked cured resin layer described below, but also increases the folding processability and scratch resistance of the decorative sheet when combined with the crosslinked cured resin layer. The primer layer is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, translucent, etc.

[0047] The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. Examples of the primer agent include urethane resin-based primer agents consisting of acrylic modified urethane resin (acrylic urethane copolymer resin), polycarbonate-based acrylic urethane copolymer resin, etc., urethane-cellulose resin-based primer agents (for example, resins obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrocellulose), and resin-based primer agents consisting of acrylic and urethane block copolymers. Among these, urethane resin-based primer agents containing polycarbonate-based acrylic urethane copolymer resins are preferably used from the viewpoint of scratch resistance and weather resistance.

[0048] The primer agent may contain additives as necessary. Examples of additives include weathering agents such as ultraviolet absorbers and light stabilizers; fillers such as silica, calcium carbonate, and clay; flame retardants such as magnesium hydroxide; antioxidants; lubricants; and foaming agents. The amount of additives to be added can be appropriately determined depending on the product characteristics.

[0049] Among the above additives, examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Examples of the light stabilizer include hindered amine-based light stabilizers (HALS). The content of these weathering agents is not limited, but it is sufficient to set the content of each of the ultraviolet absorber and light stabilizer to about 1000 to 100,000 mass ppm. In particular, in the present invention, it is preferable to use a triazine-based ultraviolet absorber and / or a hindered amine-based light stabilizer.

[0050] The thickness of the primer layer is not limited, but is preferably 0.5 μm to 12 μm, more preferably 1 μm to 8 μm. By setting the thickness within this range, the combination with the crosslinked cured resin layer makes it easier to improve the folding processability and scratch resistance of the decorative sheet. In addition, it becomes easier to include additives such as weathering agents, making it easier to impart weather resistance to the decorative sheet.

[0051] Cross-linked curing resin layer (surface protection layer) The decorative sheet of the present invention has a cross-linked curable resin layer (surface protective layer) as the outermost layer, and the cross-linked curable resin layer and the antiviral agent contained therein satisfy the specific requirements shown in (1) to (4) below, thereby enabling the sheet to exhibit excellent antiviral effects while maintaining the surface performance of the surface protective layer. (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an antiviral agent, (2) the average particle size of the antiviral agent is 1 μm or more and 5 μm or less, and the average particle size is ½ or less of the thickness of the cross-linked cured resin layer; (3) When a cross-section of the cross-linked cured resin layer is observed in the thickness direction, the area occupied by the antiviral agent in a 100% area of ​​the cross-section is 1% or more and 10% or less, (4) When the thickness of the cross-linked cured resin layer is divided into three equal parts, a lower layer, a middle layer, and an upper layer, the center points of 60% or more of the antiviral agent are present in the upper layer.

[0052] The cross-linking curable resin is not particularly limited as long as it is transparent, and may be colorless transparent, colored transparent, translucent, or the like.

[0053] The resin component of the crosslinking curable resin is not limited, but preferably contains an ionizing radiation curable resin or a two-component curable urethane resin. In practice, it is preferable that the resin is formed from these resins. When the outermost layer is formed from an ionizing radiation curable resin or a two-component curable urethane resin, it is easy to improve the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet. Among these, an ionizing radiation curable resin is preferable.

[0054] The ionizing radiation curable resin is not particularly limited, and a transparent resin mainly composed of a prepolymer (including oligomer) and / or a monomer containing a radical polymerizable double bond in the molecule that can undergo a polymerization / crosslinking reaction when irradiated with ionizing radiation such as ultraviolet light or an electron beam can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a crosslinking curing reaction.

[0055] Specifically, the prepolymer or monomer may be a compound having a radical polymerizable unsaturated group such as a (meth)acryloyl group or a (meth)acryloyloxy group, or a cationic polymerizable functional group such as an epoxy group in the molecule. In addition, a polyene / thiol-based prepolymer obtained by combining a polyene with a polythiol is also preferred. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0056] Examples of prepolymers having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, silicone (meth)acrylate, etc. The weight average molecular weight of these is usually preferably about 250 to 100,000. Here, the weight average molecular weight in this specification is the average molecular weight measured by GPC analysis (gel permeation chromatography) and converted into standard polystyrene.

[0057] Examples of the monomer having a radically polymerizable unsaturated group include monofunctional monomers such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and phenoxyethyl(meth)acrylate. Examples of the polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0058] Examples of prepolymers having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of polyenes include those obtained by adding allyl alcohol to both ends of polyurethanes made of diols and diisocyanates.

[0059] In the present invention, a mixed resin containing a urethane (meth)acrylate oligomer (A) having two radically polymerizable unsaturated groups in one molecule and a weight average molecular weight of 1000 to 3000 and an aliphatic urethane (meth)acrylate oligomer (B) having 3 to 15 radically polymerizable unsaturated groups in one molecule can be used as the ionizing radiation curable resin. When such a mixed resin is used, the crosslinking density is high, so that effects such as scratch resistance and stain resistance can be easily obtained, and by appropriately adjusting the weight average molecular weight and / or the blending amount, the crosslinking curable resin layer can be made to have excellent impact resistance or excellent processability such as V-cutting, and the surface performance can be easily adjusted according to the application.

[0060] The content ratio of the oligomer (A) and the oligomer (B) in the ionizing radiation curable resin is not limited, but it is preferable that the oligomer (A) is in the range of 50 to 90 mass% and the oligomer (B) is in the range of 10 to 50 mass%, assuming that the total amount of the oligomer (A) and the oligomer (B) is 100 mass%.

[0061] In the present invention, as the ionizing radiation curable resin, a mixed resin containing two types of aliphatic urethane (meth)acrylate, Resin A and Resin B shown below, can also be used. Here, (meth)acrylate means acrylate or methacrylate.

[0062] Resin A is an aliphatic urethane (meth)acrylate having an isocyanurate skeleton, and is not limited as long as it satisfies this requirement. For example, an aliphatic urethane (meth)acrylate having an isocyanurate skeleton formed by a trimer of a diisocyanate is preferred. Specific examples include a trimer of hexamethylene diisocyanate (particularly 1,6-hexamethylene diisocyanate), a trimer of tolylene diisocyanate, and a trimer of metaxylene diisocyanate. Note that tolylene diisocyanate and metaxylene diisocyanate may have poorer weather resistance than hexamethylene diisocyanate because they have a benzene ring, so these diisocyanates are preferably hydrogenated. These resins A have the effect of improving the contamination resistance, alkali resistance, etc. of the crosslinked cured resin layer.

[0063] Resin B is an aliphatic urethane (meth)acrylate having no isocyanurate skeleton and an alicyclic skeleton, and is not limited as long as it satisfies this requirement, but for example, it is preferable that the alicyclic skeleton has at least one of isophorone and cyclohexane.Specific examples include a urethane oligomer, which is a polymer made of isophorone diisocyanate and butanediol as monomers, to which an acrylate is added at the end, and a PG-modified diacrylate of hydrogenated dicyclohexylmethane diisocyanate (hydrogenated MDI).These resins B have the effect of imparting flexibility to the crosslinked cured resin layer, and in combination with resin A, they provide the crosslinked cured resin layer with excellent contamination resistance, alkali resistance, etc. over a long period of time, as well as the effect of suppressing the occurrence of cracks or breakage when subjected to impact or during processing.

[0064] The ionizing radiation curable resin is a transparent resin mainly composed of a prepolymer (including oligomer) and / or a monomer containing a radical polymerizable double bond in the molecule capable of undergoing a polymerization and crosslinking reaction by irradiation with ionizing radiation such as ultraviolet rays and electron beams, and the curing reaction is usually a crosslinking curing reaction. As the ionizing radiation used to cure the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of the molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion beams, etc. may also be used. Among the ionizing radiation curable resins in the present invention, it is preferable to use an electron beam curable resin because it does not contain a photopolymerization initiator, so that the properties of the raw material resin can be directly reflected in the properties of the resin component of the crosslinking curable resin layer, and because it provides a wider range of options when a weathering agent is used in combination.

[0065] The two-component curing urethane-based resin is not particularly limited, but among them, those containing a polyol component having an OH group (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) as a main component and an isocyanate component (tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, etc.) as a curing agent component can be used.

[0066] The above-exemplified crosslinking curable resins can be used alone or in combination of two or more.

[0067] The crosslinking curing resin layer contains an antiviral agent in addition to the cured product of the crosslinking curing resin. Generally, viruses are roughly classified into enveloped viruses (having an envelope) and non-enveloped viruses (not having an envelope) depending on whether they have an envelope (lipid membrane). Enveloped viruses include, for example, influenza viruses, herpes viruses, AIDS viruses, hepatitis B viruses, etc. In addition, non-enveloped viruses include, for example, noroviruses, feline caliciviruses, rhinoviruses, adenoviruses, etc.

[0068] The antiviral agent used in the present invention (hereinafter also referred to as "the antiviral agent of the present invention") includes inorganic antiviral agents and / or organic antiviral agents. In general, inorganic antiviral agents are advantageous in terms of stability, which allows the antiviral effect to last for a long period of time, while organic antiviral agents are advantageous in terms of immediate effect, which allows the antiviral effect to be exerted in a short period of time, and therefore they can be used in accordance with the expected effects of each agent. Among these antiviral agents, it is preferable to use an organic antiviral agent in the present invention in terms of immediate effect of the antiviral effect.

[0069] Examples of organic antiviral agents include quaternary ammonium salts, quaternary phosphonium salts, pyridines, pyrithiones, benzimidazoles, organic iodines, isothiazolinones, anions, and ethers.

[0070] Among the above organic antiviral agents, at least one selected from the group consisting of benzimidazole antiviral agents, anionic antiviral agents, and ether antiviral agents, which are antiviral agents that maintain a particulate shape, is preferably used. The antiviral agent maintaining a particulate shape means that the antiviral agent (particles) is not dissolved in the resin composition that forms the surface protective layer and exists in the cured resin layer while maintaining a particulate shape.

[0071] The benzimidazole antiviral agent is not particularly limited, and examples thereof include methyl benzimidazol-2-ylcarbamate (also known as carbendazim) and polymerized imidazole compounds.

[0072] As the ether-based antiviral agent, for example, a phenyl ether derivative compound is preferable. As the phenyl ether derivative compound, polyoxyethylene alkyl phenyl ether can be mentioned. In addition, as the ether-based antiviral agent, when biodegradability and cost are considered, polyoxyethylene alkyl ether can be mentioned, and it is known that these can exhibit antiviral performance as ether-type nonionic surfactants.

[0073] The anionic antiviral agent may be, for example, an antiviral agent that is considered to have an antiviral effect against non-enveloped viruses, and contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative (hereinafter, also referred to as "antiviral agent A"). It is preferable that the antiviral agent A further contains triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the styrene polymer derivative. These are positioned as compounds that are detected as components when the carboxylic acid derivative and the styrene polymer derivative are subjected to organic structure analysis, respectively.

[0074] The carboxylic acid derivative is not limited as long as the above-mentioned specified constituent components are detected by organic structure analysis. As an example of a preparation method, for example, a carboxylic acid derivative can be prepared by mixing and reacting raw materials including cyclohexanecarboxylic acid (manufactured by New Japan Chemical Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N,N-dimethylallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.), and N,N,2,2-tetramethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0075] In addition, the styrene polymer derivative is preferably one in which the above-mentioned specified constituent components are detected upon organic structure analysis. As an example of a preparation method, for example, a styrene polymer derivative can be prepared by mixing and reacting raw materials including sodium p-styrenesulfonate (manufactured by Tosoh Corporation; product name "Spinomer NaSS"), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.) and denatured ethanol (manufactured by Wako Pure Chemical Industries, Ltd.; product name "86% Ethanol-ME").

[0076] The antiviral agent A can be prepared by mixing (kneading) the carboxylic acid derivative and the styrene polymer derivative at a desired mixing ratio, and pulverizing the mixture to a desired size by a known pulverizing means such as a jet mill. The content ratio of the carboxylic acid derivative and the styrene polymer derivative is not limited, but is preferably 1:1 to 10:1 by mass, and more preferably 2:1 to 5:1 by mass. By setting the content ratio (mixing ratio) at such a ratio, it becomes easier to obtain an antiviral effect against non-enveloped viruses.

[0077] The reason why antiviral agent A has an antiviral effect against viruses (particularly non-enveloped viruses) is speculated as follows, but is not limited to the mechanism speculated as follows. Various viruses invade host cells by binding to a sugar chain receptor (the sugar chain end is neuraminic acid) on the surface of the host cell. Since the antiviral agent of the present invention has an ionic group similar to neuraminic acid, it is considered that it binds to the virus instead of the host cell and captures the virus, thereby preventing the virus from binding to the host cell receptor and exerting an antiviral effect. Specifically, the above-mentioned multiple types of amino groups, which are components of the carboxylic acid derivative, bind (capture) to the spike protein of the enveloped virus and the capsid (protein shell) of the non-enveloped virus. Simultaneously or secondary to this, the sulfonic acid group of the styrene polymer derivative destroys the envelope, thereby inactivating the enveloped virus, and the carboxy group of the carboxylic acid derivative compound oxidizes the capsid, thereby inactivating the non-enveloped virus. In addition, as mentioned above, the sulfonic acid group is considered to mainly contribute to the destruction of the envelope, but since it has oxidizing power, it is also involved in the oxidation of the capsid of non-enveloped viruses, like the carboxyl group. Therefore, in order to efficiently inactivate non-enveloped viruses while also inactivating enveloped viruses, it is effective to use a carboxylic acid derivative and a styrene polymer derivative at the same time. Antiviral agent A is superior to conventional products in that it can inactivate non-enveloped viruses at a content that does not inhibit the surface performance of the cross-linked cured resin layer, but the estimated mechanism for inactivating enveloped viruses is also as described above, and antiviral agent A has an antiviral effect not only against non-enveloped viruses but also against enveloped viruses.

[0078] When the antiviral agent A is used, a phenyl ether derivative compound exemplified as the ether-based antiviral agent can be used in combination to complement the antiviral performance. Examples of the phenyl ether derivative compound include polyoxyethylene alkyl ether.

[0079] The shape of the antiviral agent (primary particles) of the present invention is not limited, and examples thereof include a sphere, an ellipsoid, a polyhedron, and a scale shape. The average particle diameter of the antiviral agent of the present invention is a small particle diameter of 1 μm or more and 5 μm or less, and the average particle diameter is 1 / 2 or less of the thickness of the crosslinked cured resin layer. Within the above range, the average particle diameter of the antiviral agent of the present invention is preferably 1 μm or more and 3 μm or less. Note that the average particle diameter of the primary particles in this specification (the average particle diameter of the primary particles of the antiviral agent before being mixed with the crosslinked cured resin) is a value specified as the mass average particle diameter D50 in particle size distribution measurement by a laser light diffraction method.

[0080] In the crosslinked cured resin layer, the antiviral particles are not limited to primary particles, and may be aggregated particles formed by aggregation of primary particles. FIG. 8 illustrates an embodiment in which the antiviral agent exists not only as primary particles, but also as amorphous or bunch-shaped (grape bunch-shaped) aggregated particles. The particle size of the aggregated particles is determined by drawing a circle of the smallest diameter so that the aggregated particles are completely contained therein, as exemplified in the center of FIG. 8, and the diameter of the circle is the particle size. Therefore, the average particle size of the antiviral agent in the present invention is the average particle size including the particle size of the aggregated particles when aggregated particles are present, and is a value calculated by observing a cross section in the thickness direction of the crosslinked cured resin layer (width 200 μm; "width" is the direction perpendicular to the thickness direction).

[0081] The thickness of the crosslinked cured resin layer is preferably 5 μm or more and 35 μm or less when the crosslinked cured resin layer does not have convex portions due to the antiviral agent of the present invention, and when the crosslinked cured resin layer has convex portions due to the antiviral agent of the present invention, the thickness of the smooth portion excluding the convex portions is preferably 5 μm or more and 35 μm or less, and in either case, in relation to the average particle size of the antiviral agent, the average particle size may be 1 / 2 or less of the thickness of the crosslinked cured resin layer. Within the range satisfying this condition, the thickness of the crosslinked cured resin layer may be 10 μm or more and 30 μm or less.

[0082] The thickness of the cross-linked cured resin layer is the average value (average thickness) measured at a flat portion (thickness A in the drawing) where there is no embossed uneven pattern or convex portions (protrusions of the cross-linked cured resin layer) due to the antiviral agent of the present invention, and in this specification means the average thickness value of any 10 points within a width of 1 cm in an observed cross-sectional image of the cross-linked cured resin layer. The "width" is the direction perpendicular to the thickness direction.

[0083] The crosslinked cured resin layer may have a two-layer structure of a first crosslinked cured resin layer 7-1 and a second crosslinked cured resin layer 7-2, as exemplified in Fig. 4, in which the crosslinked cured resin layer 7 contains an antiviral agent 9. Even when the crosslinked cured resin layer 7 has a two-layer structure, the thickness of the crosslinked cured resin layer 7 means the thickness A (the sum of the thicknesses of 7-1 and 7-2) shown in Fig. 4. The two-layer structure makes it possible to easily distribute the antiviral agent unevenly near the outermost surface of the crosslinked cured resin layer while ensuring a thickness of the crosslinked cured resin layer that is advantageous for scratch resistance and the like.

[0084] In the present invention, when the cross-linked curable resin layer contains antiviral particles, in observation of a cross section in the thickness direction of the cross-linked curable resin layer, the area occupied by the antiviral particles in 100% of the cross-sectional area is 1% or more and 10% or less, preferably 1.5% or more and 6% or less.

[0085] Here, the method for calculating the area occupied by the antiviral particles in observing a cross section in the thickness direction of the cross-linked cured resin layer is as follows: The instrument used in this specification is a digital microscope (model number: VHX-7000, magnification 200x, manufactured by Keyence Corporation). 1) In order to observe the cross section of the decorative sheet in the thickness direction, an arbitrarily selected area is cut in the thickness direction of the decorative sheet with a sharp blade such as a single-edged trimming razor or a microtome; 2) A cross section (width 200 μm; "width" is the direction perpendicular to the thickness direction) of the cut decorative sheet is observed with a digital microscope to obtain a cross-sectional photograph. 3) Using the "area measurement" function of the digital microscope's "measurement and scale" function, a) Area of ​​antiviral particles (primary particles), b) The area of ​​antiviral particles (aggregated particles), and c) Calculate the area of ​​the cross-linked curable resin layer (width 200 μm); 4) From each calculated area, the ratio (occupancy rate) of the area occupied by the antiviral particles to 100% of the cross-sectional area of ​​the cross-linked cured resin layer is calculated. Occupancy rate (%)=[(a+b) / c]×100 5) The above procedure is repeated 10 times and the average value is defined as the occupancy rate (%) of antiviral particles.

[0086] In the present invention, when the thickness of the smooth part of the cross-linked cured resin layer is divided into thirds and divided into a lower layer, a middle layer, and an upper layer, the center points of 60% or more of the antiviral agents of the present invention (total in terms of numbers) are present in the upper layer. Fig. 5 exemplarily shows the relationship between the thickness A of the cross-linked cured resin layer and the position of the center point of the antiviral agent. Here, antiviral agent 9-1 is an example in which the position of the center point of the antiviral agent is present in the upper layer (the upper layer includes the boundary between the middle layer and the upper layer) of the third equal division of the thickness of the cross-linked cured resin layer, and antiviral agent 9-2 is an example in which the position of the center point of the antiviral agent is present in the lower layer or middle layer (the middle layer includes the boundary between the lower layer and the middle layer).

[0087] The center point of the antiviral agent is determined by drawing a circle of the smallest diameter so that the antiviral agent of the present invention, which may have various shapes (not necessarily circular), can be completely accommodated in the cross-sectional observation image of the cross-linked cured resin layer, and the center of the circle is defined as the center point. The ratio of the center point of the antiviral agent of the present invention existing in the upper layer is preferably 65% ​​or more, more preferably 90% or more. By keeping it within this range, the antiviral effect of the antiviral agent of the present invention can be easily obtained. The cross-section observation is performed by cutting the cross-linked cured resin layer in the thickness direction with a sharp blade such as a single-edged trimming razor or a microtome, and then observing the cut surface (200 μm wide) with a digital microscope (manufactured by Keyence Corporation, model number: VHX-7000, magnification: 200 times).

[0088] The crosslinking curable resin layer can be formed, for example, by applying a crosslinking curable resin layer forming composition containing a crosslinking curable resin and the antiviral agent of the present invention on a primer layer by a known coating method such as gravure coating or roll coating, and then curing the resin. Specifically, after applying the crosslinking curable resin layer forming composition, the antiviral agent of the present invention is lifted up in the coating film before it is completely cured, forming a convex portion due to the antiviral agent on the outermost surface of the crosslinking curable resin layer, or the antiviral agent is partially aggregated in the coating film, and the particle size of the antiviral agent appears to be large, but there is no problem in the expression of antiviral performance. In this way, in order to lift up the antiviral agent, an antiviral agent having a smaller specific gravity than the crosslinking curable resin can be used. Note that even when an antiviral agent having a larger specific gravity than the crosslinking curable resin is used, the proportion of the antiviral agent present in the upper layer of the crosslinking curable resin layer can be increased by dispersing it at a relatively high density on the surface of the uncured crosslinking curable resin layer.

[0089] On the other hand, the crosslinking curing resin layer may be formed by a transfer method. Figure 9 is a schematic cross-sectional view showing an example of the antiviral adhesive sheet and antiviral decorative board of the present invention obtained by using the transfer method. In (I) of Figure 9, the crosslinking curing resin layer 7 and the adhesive sheet 10 are formed in order on the release film 14. At this time, by using an antiviral agent 9 having a larger specific gravity than the crosslinking curing resin, the antiviral agent 9 is precipitated in the crosslinking curing resin layer 7 and easily unevenly distributed in the vicinity of the release film 14. Next, in (II) of Figure 9, the release film 14 is peeled off to obtain the antiviral adhesive sheet 11 of the present invention, which is laminated on a decorative board substrate 12 such as a building material, to form an antiviral decorative board 13.

[0090] In addition, various additives such as colorants such as dyes and pigments, fillers such as inorganic fillers, weather resistance agents, antifoaming agents, leveling agents, thixotropic agents, flame retardants, antibacterial agents different from the antiviral agents, and antiallergen agents different from the antiviral agents may be added to the crosslinking curing resin layer within a range that does not affect the surface performance and predetermined antiviral properties of the surface protective layer. For example, in the present invention, in addition to the antiviral agent, an embodiment containing at least one selected from the group consisting of antibacterial agents and antiallergen agents can be adopted. In addition, inorganic fillers are often mainly used as matting agents, but by including an inorganic filler in the crosslinking curing resin layer, it is also expected that the curing shrinkage of the surface protective layer can be suppressed.

[0091] The antibacterial agent includes inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are desirable because they are generally safer than organic antibacterial agents and have excellent durability and heat resistance. In this specification, inorganic antibacterial agents are those in which antibacterial metals such as silver, copper, and zinc are supported on various inorganic carriers. Among these, silver-containing inorganic antibacterial agents (silver-containing inorganic particles) are preferred, and specifically, silver-supported zeolite particles and the like are preferred.

[0092] The antiallergen agent contains either an inorganic compound or an organic compound, and may be used alone or in combination of two or more different compounds. The inorganic compound is preferably a material carrying a metal.

[0093] As the anti-allergen agent, an agent similar to or identical to the antibacterial agent may be effective. In such a case, the contents of the antibacterial agent and the anti-allergen agent may be optimized so as to obtain the desired antibacterial and anti-allergenic properties.

[0094] As the inorganic material of the inorganic compound, for example, at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate, and magnesium phosphate is preferable, and among these, titanium oxide, zirconium phosphate, etc. are preferable.

[0095] The metal supported on the inorganic material is preferably at least one selected from the group consisting of silver, gold, platinum, zinc, and copper, and among these, zinc is preferred. For example, a commercially available product such as "Atomy Ball TZ-R: Zinc-supported titanium oxide" manufactured by JGC Catalysts can be suitably used, and these anti-allergen agents are effective against various allergens such as mites and pollen.

[0096] The organic compound is preferably a water-insoluble polymer containing a phenolic hydroxyl group, a polyphenol compound supported on an inorganic solid acid, or a polymer containing at least one monomer component selected from the group consisting of styrenesulfonic acid and its salts.

[0097] As the water-insoluble polymer containing a phenolic hydroxyl group, for example, commercially available products such as "Allerbuster (trade name)" manufactured by Sekisui Chemical Co., Ltd. and "Marukalinker M (trade name)" manufactured by Maruzen Oil Co., Ltd. can be used. In addition, as a combination of a polyphenol compound and a zirconium compound, "Allerremove (trade name)" manufactured by Toa Gosei Co., Ltd. can be mentioned. These anti-allergen agents are effective against various allergens such as mites and pollen.

[0098] As the at least one monomer component selected from the group consisting of styrenesulfonic acid and its salts, materials such as those disclosed in Japanese Patent No. 6136433 can be used.

[0099] In addition, when an organic compound and an inorganic compound are mixed, for example, an anionic phenolic compound and a zinc-based material having anti-allergenic properties can be used.

[0100] The anionic phenolic material may be appropriately selected from tannin, tannic acid-tartar emetic, phenolsulfonic acid formaldehyde resin, sulfone compounds of novolac type resins, methanesulfonic acid of novolac type resins, methanesulfonic acid of resol type resins, benzylated phenolsulfonic acid, thiophenol compounds, dihydroxydiphenylsulfone compounds, ligand compounds, and metal chelate compounds thereof.

[0101] The zinc-based material is appropriately selected from a water-soluble zinc compound or a water-insoluble zinc compound, a zinc / metal oxide composite material, etc., and it is preferable that the water-insoluble zinc compound and / or water-insoluble zinc / metal oxide composite particles are dispersed in water, the particle size is 50 μm or less, and the metal oxide contains at least one of titania, silica, and alumina.

[0102] Embossing The embossing is carried out to impart a desired texture such as a wood grain pattern to the decorative sheet, and the embossing may be carried out on the transparent resin layer and / or on the cross-linked cured resin layer. For example, the cross-linked cured resin layer is heated and softened, then pressed and shaped with an embossing plate having a desired uneven pattern, and cooled and fixed to impart texture. The embossing can be carried out with a known sheet-fed or rotary embossing machine.

[0103] Examples of the uneven patterns of embossing include wood grain vessel grooves, raised patterns (raised patterns of raised annual rings), hairlines, sand grain, and matte finish.

[0104] When embossing is performed, ink may be filled into the embossed recesses by wiping, if necessary. For example, ink is filled into the embossed recesses while scratching the surface with a doctor blade. The ink to be filled (wiping ink) is usually an ink with a two-component curing urethane resin as a binder. In particular, wiping the unevenness of the wood grain vessel grooves can increase the product value by expressing a design closer to the actual wood grain.

[0105] Back primer layer A back primer layer may be provided on the back surface of the base sheet as required. For example, this is effective when a decorative board is produced by bonding the base sheet to a decorative board substrate.

[0106] The back primer layer can be formed by applying a known primer agent to the substrate sheet. Examples of the primer agent include urethane resin-based primer agents made of acrylic modified urethane resin (acrylic urethane copolymer resin), polycarbonate-based acrylic urethane copolymer resin, etc., urethane-cellulose resin-based primer agents (for example, resins obtained by adding hexamethylene diisocyanate to a mixture of urethane and soluble cellulose), and resin-based primer agents made of acrylic and urethane block copolymers.

[0107] The primer agent may contain additives as necessary. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The amount of additives to be added can be appropriately determined depending on the product characteristics.

[0108] The thickness of the back surface primer layer is not particularly limited, but is usually about 0.01 to 10 μm, and preferably about 0.1 to 1 μm.

[0109] Synthetic resin backing layer A synthetic resin backing layer may be provided on the back surface of the base sheet as necessary. By providing a synthetic resin backing layer, the impact resistance of the decorative sheet is further improved. When the above-mentioned back primer layer is also provided, the synthetic resin backing layer and the back primer layer are provided on the back surface of the base sheet in this order from the base sheet side.

[0110] Examples of resins constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, highly heat-resistant polyalkylene terephthalate (for example, polyethylene terephthalate in which part of ethylene glycol is replaced with 1,4-cyclohexanedimethanol or diethylene glycol, so-called product name PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, diene rubber such as styrene butadiene rubber, isoprene rubber, chloroprene rubber, non-diene rubber such as butyl rubber, ethylene propylene rubber, natural rubber, thermoplastic elastomer, etc. These resins can be used alone or in combination of two or more kinds.

[0111] The thickness of the synthetic resin backing layer is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.45 mm, and even more preferably 0.20 to 0.40 mm. By setting the lower limit of the thickness of the synthetic resin backing layer within the above range, the impact resistance of the decorative sheet is further improved. Also, by setting the upper limit of the thickness of the synthetic resin backing layer within the above range, the warping of the decorative sheet is further suppressed.

[0112] Vesicling of various additives contained in each layer of decorative sheets The various additives added to the above-mentioned layers of the decorative sheet of the present invention (such as inorganic fillers added to the primer layer and cross-linked cured resin layer) are preferably in the form of vesicles. The method for vesiculating the various additives is not particularly limited, and they can be vesiculated by known methods, among which supercritical reverse phase evaporation is preferred.

[0113] In addition to the supercritical reverse phase evaporation method, other vesicle-forming methods include the Bangham method, the extrusion method, the hydration method, the reverse phase evaporation method, and the freeze-thaw method. Briefly, the Bangham method involves putting chloroform or a chloroform / methanol mixed solvent into a container such as a flask, and then adding and dissolving phospholipids. The solvent is then removed using an evaporator to form a thin film of lipids, and a dispersion of additives is added, followed by hydration and dispersion in a vortex mixer to obtain vesicles. The extrusion method involves preparing a thin film of phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain vesicles. The hydration method is a preparation method that is almost the same as the Bangham method, but it is a method in which vesicles are obtained by gently stirring and dispersing the solution without using a mixer. The reverse phase evaporation method is a method in which phospholipids are dissolved in diethyl ether or chloroform, a solution containing an additive is added to make a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and water is added to obtain vesicles. The freeze-thaw method is a method in which cooling and heating are used as external perturbations, and vesicles are obtained by repeating this cooling and heating.

[0114] The supercritical reverse phase evaporation method will be described in detail below. The supercritical reverse phase evaporation method is a method in which a mixture in which a substance forming the outer membrane of a vesicle is uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure condition above the supercritical point is added with an aqueous phase containing various additives as water-soluble or hydrophilic encapsulation substances to form a capsule-like vesicle containing various additives as encapsulation substances in a single layer of membrane. Note that carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773±0.0030MPa) or higher, and carbon dioxide under a temperature or pressure condition above the critical point means carbon dioxide under a condition in which only the critical temperature or only the critical pressure exceeds the critical condition. This method can obtain unilamellar vesicles with a diameter of 50 to 800 nm. In general, a vesicle is a general term for a vesicle having a membrane structure closed in a spherical shell shape and containing a liquid phase inside, and in particular, a vesicle whose outer membrane is composed of biological lipids such as phospholipids is called a liposome.

[0115] Examples of the above-mentioned phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin; and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0116] As the substance constituting the outer membrane, a dispersant such as a nonionic surfactant or a mixture of this with cholesterol or triacylglycerol can also be used.

[0117] As the nonionic surfactant, one or more of polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. can be used.

[0118] As the cholesterols, one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadiene-3β-ol), sodium cholate, cholecalciferol, and the like can be used.

[0119] The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet of the present invention, by using a liposome having an outer membrane formed from a phospholipid, it is possible to improve the compatibility between the resin composition, which is the main component of each layer, and various additives.

[0120] 2. Antiviral adhesive sheet The antiviral adhesive sheet of the present invention (adhesive sheet of the present invention) is composed of a laminate including at least an adhesive sheet and the decorative sheet of the present invention in this order in the thickness direction. The adhesive sheet is not particularly limited, and adhesive sheets used in the field of decorative sheets and other functional sheets can be used as appropriate. The adhesive sheet of the present invention has an adhesive sheet on the back side, so that it can be attached to the surface of various items and adherends for flooring, and can be given antiviral properties as desired.

[0121] FIG. 2 shows an example of an antiviral adhesive processed sheet 11 in which a decorative sheet 1 of the present invention (the adhesive sheet 10 is attached to the side opposite the cross-linked curable resin layer) is laminated in this order on an adhesive sheet 10.

[0122] 3. Antiviral decorative panels The antiviral decorative board of the present invention (the decorative board of the present invention) is composed of a laminate having at least, in order in the thickness direction, a decorative board substrate and the decorative sheet of the present invention or the adhesive sheet of the present invention.

[0123] FIG. 3 shows an example of an antiviral decorative board 13 in which the decorative sheet 1 of the present invention (the side opposite the cross-linked curable resin layer side and the decorative board substrate 12 are laminated in this order) is a decorative board substrate 12.

[0124] The decorative board substrate is not limited, but may be at least one of medium density wood fiberboard, high density wood fiberboard, particle board, softwood plywood, hardwood plywood, fast-growing plywood, cork sheet, cork-containing composite substrate, thermoplastic resin board (resin board mainly composed of polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc., or foamed resin thereof), etc. These decorative board substrates may be used alone or in combination of two or more types, which may be laminated.

[0125] Here, examples of coniferous trees include linden pine, larch, Hokkaido pine, cedar, cypress, pine, sequoia, spruce, etc. Examples of broad-leaved trees include lauan, china, birch, ash, beech, oak, meranti, etc. Examples of fast-growing trees include poplar, falcata, acacia, camellia, eucalyptus, terminalia, etc.

[0126] When using wood plywood such as softwood plywood, hardwood plywood, and fast-growing plywood, the number of layers (number of plies) of the wood veneer is not limited, but is usually preferably 3 to 7, more preferably 5 to 7. The adhesive used in producing the wood plywood is also not limited, and known woodworking adhesives can be widely used. Examples of adhesives include adhesives containing polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc. as active ingredients. Examples of thermosetting adhesives include melamine-based, phenol-based, and urea-based (vinyl acetate-urea, etc.) adhesives.

[0127] The cork sheet can be made of so-called natural cork, which is a highly elastic material made by peeling and processing the cork tissue from the bark of the cork oak tree, or so-called synthetic cork, which is made to resemble cork. The cork sheet can be a single layer or a laminate of multiple cork sheets with different elastic moduli and densities.

[0128] The cork-containing composite substrate may be a composite material obtained by laminating and bonding a cork sheet with another material (for example, a medium-density wood fiberboard or a high-density wood fiberboard).

[0129] The thickness of the decorative board substrate is not limited, but is preferably about 2 to 15 mm, and more preferably about 2 to 12 mm.

[0130] The lamination method for laminating the decorative sheet or adhesive sheet and the decorative board substrate is not limited, and for example, a method of attaching each of them with an adhesive can be adopted. In addition, if the adhesive sheet has sufficient adhesion to the decorative board substrate, a method of attaching the adhesive sheet and the decorative board substrate without further adhesive can be adopted. The adhesive may be appropriately selected from known adhesives depending on the type of adherend, etc. For example, urethane, acrylic, urethane-acrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc. can be mentioned. These adhesives are used alone or in combination of two or more. EXAMPLES

[0131] The present invention will be specifically described below with reference to examples, comparative examples, and test examples, although the present invention is not limited to the contents shown in the examples.

[0132] Example 1 (crosslinked cured resin layer is a single layer structure) A 60 μm thick colored polypropylene film was prepared as a base sheet.

[0133] A back primer layer (thickness: 2 μm) was formed on the back surface of the substrate sheet.

[0134] A primer agent containing a two-component curing urethane resin was applied to the front surface of the base sheet to a thickness of 2 μm to form a primer layer.

[0135] The following composition for forming a crosslinking curable resin layer was applied to the front surface of the primer layer by gravure coating in a coating amount of 5 μm, and then the electron beam curable resin was cured by irradiating it with an electron beam under conditions of an acceleration voltage of 165 KeV and 5 Mrad using an electron beam irradiation device in an environment with an oxygen concentration of 200 ppm or less to form a crosslinking curable resin layer, thereby producing a decorative sheet. In addition, in cross-sectional observation of the crosslinking curable resin layer in the thickness direction, the area occupied by the antiviral agent in 100% of the cross-sectional area was 5%. In addition, when the thickness of the crosslinking curable resin layer was divided into three equal parts into a lower layer, a middle layer, and an upper layer, the proportion of the center point of the antiviral agent present in the upper layer among the entire antiviral agent was 65%.

[0136] (Crosslinked curable resin layer forming composition) A cross-linking curable resin, a total of 100 parts by mass of a urethane acrylate resin consisting of 30 parts by mass of a multifunctional urethane oligomer and 70 parts by mass of a bifunctional oligomer Antiviral agent (the amount of antiviral agent added to the cross-linked curable resin was set in each Example and Comparative Example so that, when a cross-section of the cross-linked curable resin layer was observed in the thickness direction, the area occupied by the antiviral agent in 100% of the cross-section was a predetermined value.).

[0137] The carboxylic acid derivative was prepared by mixing and reacting raw materials including cyclohexanecarboxylic acid (manufactured by New Japan Chemical Industry Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N,N-dimethylallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.), and N,N,2,2-tetramethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0138] In addition, the styrene polymer derivative was prepared by mixing and reacting raw materials including sodium p-styrenesulfonate (manufactured by Tosoh Corporation; product name "Spinomer NaSS"), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.), and denatured ethanol (manufactured by Wako Pure Chemical Industries, Ltd.; product name "86% Ethanol-ME").

[0139] The antiviral agent was prepared by mixing the carboxylic acid derivative and the styrene polymer derivative in a mass ratio of 3:1, followed by pulverization with a jet mill (Nisshin Engineering, product name "SJ-100"). The antiviral agent had an average particle size of 2 μm when measured using a laser diffraction particle size distribution analyzer (HORIBA) in accordance with JIS Z8825-1.

[0140] Example 2 (crosslinked cured resin layer has two layers) A 60 μm thick colored polypropylene film was prepared as a base sheet.

[0141] A back primer layer (thickness: 2 μm) was formed on the back surface of the substrate sheet.

[0142] A primer agent containing a two-component curing urethane resin was applied to the front surface of the base sheet to a thickness of 2 μm to form a primer layer.

[0143] The crosslinked curable resin (not including the antiviral agent) was applied to the front surface of the primer layer in a coating amount of 25 μm by gravure coating to form a second crosslinked curable resin layer, and then the crosslinked curable resin layer forming composition (the average particle size of the antiviral agent was changed to 4 μm by changing the pulverization conditions) was applied to the front surface of the primer layer in a coating amount of 10 μm by gravure coating to form a first crosslinked curable resin layer. Next, in an environment with an oxygen concentration of 200 ppm or less, an electron beam was irradiated using an electron beam irradiation device under conditions of an acceleration voltage of 165 KeV and 5 Mrad to cure the electron beam curable resin, thereby forming a crosslinked curable resin layer (the second crosslinked curable resin layer and the first crosslinked curable resin layer), and a decorative sheet was produced. In addition, in cross-sectional observation in the thickness direction of the crosslinked curable resin layer, the area occupied by the antiviral agent in the 100% cross-sectional area was 1.5%. Furthermore, when the thickness of the cross-linked cured resin layer was divided into thirds into a lower layer, a middle layer, and an upper layer, the proportion of the antiviral agent whose center point was present in the upper layer among the entire antiviral agent was 100%.

[0144] Example 3 (Cross-linked curable resin layer produced by transfer method) A release-treated PET film was prepared as the release film.

[0145] The composition for forming a crosslinking curable resin layer was applied to the front surface of a release film by gravure coating in a coating amount of 20 μm, and the antiviral agent was sufficiently precipitated in the coating film. Next, an adhesive sheet (heat seal layer) was laminated on the front surface of the coating film. Next, in an environment with an oxygen concentration of 200 ppm or less, an electron beam was irradiated using an electron beam irradiation device under conditions of an acceleration voltage of 165 KeV and 5 Mrad to cure the electron beam curable resin, thereby forming a crosslinking curable resin layer, and producing an adhesive processed sheet.

[0146] Next, the release film was peeled off from the adhesive sheet, and the adhesive sheet side was pressed against a decorative board substrate (a 5 mm thick aluminum panel) to produce a decorative board. In cross-sectional observation of the cross-linked cured resin layer in the thickness direction of the decorative board, the area occupied by the antiviral agent in 100% of the cross-sectional area was 3%. In addition, when the thickness of the cross-linked cured resin layer was divided into three equal parts, the lower layer, the middle layer, and the upper layer, the proportion of the center point of the antiviral agent present in the upper layer among the entire antiviral agent was 95%.

[0147] Comparative Example 1 A decorative sheet was produced in the same manner as in Example 1, except that the content of the antiviral agent relative to the cross-linked curable resin was changed. In cross-sectional observation in the thickness direction of the cross-linked curable resin layer, the area occupied by the antiviral agent in 100% of the cross-sectional area was 0.5%. In addition, when the thickness of the cross-linked curable resin layer was divided into three equal parts, a lower layer, a middle layer, and an upper layer, the proportion of the center point of the antiviral agent present in the upper layer among the entire antiviral agent was 65%.

[0148] Comparative Example 2 A decorative sheet was produced in the same manner as in Example 1, except that the content of the antiviral agent relative to the cross-linked curable resin was changed and the thickness of the cross-linked curable resin layer was set to 15 μm. In cross-sectional observation of the cross-linked curable resin layer in the thickness direction, the area occupied by the antiviral agent in 100% of the cross-sectional area was 10%. In addition, when the thickness of the cross-linked curable resin layer was divided into three equal parts, a lower layer, a middle layer, and an upper layer, the proportion of the center point of the antiviral agent present in the upper layer among the entire antiviral agent was 40%.

[0149] Comparative Example 3 A decorative sheet was produced in the same manner as in Example 1, except that the content of the antiviral agent relative to the cross-linked curable resin was changed, the grinding conditions were changed to set the average particle size of the antiviral agent to 11 μm, and the thickness of the cross-linked curable resin layer to 15 μm. In addition, in cross-sectional observation of the cross-linked curable resin layer in the thickness direction, the area occupied by the antiviral agent in 100% of the cross-sectional area was 12%. In addition, when the thickness of the cross-linked curable resin layer was divided into three equal parts into a lower layer, a middle layer, and an upper layer, the proportion of the center point of the antiviral agent present in the upper layer among the entire antiviral agent was 90%.

[0150] Fabrication of decorative panels The decorative sheets produced in Examples 1 and 2 and Comparative Examples 1 to 3 were used to produce decorative boards. A water-based emulsion adhesive (BA-10L (base agent):BA-11B (hardener) = 100:2.5 (mass ratio) manufactured by Japan Coating Resin Co., Ltd.) was applied at 80 g / m on a 2.5 mm thick medium density wood fiberboard (MDF). 2 The mixture was then attached to the back primer layer side of a decorative sheet and allowed to cure at room temperature for 3 days to produce a decorative floor board.

[0151] Test Example 1 For the decorative boards produced in Example 3 and above, 1) the ratio of the area occupied by the antiviral agent to 100% of the cross-sectional area in the thickness direction of the cross-linked cured resin layer, 2) the ratio of the center point of the antiviral agent existing in the upper layer of the cross-linked cured resin layer, 3) antiviral performance, and 4) scratch resistance were evaluated. The calculation methods for 1) and 2) above were the same as those described in this specification. The evaluation methods for 3) and 4) were as follows.

[0152] <Anti-virus performance> The decorative panels produced in the Examples and Comparative Examples were subjected to an antiviral performance test in accordance with the antiviral test method (ISO21702), and the antiviral activity value against feline calicivirus was evaluated based on the following evaluation criteria. The evaluation criteria were as follows: Virus species: Feline calicivirus +: Antiviral activity value was 2.0 or higher after 6 hours -: Antiviral activity value was 2.0 or higher after 24 hours --: Antiviral activity value after 24 hours was less than 2.0. The results are shown in Table 1 below.

[0153] <Light load scratch resistance test (Hoffman scratch test)> The test was carried out using a Hoffman scratch tester manufactured by BYK-GADNER, USA. Specifically, a scratch blade (a cylindrical blade with a diameter of 7 mm) was set so that it contacted each decorative panel at an angle of 45°, and the tester was moved over the decorative material. The load (weight) was gradually increased, and the test was repeated until scratches, indentations, etc. appeared on the surface of the decorative panel. The evaluation criteria were as follows: +: No damage was observed under a load of 100g - : Scratches were observed at a load of 100g. The results are shown in Table 1 below. [Table 1]

[0154] As can be seen from the results in Table 1, the decorative sheets and decorative boards of Examples 1 to 3, which contain the antiviral agent of the present invention, exhibit excellent antiviral performance without impairing the surface performance of the surface protective layer. [Explanation of symbols]

[0155] 1. Antiviral cosmetic sheet 2. Base sheet 3.Pattern layer 4.Transparent adhesive layer 5.Transparent resin layer 6. Primer layer 7.Crosslinked curing resin layer (surface protection layer) 7-1. First cross-linked hardening resin layer 7-2.Second cross-linked curing resin layer 8. Back primer layer 9. Antiviral Agents 9-1.Antiviral agent with a central point in the upper layer a of the cross-linked cured resin layer 9-2.Antiviral agent with a central point in the middle layer b or the lower layer c of the cross-linked cured resin layer 10. Adhesive Sheet 11. Antiviral adhesive sheet 12. Decorative board base material 13. Antiviral decorative panels 14.Release film A. Thickness of cross-linked cured resin layer (surface protection layer) A. Upper layer b. Middle layer c. lower layer

Claims

1. A decorative sheet having a cross-linked curable resin layer on the outermost layer, (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an antiviral agent, (2) The average particle diameter of the antiviral agent is 1 μm or more and 5 μm or less, and the average particle diameter is ½ or less of the thickness of the cross-linked cured resin layer, (3) In the cross-linked cured resin layer, when a cross section is observed in the thickness direction, an area occupied by the antiviral agent in a 100% area of ​​the cross section is 1% or more and 10% or less, (4) When the thickness of the cross-linked cured resin layer is divided into three equal parts, a lower layer, a middle layer, and an upper layer, the center points of 60% or more of the antiviral agent are present in the upper layer. An antiviral decorative sheet characterized by:

2. 2. The anti-viral decorative sheet according to claim 1, wherein the cross-linked cured resin layer has a two-layer structure of a first cross-linked cured resin layer and a second cross-linked cured resin layer in that order from the front surface to the back surface, and the first cross-linked cured resin layer contains the anti-viral agent.

3. The anti-viral decorative sheet according to claim 1 , wherein the cross-linking curable resin contains an ionizing radiation curable resin.

4. 2. The anti-viral decorative sheet according to claim 1, wherein the thickness of the cross-linked curable resin layer is from 5 μm to 35 μm.

5. 2. The anti-viral decorative sheet according to claim 1, wherein the specific gravity of the anti-viral agent is smaller than the specific gravity of the curable resin.

6. 2. The anti-viral decorative sheet according to claim 1, wherein the specific gravity of the anti-viral agent is greater than the specific gravity of the curable resin.

7. 2. The anti-viral decorative sheet according to claim 1, wherein the anti-viral agent is at least one selected from the group consisting of benzimidazole anti-viral agents, anionic anti-viral agents, and ether anti-viral agents.

8. The antiviral decorative sheet according to claim 1, wherein the antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative.

9. The antiviral decorative sheet according to claim 8, wherein the antiviral agent contains all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the styrene polymer derivative.

10. 2. The anti-viral decorative sheet according to claim 1, which is composed of a laminate having at least a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and the cross-linked cured resin layer in that order in the thickness direction.

11. 13. An antiviral adhesive processed sheet comprising a laminate having at least an adhesive sheet and the antiviral decorative sheet according to claim 1 in that order in the thickness direction.

12. 13. An anti-viral decorative board comprising a laminate comprising at least a decorative board substrate and the anti-viral decorative sheet according to claim 1 in that order in the thickness direction.

13. An antiviral decorative board comprising a laminate having at least a decorative board substrate and the antiviral adhesive sheet according to claim 11 in that order in the thickness direction.

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