Antiviral decorative sheet, antiviral adhesive processed sheet using the same, and antiviral decorative panel

Abstract

The present invention provides an antiviral decorative sheet which maintains the surface properties of a surface protective layer and which is capable of exerting an antiviral effect even on nonenveloped viruses. Specifically, the antiviral decorative sheet of the present invention has a crosslinking and curing type resin layer in the outermost surface layer, and is characterized in that: (1) the crosslinking and curing type resin layer contains a cured product of a crosslinking and curing type resin and an antiviral agent; and (2) the antiviral agent has antiviral properties against nonenveloped viruses, and contains a carboxylic acid derivative and a styrene polymer derivative, and contains all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine as constituent components of the carboxylic acid derivative.

Description

Technical Field

[0001] This invention relates to antiviral decorative sheets, antiviral adhesive processing sheets using the decorative sheets, and antiviral decorative panels, and particularly to antiviral decorative sheets with antiviral properties against non-enveloped viruses, antiviral adhesive processing sheets using the decorative sheets, and antiviral decorative panels. Background Technology

[0002] Currently, various decorative sheets are used for surface decoration of doors, windows, partitions, floors, walls, and other interior decoration materials in buildings. For example, decorative sheets composed of a laminate consisting of a substrate sheet, a transparent resin layer, and a surface protective layer in the thickness direction are widely used. Depending on the needs, a decorative layer is set on the substrate sheet, a primer layer is set between the transparent resin layer and the surface protective layer to improve adhesion, or the resin component of the surface protective layer contains an ionizing radiation curing resin to improve the scratch resistance of the surface protective layer.

[0003] As an example of giving decorative sheets functionality, antiviral decorative sheets are known. For instance, Patent Document 1 discloses "a decorative sheet in which a surface protective layer formed in a single or multiple layers is provided on a substrate sheet, and an antiviral agent is added to the outermost layer located on the outermost surface of the aforementioned surface protective layer."

[0004] Patent Document 1 describes an antiviral agent containing at least one of a carboxylic acid-based material, a sulfonic acid-based material, or a quaternary ammonium salt as an organic material, which can exert antiviral effects against both enveloped and non-enveloped viruses (claims 7 and

[0044] to

[0047] ). However, while the embodiments in Patent Document 1 describe the confirmation of antiviral activity against enveloped viruses through antiviral performance tests, they do not specifically confirm the antiviral activity against non-enveloped viruses.

[0005] Generally, enveloped viruses are relatively easy to inactivate by disrupting their envelope (lipid layer), thus allowing for relatively easy achievement of antiviral effects using a wide variety of known antiviral agents. Even small amounts are readily effective, allowing the surface protective layer to maintain its original surface properties while imparting antiviral properties. In contrast, inactivation of non-enveloped viruses is more difficult, and achieving the same effect with the same antiviral agent and dosage is challenging. In the decorative sheet of Patent Document 1, increasing the dosage is necessary to achieve an effect against non-enveloped viruses using the same antiviral agent, which may interfere with the original surface properties of the surface protective layer.

[0006] Therefore, it is desirable to develop antiviral decorative sheets that can maintain the surface properties of the protective layer and, in particular, exert antiviral effects against non-enveloped viruses.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2022-41101 Summary of the Invention

[0010] The technical problem that the invention aims to solve

[0011] The object of this invention is to provide an antiviral decorative sheet that maintains the surface properties of the protective layer and, in particular, exhibits antiviral effects against non-enveloped viruses. A further object of this invention is to provide antiviral adhesive processing sheets and antiviral decorative panels using the aforementioned decorative sheet.

[0012] Technical solutions for solving technical problems

[0013] Through repeated and dedicated research, the inventors of this invention discovered that by containing specific antiviral agents in the surface protective layer, the above-mentioned objectives could be achieved, thus completing this invention.

[0014] That is, the present invention relates to the following antiviral decorative sheet, the antiviral adhesive processing sheet using the decorative sheet, and the antiviral decorative panel.

[0015] 1. An antiviral decorative sheet, wherein the outermost layer has a cross-linked curable resin layer, wherein,

[0016] (1) The above-mentioned cross-linked curing resin layer contains the cured product of the cross-linked curing resin and an antiviral agent.

[0017] (2) The above-mentioned antiviral agent is an antiviral agent that is effective against non-enveloped viruses. The antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative. At least as a component of the above-mentioned carboxylic acid derivative, it contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine.

[0018] 2. The antiviral decorative sheet as described in item 1 above, wherein the antiviral agent, as a component of the styrene polymer derivative, contains all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine.

[0019] 3. The antiviral decorative sheet as described in item 1 or 2 above, wherein the cross-linked cured resin layer has fine irregularities on its outermost surface with an arithmetic mean roughness Ra of 0.1 μm or more.

[0020] 4. The antiviral decorative sheet as described in item 3 above, wherein the arithmetic mean roughness Ra of the aforementioned micro-uneven surface is 40 μm or less.

[0021] 5. The antiviral decorative sheet as described in any one of items 1 to 4 above, wherein the cross-linked cured resin layer further contains an antibacterial agent composed of silver-containing inorganic particles.

[0022] 6. The antiviral decorative sheet as described in any one of items 1 to 5 above, wherein the cross-linked cured resin layer further contains a triazine-based ultraviolet absorber and / or a light stabilizer.

[0023] 7. The antiviral decorative sheet as described in any one of items 1 to 6 above, wherein the ratio of the carboxylic acid derivative and the styrene polymer derivative contained in the antiviral agent is 1:1 to 10:1 by mass.

[0024] 8. The antiviral decorative sheet as described in any one of items 1 to 7 above, wherein when the thickness of the smooth portion of the cross-linked cured resin layer is divided into a lower layer, a middle layer, and an upper layer in three equal parts, the center point of more than 50% of the total antiviral agent exists in the middle layer or the upper layer.

[0025] 9. The antiviral decorative sheet as described in any one of items 1 to 8 above, wherein, relative to 100 parts by weight of the cross-linked curing resin, it contains 1 to 10 parts by weight of the antiviral agent described above.

[0026] 10. The antiviral decorative sheet as described in any one of items 1 to 9 above, wherein the average thickness of the smooth portion of the cross-linked cured resin layer is 2 μm or more and 35 μm or less.

[0027] 11. The antiviral decorative sheet as described in any one of items 1 to 10 above, wherein the average particle size of the antiviral agent is 2 μm or more and 15 μm or less.

[0028] 12. The antiviral decorative sheet as described in any one of items 1 to 11 above, wherein the cross-linking curing resin contains an ionizing radiation curing resin.

[0029] 13. The antiviral decorative sheet as described in any one of items 1 to 12 above, wherein the Martens hardness of the cross-linked cured resin layer is 30 N / mm. 2 Above 180N / mm 2 the following.

[0030] 14. The antiviral decorative sheet as described in any one of items 1 to 13 above, comprising a laminate having at least, in the thickness direction, a substrate sheet, a patterned layer, a transparent thermoplastic resin layer and the aforementioned cross-linked curable resin layer in sequence.

[0031] 15. The antiviral decorative sheet as described in item 14 above, wherein the martensitic hardness of the substrate sheet and / or the transparent thermoplastic resin layer is 30 N / mm. 2 Above 80N / mm 2 the following.

[0032] 16. An antiviral adhesive processing sheet, comprising a laminate having at least an adhesive sheet and an antiviral decorative sheet as described in any one of items 1 to 15 in the thickness direction.

[0033] 17. An antiviral decorative panel, comprising a laminate having at least a decorative panel substrate and an antiviral decorative sheet as described in any one of items 1 to 15 in the thickness direction.

[0034] 18. An antiviral decorative panel comprising a laminate having at least a decorative panel substrate and the antiviral adhesive processing sheet described in item 16 above in a thickness direction in sequence.

[0035] Invention Effects

[0036] The antiviral decorative sheet of the present invention contains a specific antiviral agent in its outermost cross-linked cured resin layer (surface protective layer), which maintains the surface properties of the surface protective layer (any surface properties inherent in the surface protective layer, such as scratch resistance, impact resistance, and chemical resistance), and is particularly effective against non-enveloped viruses. Furthermore, by combining this decorative sheet with an adhesive sheet, an antiviral adhesive-processed sheet can be manufactured; and by combining both the decorative sheet and the adhesive-processed sheet with a decorative panel substrate, an antiviral decorative panel can be manufactured. Attached Figure Description

[0037] Figure 1 This is a cross-sectional schematic diagram illustrating an example of the antiviral decorative sheet of the present invention.

[0038] Figure 2 This is a cross-sectional schematic diagram illustrating an example of the antiviral adhesive processing sheet of the present invention.

[0039] Figure 3 This is a cross-sectional view schematically showing an example of the constituent components of the antiviral decorative panel of the present invention.

[0040] Figure 4 This is a cross-sectional schematic diagram illustrating the relationship between the thickness A of the smooth portion of the cross-linked cured resin layer (surface protective layer) of the antiviral decorative sheet of the present invention and the position of the center point of the antiviral agent.

[0041] Figure 5This is a diagram illustrating (a) the diamond indenter used in this specification for determining martensitic hardness, a schematic diagram (b) of the indentation operation, and an example (c) of the indentation load and displacement. Detailed Implementation

[0042] 1. Antiviral decorative film

[0043] The antiviral decorative sheet of the present invention (hereinafter also referred to as "the decorative sheet of the present invention") has a cross-linked curable resin layer on its outermost surface, and the decorative sheet is characterized in that:

[0044] (1) The above-mentioned cross-linked curing resin layer contains the cured product of the cross-linked curing resin and an antiviral agent.

[0045] (2) The above-mentioned antiviral agent is an antiviral agent that is effective against non-enveloped viruses. The antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative. At least as a component of the above-mentioned carboxylic acid derivative, it contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine.

[0046] The decorative sheet of the present invention contains a specific antiviral agent in its outermost cross-linked cured resin layer (surface protective layer), which maintains the surface properties of the surface protective layer (any surface properties inherent to the surface protective layer, such as scratch resistance, impact resistance, and chemical resistance), and is particularly effective against non-enveloped viruses. Furthermore, by combining this decorative sheet with an adhesive sheet, an antiviral adhesive-processed sheet can be produced; and by combining both the decorative sheet and the adhesive-processed sheet with a decorative panel substrate, an antiviral decorative panel can be produced.

[0047] The decorative sheet of the present invention only needs to have a cross-linked curable resin layer on its outermost surface, and the cross-linked curable resin layer and the antiviral agent contained therein need to meet the conditions specified in (1) and (2) above. Its specific composition (layer composition) is not limited.

[0048] In specific embodiments, the decorative sheet of the present invention can be composed of a laminate having, for example, a substrate sheet, a transparent thermoplastic resin layer, and a cross-linked curable resin layer sequentially in the thickness direction. Alternatively, the decorative sheet of the present invention can also be composed of a laminate having, for example, a substrate sheet, a pattern layer, a transparent thermoplastic resin layer, and a cross-linked curable resin layer sequentially in the thickness direction. Furthermore, in the decorative sheet of the present invention, the outermost cross-linked curable resin layer serves as a so-called surface protective layer.

[0049] Figure 1 This is a cross-sectional schematic diagram illustrating an example of the decorative piece of the present invention. Figure 1In this design, a patterned layer 3, a transparent adhesive layer 4, a transparent thermoplastic resin layer 5, a primer layer 6, and a cross-linking curable resin layer 7 are sequentially stacked on a substrate sheet 2. A back primer layer 8 is also present on the back side of the substrate sheet 2. An embossed pattern is also formed. The presence of the antiviral agent 9 in the cross-linking curable resin layer 7 is also schematically shown. The thickness of the cross-linking curable resin layer 7 (excluding the thickness of the smooth portion on the outermost surface) is the thickness shown as A in the figure, but a bulge (protrusion) greater than the thickness A of the smooth portion can also be formed due to the presence of the antiviral agent 9 on the front side of the cross-linking curable resin layer 7. Furthermore, in addition to the protrusions caused by the antiviral agent 9, fine irregularities can also be formed on the outermost surface of the cross-linking curable resin layer 7. Figure 1 The protrusion shown is a bulge caused by antiviral agent 9, not an exposure of antiviral agent 9 itself, but a bulge as a cross-linked cured resin layer.

[0050] Additionally, the present invention also includes inventions of antiviral adhesive-processed sheets (hereinafter also referred to as "adhesive-processed sheets of the present invention") composed of a laminate having at least an adhesive sheet and a decorative sheet of the present invention sequentially in the thickness direction (e.g., Figure 2 (as shown). Among them, in Figure 2 The example in Figure 1 The decorative piece 1 shown has an adhesive processing piece 11 on the back side of the adhesive piece 10, but the structure of the decorative piece 1 is not limited to this.

[0051] Additionally, the present invention also includes an antiviral decorative panel (hereinafter also referred to as "the decorative panel of the present invention") composed of a laminate having at least a decorative panel substrate and a decorative sheet or an adhesive processing sheet of the present invention sequentially in the thickness direction. Figure 3 (as shown). Among them, in Figure 3 The example in Figure 1 The decorative panel 1 shown has a decorative panel 13 on its back side, which is composed of a decorative panel substrate 12. Alternatively, it can also be formed on... Figure 2 The back of the adhesive processing sheet 11 shown has a decorative panel 13 consisting of a decorative panel substrate 12.

[0052] In this specification, the side of the decorative sheet of the present invention that is viewed after construction, i.e., the direction from which the laminated cross-linked curing resin layer (surface protective layer) is viewed from the substrate sheet, is referred to as "upper" or "front," and the direction from which the undercoat layer on the back of the laminate is viewed from the substrate sheet is referred to as "lower" or "back." This relationship is also the same in the case of the adhesive processing sheet and the decorative panel of the present invention. In addition, when described in the laminate as "one side of the cross-linked curing resin layer (surface protective layer)," it is also simply referred to as "the side of the cross-linked curing resin layer (surface protective layer)."

[0053] In the following, examples are used Figure 1 The layers of the decorative sheet of the present invention will be described. However, the layer composition of the decorative sheet of the present invention is not limited to... Figure 1 As described above, as a laminated body, it can be constructed using various layers. In the following description, the lower and upper limits of the numerical range indicated by "~" mean "above and below" (for example, if it is α to β, then it is α above and β below).

[0054] substrate sheet

[0055] The substrate sheet has layers of patterned textures stacked sequentially on its surface (front side). The outermost layer is a cross-linked cured resin layer (surface protective layer).

[0056] Examples of substrate materials include resin films, paper, and resin-impregnated paper. In resin films, thermoplastic resins are preferred as the resin component. Specific examples include polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PET), polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate (PEG), ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ionomers, acrylates, and methacrylates. In this invention, at least one of polyvinyl chloride and polyolefins (polyethylene, polypropylene, etc.) is preferred.

[0057] The substrate sheet can be colored. For example, colorants (pigments or dyes) can be added to thermoplastic resins for coloring. As colorants, in addition to inorganic pigments such as titanium dioxide, carbon black, and iron oxide, and organic pigments such as phthalocyanine blue, various dyes can also be used. One or more of these can be selected. Furthermore, the amount of colorant added can be appropriately set according to the desired hue, etc.

[0058] The substrate sheet may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers, as needed.

[0059] The thickness of the substrate sheet can be appropriately set according to the purpose and usage of the final product, and is usually preferably 50 to 250 μm.

[0060] Regarding the substrate sheet, corona discharge treatment can be applied to the surface (front side) as needed to improve the adhesion of the ink forming the patterned layer. The corona discharge treatment method and conditions can be implemented according to known methods. Alternatively, corona discharge treatment can be applied to the back side of the substrate sheet to form a patterned layer (so-called back printing), or to form a back undercoat layer or substrate layer as described later, as needed.

[0061] Pattern layer

[0062] The pattern layer is an optional layer that imbues the decorative sheet of the present invention with a desired pattern (design), and there are no limitations on the type of pattern. Examples include wood grain patterns, leather patterns, stone patterns, sand patterns, tile patterns, bricklaying patterns, fabric patterns, geometric shapes, text, symbols, abstract patterns, floral patterns, landscapes, letters, etc.

[0063] There are no particular limitations on the method for forming the patterned layer. For example, ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) together with a binder resin in a solvent (or dispersion medium) can be used to form the pattern on the surface of the substrate using a known printing method. From the viewpoint of reducing the VOCs of the decorative sheet, a water-based composition can also be used as the ink.

[0064] Examples of colorants include: inorganic pigments such as carbon black, titanium dioxide, zinc dioxide, iron oxide red, dark blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metallic pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium dioxide-coated mica and bismuth oxychloride; fluorescent pigments; and luminescent pigments. These colorants can be used alone or in combination of two or more. They can also be used with fillers such as silica, extender pigments such as organic beads, neutralizing agents, and surfactants.

[0065] In addition to hydrophilic treated polyester-based polyurethane resins, other adhesive resins can be used in combination with polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymers, rosin derivatives, alcohol adducts of styrene-maleic anhydride copolymers, and cellulose resins. More specifically, polyacrylamide resins, poly(meth)acrylic acid resins, polyethylene oxide resins, polyN-vinylpyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino resins, water-soluble phenolic resins, and other water-soluble synthetic resins can also be used; water-soluble natural polymers such as polynucleotides, polypeptides, and polysaccharides can also be used. Furthermore, natural rubber, synthetic rubber, polyvinyl acetate resins, (meth)acrylic acid resins, polyvinyl chloride resins, polyurethane-polyacrylic acid resins, or their modified forms and other resins can also be used. The above-mentioned adhesive resins can be used alone or in combination of two or more.

[0066] Examples of solvents (or dispersion media) 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 methanol, ethanol, n-propanol, isopropanol, isobutanol, 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 media) can be used alone or in combination of two or more.

[0067] Examples of printing methods for forming patterned layers include gravure printing, offset printing, screen printing, aniline printing, electrostatic printing, and inkjet printing. Furthermore, for forming a full-surface patterned layer, various coating methods can be used, such as roller coating, doctor blade coating, air knife coating, die coating, lip coating, comma coating, roller coating, flow coating, and dip coating. In addition, hand-painting, ink application, photographic methods, transfer printing, laser beam lithography, electron beam lithography, partial vapor deposition of metals, etching, etc., can also be used, or in combination with other forming methods.

[0068] There is no particular limitation on the thickness of the pattern layer; it can be set appropriately according to the characteristics of the product, with a layer thickness of approximately 0.1–15 μm.

[0069] transparent resin layer

[0070] The transparent resin layer is an optional layer, and there are no particular limitations as long as it is transparent; colorless transparent, colored transparent, semi-transparent, etc., are all acceptable. The material of the aforementioned transparent resin layer is not limited, but it is preferably formed from a thermoplastic resin. Specific examples include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ionomers, acrylates, methacrylates, etc. In this invention, at least one of polyvinyl chloride and polyolefins (polyethylene, polypropylene, etc.) is preferably used. In this specification, when the transparent resin layer contains a thermoplastic resin, the transparent resin layer is specifically referred to as a "transparent thermoplastic resin layer."

[0071] Transparent resin layers can be colored as long as they are transparent.

[0072] In addition, as long as the transparent resin layer is transparent, it can also contain various additives such as flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers as needed.

[0073] 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, deep embossing can be formed, and it is easy to obtain the effect of suppressing scratches or pattern layer reduction due to wear (pattern elimination).

[0074] Transparent adhesive layer

[0075] To improve the adhesion between the patterned layer and the transparent resin layer or the cross-linked curable resin layer (surface protective layer) described later, a transparent adhesive layer can be formed. There are no particular limitations on the transparency of the transparent adhesive layer; it can be colorless transparent, colored transparent, semi-transparent, etc.

[0076] There are no particular limitations on the adhesive used; adhesives known in the field of decorative panels can be used. Examples of adhesives known in the field of decorative panels include thermoplastic resins such as polyamide resins, acrylic resins, and vinyl acetate resins, and thermosetting resins such as polyurethane resins. These adhesives can be used alone or in combination of two or more. Alternatively, two-component curing polyurethane resins or polyester resins using isocyanate as a curing agent can also be used.

[0077] The thickness of the transparent adhesive layer is not particularly limited, but is approximately 0.1 to 30 μm, preferably approximately 1 to 20 μm.

[0078] Primer

[0079] A primer layer for a cross-linked curing resin layer (surface protective layer) can be applied to the transparent resin layer. This primer layer, in addition to improving the adhesion between the transparent resin layer and the cross-linked curing resin layer (described later), can also improve the bending processability and scratch resistance of the decorative sheet by combining with the cross-linked curing resin layer. There are no particular limitations on the primer layer's transparency; colorless transparent, colored transparent, and semi-transparent types are all acceptable.

[0080] The primer layer can be formed by applying a known primer to the surface of a transparent resin layer. Examples of primers include polyurethane resin primers composed of acrylic-modified polyurethane resins (acrylic-polyurethane copolymer resins), polycarbonate-based acrylic-polyurethane copolymer resins, etc.; primers composed of polyurethane-cellulose resins (e.g., resins formed by adding hexamethylene diisocyanate to a mixture of polyurethane and nitrocellulose); and resin primers composed of block copolymers of acrylic and polyurethane. Among these, from the viewpoint of scratch resistance and weather resistance, polyurethane resin primers containing polycarbonate-based acrylic-polyurethane copolymer resins are preferred.

[0081] Additives can be added to the primer as needed. Examples of additives include: UV absorbers, light stabilizers, and other weather-resistant agents; fillers such as silica, calcium carbonate, and clay; flame retardants such as magnesium hydroxide; antioxidants; lubricants; and foaming agents. The amount of additives can be appropriately determined based on the characteristics of the product.

[0082] Among the aforementioned additives, examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. As light stabilizers, hindered amine light stabilizers (HALS) are preferred. The content of these weathering agents is not limited, and the ultraviolet absorber and light stabilizer can each be approximately 1000 to 100000 ppm by mass. Particularly in this invention, triazine-based ultraviolet absorbers and / or hindered amine light stabilizers are preferred.

[0083] The thickness of the base coating is not limited, but is preferably 0.5 μm to 12 μm, more preferably 1 μm to 8 μm. By setting it within this range, the bending processability and scratch resistance of the decorative sheet can be easily improved by combining it with a cross-linked curable resin layer. In addition, it is easy to include additives such as weather-resistant agents, which can easily impart weather resistance to the decorative sheet.

[0084] Cross-linked curing resin layer (surface protective layer)

[0085] The decorative sheet of the present invention has a cross-linked curable resin layer (surface protective layer) on its outermost surface. The cross-linked curable resin layer and the antiviral agent contained therein meet the specified conditions shown in (1) and (2) below, thereby maintaining the surface properties of the surface protective layer and, in particular, exerting an antiviral effect against non-enveloped viruses.

[0086] (1) The above-mentioned cross-linked curing resin layer contains the cured product of cross-linked curing resin and antiviral agent;

[0087] (2) The above-mentioned antiviral agent is an antiviral agent that is effective against non-enveloped viruses. The antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative. At least as a component of the above-mentioned carboxylic acid derivative, it contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine.

[0088] There are no particular limitations on the transparency of cross-linked curing resins; they can be colorless transparent, colored transparent, semi-transparent, etc.

[0089] The resin composition of the cross-linking curing resin is not limited, but it preferably contains ionizing radiation curing resin or two-component curing polyurethane resin. It is preferable that the resin is substantially formed from these resins. When the outermost layer is formed from ionizing radiation curing resin or two-component curing polyurethane resin, the wear resistance, impact resistance, stain resistance, scratch resistance, and weather resistance of the decorative sheet are easily improved. Among these, ionizing radiation curing resin is preferred. By using these resins, the Martens hardness of the cross-linking curing resin layer can be easily adjusted to 30 N / mm. 2 Above 180N / mm 2 Therefore, it is easy to adjust the sliding resistance value (CSR value), which is an indicator of anti-slip performance, to above 0.25.

[0090] Among them, the anti-slip index of the above-mentioned CSR value in various applications is as follows: if it is 0.25 or above (especially 0.25 or above and less than 0.30), it is judged to be suitable for use as a door and window partition; if it is 0.30 or above (especially 0.30 or above and less than 0.38), it is judged to be suitable for use as a general floor; if it is 0.38 or above (especially 0.38 or above and less than 0.50), it is judged to be suitable for use as an anti-slip floor with high anti-slip properties.

[0091] As an ionizing radiation-curing resin, there are no particular limitations; transparent resins whose main components are prepolymers (including oligomers) containing free radical polymerizable double bonds capable of polymerization and crosslinking upon irradiation with ionizing rays such as ultraviolet light or electron beams, and / or monomers, can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is typically a crosslinking curing reaction.

[0092] Specifically, compounds containing free radical polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, or cationic polymerizable functional groups such as epoxy groups, can be listed as prepolymers or monomers. Furthermore, polyene / thiol prepolymers obtained by combining polyenes and polythiols are also preferred. Here, (meth)acryloyl group refers to acryloyl group or methacryloyl group.

[0093] Examples of prepolymers containing free radical polymerizable unsaturated groups include polyester (meth)acrylates, polyurethane (meth)acrylates, epoxy (meth)acrylates, melamine (meth)acrylates, triazine (meth)acrylates, and silicone (meth)acrylates. Their weight-average molecular weight is typically preferably around 250 to 100,000. The weight-average molecular weight in this specification is the average molecular weight determined using GPC analysis (gel permeation chromatography) and converted to standard polystyrene.

[0094] Monomers possessing unsaturated groups capable of free radical polymerization can be categorized as follows: methyl methacrylate, 2-ethylhexyl methacrylate, and phenoxyethyl methacrylate, among others, as monofunctional monomers. Additionally, polyfunctional monomers include diethylene glycol dimethacrylate, propylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexamethacrylate.

[0095] Examples of prepolymers with cationic polymerizable functional groups include prepolymers of epoxy resins such as bisphenol-type epoxy resins and phenolic varnish-type epoxy compounds, as well as prepolymers of vinyl ether resins such as fatty acid-based vinyl ethers and aromatic vinyl ethers. Additionally, examples of thiols include polythiols such as trimethylolpropane trimercaptoacetate and pentaerythritol tetramercaptoacetate. Examples of polyenes include compounds in which allyl alcohol is added to both ends of a polyurethane using a diol and a diisocyanate.

[0096] In this invention, as an ionizing radiation curable resin, a mixed resin containing a polyurethane (meth)acrylate oligomer (A) with a weight average molecular weight of 1000 to 3000 having two free radical polymerizable unsaturated groups per molecule and an aliphatic polyurethane (meth)acrylate oligomer (B) having three to 15 free radical polymerizable unsaturated groups per molecule can be used. When using such a mixed resin, due to the high crosslinking density, it is easy to obtain effects such as scratch resistance and stain resistance. Furthermore, by appropriately adjusting the weight average molecular weight and / or the amount of compounding, it has the advantage of easily adjusting the crosslinked curable resin layer into a form with excellent impact resistance or a form with excellent processing adaptability such as V-CUT, and other surface properties corresponding to the application.

[0097] The content ratio of oligomer (A) and oligomer (B) in the ionizing radiation curable resin is not limited. However, when the total amount of oligomer (A) and oligomer (B) is set to 100% by mass, it is preferable that oligomer (A) is in the range of 50-90% by mass and oligomer (B) is in the range of 10-50% by mass. Within this range, it is easy to set the Martens hardness of the cross-linked curable resin layer (after curing) to 30 N / mm. 2 Above 180N / mm 2 The anti-slip properties of the cross-linked cured resin layer can be easily adjusted for various applications (slip resistance value (CSR value) of 0.25 or higher).

[0098] In this invention, as an ionizing radiation curable resin, a mixed resin containing two aliphatic polyurethane (meth)acrylates, resin A and resin B, can also be used. Here, (meth)acrylate refers to acrylate or methacrylate.

[0099] Resin A is an aliphatic polyurethane (meth)acrylate with an isocyanurate backbone. There are no limitations as long as this condition is met; for example, an aliphatic polyurethane (meth)acrylate with an isocyanurate backbone formed from a trimer of diisocyanate is preferred. Specific examples include trimers of hexamethylene diisocyanate (especially 1,6-hexamethylene diisocyanate), trimers of toluene diisocyanate, and trimers of m-xylene diisocyanate. Among these, toluene diisocyanate and m-xylene diisocyanate may have poorer weather resistance than hexamethylene diisocyanate due to the presence of a benzene ring; therefore, hydrogenation of these diisocyanates is preferred. These resins A have the effect of improving the stain resistance and alkali resistance of the cross-linked cured resin layer.

[0100] Resin B is an aliphatic polyurethane (meth)acrylate that has an alicyclic backbone but not an isocyanurate backbone. There are no limitations as long as this condition is met; for example, it is preferable to have at least one of isophorone and cyclohexane as the alicyclic backbone. Specific examples include substances with acrylate added to the ends of polymers (polyurethane oligomers) using isophorone diisocyanate and butanediol as monomers, and PG-modified diacrylates of hydrogenated dicyclohexylmethane diisocyanate (hydrogenated MDI). These resins B impart flexibility to cross-linked cured resin layers. By combining with resin A, they can impart excellent long-term stain resistance, alkali resistance, and the ability to suppress the formation of cracks or fissures during impact or processing to cross-linked cured resin layers.

[0101] Furthermore, ionizing radiation-curable resins are transparent resins whose main components are prepolymers (including oligomers) and / or monomers containing free radical polymerizable double bonds in their molecules that can undergo polymerization and crosslinking reactions when irradiated by ionizing rays such as ultraviolet rays or electron beams. The curing reaction is typically a crosslinking curing reaction. As the ionizing rays used to cure the ionizing radiation-curable resin, electromagnetic waves or charged particles with energy capable of causing a curing reaction in the molecules of the ionizing radiation-curable resin (composition) can be used. Ultraviolet rays or electron beams are commonly used, but visible light, X-rays, ionizing rays, etc., can also be used. In this invention, considering that the ionizing radiation-curable resin does not contain a photopolymerization initiator, that the properties of the raw material resin can be directly reflected in the properties of the resin components in the crosslinking-curable resin layer, and that the range of choices can be expanded when using weathering agents, electron beam-curable resins are preferred.

[0102] As a two-component curing polyurethane resin, there are no particular limitations. Among them, a resin containing a polyol component with OH groups as the main agent (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) and an isocyanate component as the curing agent (toluene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, etc.) can be used.

[0103] The cross-linking curing resins exemplified above can be used in combination with one or more types.

[0104] In addition to the cured product of the cross-linked resin, the cross-linked cured resin layer also contains antiviral agents. Generally speaking, based on the presence or absence of an envelope (lipid membrane), viruses are broadly classified into enveloped viruses (with an envelope) and non-enveloped viruses (without an envelope). Enveloped viruses include, for example, influenza viruses, herpesviruses, HIV, and hepatitis B viruses. Non-enveloped viruses include, for example, norovirus, feline calicivirus, rhinovirus, and adenovirus.

[0105] The antiviral agent used in this invention (hereinafter also referred to as "the antiviral agent of this invention") is an antiviral agent with antiviral activity against non-enveloped viruses. This antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative. At least as a constituent component of the aforementioned carboxylic acid derivative, it contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine. Furthermore, in the antiviral agent of this invention, it is preferable that, as a constituent component of the styrene polymer derivative, it also contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine. These are positioned as compounds detected as constituent components during organic structure analysis of the carboxylic acid derivative and the styrene polymer derivative, respectively.

[0106] As for the aforementioned carboxylic acid derivatives, there are no limitations as long as the specified constituent components are detected during organic structure analysis. For example, a carboxylic acid derivative can be prepared by mixing and reacting a mixture containing cyclohexanecarboxylic acid (manufactured by Shin Nippon Rikka 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.).

[0107] Furthermore, as the aforementioned styrene polymer derivative, it is preferable to use a substance that detects the aforementioned constituent components during organic structure analysis. As an example of the preparation method, the styrene polymer derivative can be prepared by mixing and reacting raw materials containing sodium p-styrene sulfonate (manufactured by Tosoh Corporation, trade name "SPINOMAR NaSS"), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.), and modified ethanol (manufactured by Wako Pure Chemical Industries, Ltd., trade name "86% ethanol-ME").

[0108] The antiviral agent of the present invention can be prepared by mixing (kneading) the above-mentioned carboxylic acid derivative and the above-mentioned styrene polymer derivative in a desired mixing ratio and pulverizing them to a desired size using a known pulverizing method such as a jet mill. The content ratio of the above-mentioned carboxylic acid derivative and the above-mentioned 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 setting such a content ratio (mixing ratio), an antiviral effect against non-enveloped viruses can be easily obtained.

[0109] The shape of the antiviral agent (primary particles) of the present invention is not limited, and examples include spheres, ellipsoids, polyhedra, and scales. Furthermore, the average particle size of the antiviral agent of the present invention is not limited, but is preferably 2 μm to 15 μm, more preferably 3 μm to 12 μm. The average particle size in this specification is a specific value of the mass average value D50 obtained from particle size distribution determination using laser diffraction.

[0110] The reasoning behind the antiviral activity of the antiviral agent of the present invention against viruses (especially non-enveloped viruses) is as follows, but is not limited to the mechanism hypothesized below. After various viruses bind to glycan receptors (with neuraminic acid at the glycan terminal) on the surface of host cells and invade the host cells, the antiviral agent of the present invention, having ionic groups similar to neuraminic acid, captures the virus by binding to it instead of the host cell, thus preventing the virus from binding to the receptors on the host cell, and can be considered to exert an antiviral effect. Specifically, the aforementioned various amino groups, as components of the carboxylic acid derivative, bind (capture) to the spike protein of enveloped viruses and the capsid (protein shell) of non-enveloped viruses. It can be considered that the sulfonic acid groups of the styrene polymer derivative simultaneously or subsequently destroy the envelope, inactivating enveloped viruses, while the carboxyl groups of the carboxylic acid derivative compound oxidize the capsid, inactivating non-enveloped viruses. Furthermore, as mentioned above, it can be considered that the sulfonic acid groups mainly contribute to envelope destruction, but due to their oxidizing ability, they are also related to the oxidation of the capsid of non-enveloped viruses, similar to the carboxyl groups. Therefore, the simultaneous use of carboxylic acid derivatives and styrene polymer derivatives is effective in both inactivating non-enveloped viruses and, further, inactivating enveloped viruses. Considering the ability to inactivate non-enveloped viruses at a concentration that does not impair the surface properties of the protective layer, the antiviral agent of the present invention has advantages over existing products. However, the hypothesized mechanism for inactivating enveloped viruses is the same as described above. Therefore, the antiviral agent of the present invention exhibits antiviral effects not only against non-enveloped viruses but also against enveloped viruses.

[0111] Relative to 100 parts by weight of the cross-linked curing resin, the content of the antiviral agent of the present invention is preferably 1 part by weight or more and 10 parts by weight or less, more preferably 2 parts by weight or more and 6 parts by weight or less. Within such a content range, the surface properties of the surface protective layer are generally not affected, and the prescribed antiviral effect can be achieved.

[0112] Regarding the thickness of the cross-linked curable resin layer, when the cross-linked curable resin layer does not have protrusions caused by the antiviral agent of the present invention, the average thickness of the smooth portion is preferably 2 μm or more. When it has protrusions caused by the antiviral agent of the present invention, the average thickness of the smooth portion excluding the protrusions is preferably 2 μm or more. When the average thickness of the smooth portion is 2 μm or more, it is more preferably 4 μm or more, and the upper limit of the average thickness is about 35 μm. The average thickness of the cross-linked curable resin layer refers to the flat portion (see reference) where no embossed patterns or protrusions (raised areas of the cross-linked curable resin layer) are formed. Figure 1 The average value of the thickness A) refers to the average thickness of any 10 points with a width of 1 cm in the cross-sectional view of the cross-linked cured resin layer in this specification. "Width" is the direction perpendicular to the thickness direction.

[0113] The cross-linking curable resin layer can be formed, for example, by applying a cross-linking curable resin layer forming composition containing the cross-linking curable resin and the antiviral agent of the present invention onto a base layer using known coating methods such as gravure coating or roller coating, followed by resin curing. Specifically, after applying the cross-linking curable resin layer forming composition but before complete curing, the antiviral agent of the present invention rises in the coating film, thereby forming protrusions due to the antiviral agent on the outermost surface of the cross-linking curable resin layer, or the antiviral agent partially aggregates in the coating film, resulting in an apparent increase in the particle size of the antiviral agent. Even if this occurs, there is no problem in terms of exhibiting antiviral performance.

[0114] In this invention, when the thickness of the smooth portion of the cross-linked cured resin layer is divided into three equal parts to form a lower layer, a middle layer, and an upper layer, it is preferable that the center point of more than 50% of the total antiviral agent (in numerical form) of the antiviral agent of this invention is located in the middle layer or the upper layer (i.e., above the middle layer). Figure 4 The following examples illustrate the positional relationship between the thickness A of the smooth portion of the cross-linked cured resin layer and the center point of the antiviral agent. Antiviral agents 9-1 and 9-2 are examples where the center point of the antiviral agent is located in the middle or upper layer (the middle layer includes the boundary between the lower and middle layers, and the upper layer includes the boundary between the middle and upper layers) obtained by dividing the thickness of the smooth portion of the cross-linked cured resin layer into three equal parts. Antiviral agent 9-3 is an example where the center point of the antiviral agent is located in the lower layer. Furthermore, regarding the center point of the antiviral agent, in a cross-sectional view of the cross-linked cured resin layer, a circle of the smallest diameter is drawn in a manner that completely includes the antiviral agent of the present invention, regardless of its shape, and the center point of this circle is defined as the center point. As described above, the proportion of the center point of the antiviral agent of the present invention located in the middle or upper layer (i.e., above the middle layer) is preferably 50% or more, more preferably 67% or more. Within this range, the antiviral effect of the antiviral agent of the present invention is easily obtained. Furthermore, in this preferred embodiment, as described above, when the content of the antiviral agent of the present invention is less than 10 parts by mass relative to 100 parts by mass of the cross-linked curing resin, it generally does not affect the surface properties of the surface protective layer and can still exert the specified antiviral effect. Specifically, cross-sectional observation is performed by cutting the cross-linked curing resin layer in the thickness direction using a sharp tool such as a single-edged razor or a slicer, and then observing the cut surface (with a width of 200 μm) using a digital microscope (Manufactured by Keyence, Model: VHX-7000, magnification: 200x).

[0115] In this invention, the cross-linked curable resin layer preferably has fine irregularities on its outermost surface with an arithmetic mean roughness Ra of 0.1 μm or more. Such fine irregularities can be formed due to the rise of the antiviral agent, or by physical processing such as sandblasting or micro-embossing. Furthermore, the arithmetic mean roughness Ra on the outermost surface is more preferably 1.0 μm or more, and the preferred upper limit of Ra is approximately 40 μm or less. By forming such fine irregularities, the surface area of ​​the outermost surface increases, thus making it easier to obtain an antiviral effect compared to the case without fine irregularities. The arithmetic mean roughness Ra in this specification is a value measured according to JIS B0601 (2001) using a surface roughness measuring instrument (“SURFCOM-FLEX-50A”, manufactured by Tokyo Seimitsu Co., Ltd.).

[0116] In this invention, the Martens hardness of the cross-linked cured resin layer is preferably 30 N / mm. 2 Above 180N / mm 2 The preferred value is 60 N / mm. 2 Above 180N / mm 2 the following.

[0117] The martensite hardness in this specification is based on values ​​measured using a PICODENTORHM-500 martensite hardness tester (manufactured by Fischer Instruments) according to ISO 14577. Specifically, using... Figure 5 The diamond indenter (Vickers indenter) shown in (a) is as follows: Figure 5 As shown in (b), the diamond indenter is pressed into the test specimen for measurement. Regarding the indentation conditions, at room temperature (laboratory ambient temperature), as follows... Figure 5 As shown in (c), a load from 0 mN to 5 mN is first applied over 10 seconds, followed by a 5 mN load held for 5 seconds, and finally unloaded from 5 mN to 0 mN over 10 seconds. Furthermore, in this specification, to avoid the influence of the hardness of layers other than the cross-linked curable resin layer, the Martens hardness of the cross-section of the cross-linked curable resin layer is measured. In this case, a decorative sheet is embedded in resin (such as a cold-curing epoxy two-component curing resin or a UV-curing resin), cured at room temperature (23±5℃) for at least 24 hours, and then the cured embedded sample is cut and mechanically ground to expose the cross-section of the cross-linked curable resin layer. A diamond indenter is then pressed into this cross-section (avoiding the location of particles such as filler material in the layer), and the Martens hardness of the cross-section is measured.

[0118] In this invention, the Martens hardness of the cross-linked cured resin layer is preferably set to 30 N / mm. 2 Above 180N / mm 2Hereinafter, the sliding resistance value (CSR value), which serves as an indicator of slip resistance, can be easily adjusted to 0.25 or higher. Specifically, regarding the slip resistance index of the CSR value in various applications, a value of 0.25 or higher (especially 0.25 or higher and less than 0.30) indicates suitability for use as door and window partitions; a value of 0.30 or higher (especially 0.30 or higher and less than 0.38) indicates suitability for use as general flooring; and a value of 0.38 or higher (especially 0.38 or higher and less than 0.50) indicates suitability for use as anti-slip flooring with high slip resistance. Furthermore, the sliding resistance value (CSR value) in this specification is obtained by measuring the sliding resistance value (CSR value) produced by socks using a Tokyo Tech-type sliding tester (O-Y·PSM). The Martens hardness of the cross-linked cured resin layer is 30 N / mm. 2 Above 180N / mm 2 In the following cases, the Martens hardness of the corresponding substrate sheet and / or transparent thermoplastic resin layer is preferably, for example, 30 N / mm. 2 Above 80N / mm 2 the following.

[0119] In this invention, to supplement the antiviral properties of the cross-linked cured resin layer, the cross-linked cured resin layer may contain a phenyl ether derivative compound. Examples of phenyl ether derivative compounds include polyoxyethylene alkyl ethers, which are known to exhibit antiviral properties as ether-type nonionic surfactants.

[0120] Furthermore, in the cross-linked curing resin layer, various additives can be added within a range that does not affect the surface properties and specified antiviral properties of the surface protective layer, such as dyes, pigments, colorants, inorganic fillers, weathering agents, defoamers, leveling agents, thixotropic agents, flame retardants, antibacterial agents different from the aforementioned antiviral agents, and anti-allergens different from the aforementioned antiviral agents. For example, in this invention, in addition to the aforementioned antiviral agents, at least one selected from antibacterial agents and anti-allergens can be used. Additionally, while inorganic fillers are mostly used as matting agents, by including inorganic fillers in the cross-linked curing resin layer, it is also expected to achieve the effect of suppressing the curing shrinkage of the surface protective layer.

[0121] As the aforementioned antibacterial agents, there are inorganic and organic antibacterial agents. In particular, inorganic antibacterial agents generally have higher safety, better durability, and superior heat resistance compared to organic antibacterial agents, and are therefore preferred. The inorganic antibacterial agents in this specification are obtained by supporting antibacterial metals such as silver, copper, and zinc on various inorganic carriers. Among them, silver-containing inorganic antibacterial agents (silver-containing inorganic particles) are preferred, specifically silver-supported zeolite particles, etc.

[0122] The aforementioned anti-allergy agents comprise either inorganic or organic compounds, which may be used individually or in combination of two or more different compounds. As inorganic compounds, materials supported by metals are preferred.

[0123] As an anti-allergy agent, sometimes similar or identical agents to antibacterial agents can also be effective. In such cases, the concentrations of both the antibacterial and anti-allergy agents can be optimized to achieve the desired antibacterial and anti-allergic properties.

[0124] Inorganic materials that are inorganic compounds are preferably selected from at least one of titanium dioxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate, and magnesium phosphate, with titanium dioxide and zirconium phosphate being preferred.

[0125] The metal used as a carrier for inorganic materials is preferably selected from at least one of silver, gold, platinum, zinc, and copper, with zinc being the most preferred. Commercially available products, such as "Atomy Ball TZ-R: Titanium Oxide Supported Zinc" manufactured by Nichibukai Catalyst, are preferred; these anti-allergy agents are effective against various allergens such as dust mites and pollen.

[0126] As organic compounds, preferred are non-water-soluble polymers containing phenolic hydroxyl groups or compounds formed by inorganic solid acids, or polymers containing at least one monomer component selected from styrene sulfonic acid and its salts.

[0127] As non-water-soluble polymers containing phenolic hydroxyl groups, commercially available products include, for example, "Aller Buster" manufactured by Sekisui Chemicals Co., Ltd., and "MARUKALYNCUR M" manufactured by Maruzen Oil Co., Ltd. Additionally, commercially available products combining polyphenolic compounds and zirconium compounds include "AlleRemove" manufactured by Toa Synthetic Co., Ltd. These anti-allergy agents are effective against various allergens such as dust mites and pollen.

[0128] The material shown in Japanese Patent No. 6136433 may be used as at least one monomer component selected from styrene sulfonic acid and its salts.

[0129] Furthermore, when organic and inorganic compounds are mixed, examples include anionic phenolic materials and zinc-based materials with anti-allergic properties.

[0130] As anionic phenolic materials, appropriate selections can be made from tannins, tannic acid-tartaric acid, phenol sulfonic acid formaldehyde resin, sulfone compounds of phenolic varnish resin, methanesulfonic acid of phenolic varnish resin, methanesulfonic acid of methyl phenolic resin, benzylated phenol sulfonic acid, thiophenol compounds, dihydroxy compounds, diphenyl sulfone compounds, ligand compounds and their metal chelate compounds.

[0131] As a zinc-based material, it can be appropriately selected from water-soluble zinc compounds or non-water-soluble zinc compounds, zinc / metal oxide composite materials, etc. Preferably, the composite particles of non-water-soluble zinc compounds and / or non-water-soluble zinc-metal oxides are dispersed in water and have a particle size of less than 50 μm. The aforementioned metal oxides include at least one of titanium dioxide, silicon dioxide, and aluminum oxide.

[0132] Embossing

[0133] Embossing is a process used to impart desired textures, such as wood grain patterns, to decorative sheets. Embossing can be performed on transparent resin layers and / or cross-linked curing resin layers. For example, after heating and softening the cross-linked curing resin layer, pressure is applied and shaped using an embossing plate with the desired raised or recessed pattern, followed by cooling to fix the texture. Embossing can be performed using known single-piece or rotary embossing machines.

[0134] Embossing patterns include, for example, wood grain grooves, raised patterns (raised annual rings), hairline, sanding, and pear skin patterns.

[0135] When embossing is performed, ink can be filled into the embossed recesses using a wiping process as needed. For example, ink is filled into the embossed recesses while scraping the surface with a scraper. The ink used for filling (wiping ink) is typically an ink with a two-component curing polyurethane resin as a binder. In particular, by wiping the grooves and recesses of the wood grain, a design that more closely resembles actual wood grain can be achieved, thereby enhancing the product's value.

[0136] Backside base coating

[0137] A backing coating can be applied to the back of the substrate sheet as needed. This is effective, for example, when bonding the substrate sheet to a decorative panel substrate to create a decorative panel.

[0138] The back primer layer can be formed by applying a known primer onto the substrate sheet. Examples of primers include polyurethane resin primers composed of acrylic-modified polyurethane resin (acrylic-polyurethane copolymer resin), polycarbonate-based acrylic-polyurethane copolymer resin, etc.; primers composed of polyurethane-cellulose resin (e.g., a resin formed by adding hexamethylene diisocyanate to a mixture of polyurethane and nitrocellulose); and resin primers composed of block copolymers of acrylic and polyurethane.

[0139] Primers can be formulated with additives as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, and light stabilizers. The amount of additives can be appropriately determined based on the characteristics of the product.

[0140] The thickness of the back undercoat layer is not particularly limited, but is usually 0.01 to 10 μm, preferably about 0.1 to 1 μm.

[0141] Synthetic resin substrate

[0142] A synthetic resin substrate layer can be provided on the back side of the substrate sheet as needed. The impact resistance of the decorative sheet is further improved by having a synthetic resin substrate layer. Alternatively, if the aforementioned back undercoating layer is also provided, the synthetic resin substrate layer and the back undercoating layer are sequentially provided on the back side of the substrate sheet, starting from the substrate sheet side.

[0143] Examples of resins constituting the substrate layer of synthetic resins include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, heat-resistant polyalkylene terephthalate (e.g., polyethylene terephthalate obtained by replacing part of ethylene glycol with 1,4-cyclohexanediol or diethylene glycol, the so-called trade name PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-ethylene isophthalate copolymer, polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, diene rubbers such as styrene-butadiene rubber, isoprene rubber, and chloroprene rubber, non-diene rubbers such as butyl rubber and ethylene propylene rubber, natural rubber, and thermoplastic elastomers. These resins can be used alone or in combination.

[0144] The thickness of the synthetic resin substrate 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 limiting the thickness of the synthetic resin substrate layer to the above range, the impact resistance of the decorative sheet is further improved. Furthermore, by limiting the thickness of the synthetic resin substrate layer to the above range, warping of the decorative sheet can be further suppressed.

[0145] Vesicle formation of various additives contained in each layer of the decorative sheet

[0146] Regarding the various additives added to the decorative sheet of the present invention (such as inorganic fillers added to the base layer or cross-linked curing resin layer), it is preferable that these various additives are vesicled. As for the method of vesicledizing the various additives, there is no particular limitation, and known methods can be used for vesicledization, among which supercritical reverse phase evaporation is preferred.

[0147] Besides supercritical reverse-phase evaporation, other methods for vesicle formation include the Bangham process, extrusion, hydration, reverse-phase evaporation, and freeze-thaw processes. A brief explanation of these vesicle formation methods: The Bangham process involves adding chloroform or a chloroform / methanol mixture to a flask or similar container, then adding phospholipids to dissolve them. The solvent is then removed using an evaporator, forming a lipid-based film. A dispersion of additives is then added, followed by hydration and dispersion using a vortex mixer to obtain vesicles. The extrusion process uses a phospholipid solution to prepare the film, replacing the mixer used for external agitation in the Bangham process, and passes it through a filter to obtain vesicles. The hydration process is essentially the same as the Bangham process, but instead of using a mixer, the film is gently stirred to disperse it, resulting in vesicles. The reverse-phase evaporation process involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method uses cooling and heating as external disturbances to obtain vesicles by repeatedly performing this cooling and heating process.

[0148] The supercritical reverse-phase evaporation method is described in detail below. Supercritical reverse-phase evaporation involves uniformly dissolving the substance forming the vesicle outer membrane in carbon dioxide at a supercritical state or above the supercritical point temperature or pressure. A water-soluble or hydrophilic aqueous phase containing various additives is added to the resulting mixture as an encapsulating material, forming capsule-like vesicles containing these additives encapsulated by a single membrane. Supercritical carbon dioxide refers to carbon dioxide at or above the critical temperature (30.98℃) and critical pressure (7.3773±0.0030MPa). Carbon dioxide at or above the critical point temperature or pressure refers to carbon dioxide at only the critical temperature or only the critical pressure exceeding the critical conditions. Using this method, monolayer sheet-like vesicles with diameters of 50–800 nm can be obtained. Generally, a vesicle is a general term for a small cell containing a liquid phase within a closed, spherical membrane structure. Specifically, vesicles whose outer membrane is composed of biological lipids such as phospholipids are called liposomes.

[0149] Examples of the aforementioned phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, myocardial phospholipids, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and other glycerophospholipids, as well as sphingomyelin, ceramide phosphorylethanolamine, ceramide phosphorylglycerol, and other sphingomyelins.

[0150] As a substance constituting the outer membrane, nonionic surfactants, or mixtures thereof with cholesterol or triacylglycerols, can also be used as dispersants.

[0151] As the aforementioned nonionic surfactant, one or more of the following can be used: polyglycerol ether, dialkyl glycerol, polyoxyethylene hardened 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, and polyoxyethylene-polycaprolactam copolymer.

[0152] As the aforementioned cholesterol class, one or more of the following can be used: cholesterol, α-cholesterol, β-cholesterol, cholesterol, sterol (5,24-cholestipen-3β-ol), sodium cholate, cholecalciferol, etc.

[0153] The outer membrane of the aforementioned liposomes can be formed from a mixture of phospholipids and dispersants. In the decorative sheet of the present invention, by producing liposomes with an outer membrane formed of phospholipids, the compatibility of the resin composition, which is the main component of each layer, with various additives can be improved.

[0154] 2. Antiviral adhesive processing sheet

[0155] The antiviral adhesive sheet of the present invention (the adhesive sheet of the present invention) is composed of a laminate having at least an adhesive sheet and a decorative sheet of the present invention sequentially in the thickness direction. The adhesive sheet is not particularly limited; adhesive sheets used in the fields of decorative sheets and other functional sheets can be appropriately used. The adhesive sheet of the present invention, by having an adhesive sheet on its back side, can adhere to the surface of various flooring items and the surface of the adhered object, and can arbitrarily impart antiviral properties.

[0156] Figure 2 The image shows an example of an antiviral adhesive processing sheet 11 on which the decorative sheet 1 of the present invention (the side opposite to the cross-linked cured resin layer side is bonded to the adhesive sheet 10) is sequentially stacked on the adhesive sheet 10.

[0157] 3. Antiviral decorative panels

[0158] The antiviral decorative panel of the present invention (the decorative panel of the present invention) is composed of a laminate having at least a decorative panel substrate and the decorative sheet of the present invention or the adhesive processing sheet of the present invention in sequence in the thickness direction.

[0159] Figure 3 The image shows an example of an antiviral decorative panel 13 in which the decorative sheet 1 of the present invention (with the side opposite to the cross-linked cured resin layer side bonded to the decorative panel substrate 12) is sequentially stacked on the decorative panel substrate 12.

[0160] There are no limitations on the substrate material for decorative panels. Examples include at least one of the following: medium-density fiberboard (MDF), high-density fiberboard (HDF), particleboard, coniferous plywood, hardwood plywood, fast-growing plywood, cork chips, cork-containing composite substrates, and thermoplastic resin boards (resin boards mainly composed of polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc., or boards made by foaming these). These decorative panel substrate materials can be used alone or in combination and layered.

[0161] Examples of coniferous trees include fir, larch, Japanese pine, cedar, cypress, pine, redwood, and spruce. Examples of broadleaf trees include willow, linden, birch, prickly ash, beech, oak, and Meranti. Additionally, examples of fast-growing trees include poplar, jacaranda, black locust, eucalyptus, eucalyptus, and terminalia.

[0162] The number of wood veneer layers used in wood-based plywood, such as coniferous plywood, hardwood plywood, and fast-growing plywood, is not limited, but is generally preferred to be 3 to 7 layers, and more preferably 5 to 7 layers. Furthermore, the adhesive used in the production of wood-based plywood is not limited, and widely known woodworking adhesives can be used. Examples of adhesives that contain polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomers, butadiene-acrylonitrile rubber, chloroprene rubber, and natural rubber as active ingredients can be included. Additionally, thermosetting adhesives such as melamine-based, phenolic-based, and urea-based adhesives (vinyl acetate-urea-based, etc.) can also be included.

[0163] As the aforementioned cork chips, not only can natural cork, a flexible raw material obtained by peeling and processing the cork tissue from the bark of the cork oak tree, be used, but any type of so-called synthetic cork, which is similar to cork, can also be used. Furthermore, the cork chips can be a single layer or a laminate of multiple cork chips with different moduli of elasticity and densities.

[0164] Examples of cork-containing composite substrates include composite materials made by laminating and bonding cork sheets with other materials (such as medium-density fiberboard and high-density fiberboard).

[0165] The thickness of the decorative panel substrate is not limited, but it is preferably about 2 to 15 mm, and more preferably about 2 to 12 mm.

[0166] There are no limitations on the lamination method for combining decorative sheets or adhesive-bonded sheets with the decorative panel substrate. For example, methods such as bonding them together using an adhesive can be employed. Furthermore, if the adhesive-bonded sheet and the decorative panel substrate have sufficient adhesion, methods can be used to bond the adhesive-bonded sheet and the decorative panel substrate without the use of an adhesive. The adhesive can be appropriately selected from known adhesives depending on the type of material being adhered to. Examples include polyurethane, acrylic, polyurethane-acrylic acid, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomers, butadiene-acrylonitrile rubber, chloroprene rubber, and natural rubber. These adhesives can be used alone or in combination of two or more.

[0167] Example

[0168] The present invention will be specifically described below with reference to illustrative examples, comparative examples, and experimental examples. However, the present invention is not limited to the contents shown in the examples.

[0169] Example 1

[0170] Prepare a 60μm thick colored polypropylene film as the substrate sheet.

[0171] A back undercoat (2μm thick) is formed on the back side of the substrate sheet. Additionally, on the front side of the substrate sheet, a pattern layer with a thickness of 2μm is formed by gravure printing using a two-component polyurethane ink (trade name "V180", manufactured by Toyo Ink Co., Ltd.).

[0172] A transparent adhesive layer with a thickness of 2μm is formed on the patterned layer using polyurethane resin.

[0173] A transparent resin layer is formed by laminating transparent random polypropylene resin sheets to a thickness of 80 μm on a transparent adhesive layer using an extrusion lamination method.

[0174] After corona discharge treatment is applied to the front side of the transparent resin layer, a primer containing a two-component curable polyurethane resin is applied to a thickness of 2μm to form a base layer.

[0175] On the front side of the base coating, the following cross-linking curable resin layer forming composition is applied at a coating thickness of 15 μm using a gravure coating method. Then, under an oxygen concentration of 200 ppm or less, electron beams are applied using an electron beam irradiation device at an accelerating voltage of 165 keV and 5 Mrad to cure the electron beam curable resin, thereby forming a cross-linking curable resin layer to produce a decorative sheet. The composition includes 3 parts by mass of the following antiviral agent per 100 parts by mass of the cross-linking curable resin. Furthermore, when observing the cross-section of the cross-linking curable resin layer, the proportion of the antiviral agent's center point located in the middle or upper layer (i.e., above the middle layer) is 60% of the total.

[0176] (Composition for forming cross-linking cured resin layers)

[0177] • As a cross-linking curable resin, a polyurethane acrylate resin comprising 30 parts by mass of a multifunctional polyurethane oligomer and 70 parts by mass of a difunctional oligomer, totaling 100 parts by mass (the cured cross-linking curable resin layer has a Martens hardness of 110 N / mm). 2 (The recipe)

[0178] • Antiviral agent (3 parts by weight relative to 100 parts by weight of resin)

[0179] The carboxylic acid derivative is prepared by mixing and reacting a mixture of raw materials containing cyclohexanecarboxylic acid (manufactured by Shin Nippon Rikka 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.).

[0180] In addition, styrene polymer derivatives are prepared by mixing and reacting raw materials containing sodium p-styrene sulfonate (manufactured by Tosoh Corporation, trade name "SPINOMAR NaSS"), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.) and modified ethanol (manufactured by Wako Pure Chemical Industries, Ltd., trade name "86% ethanol-ME").

[0181] The antiviral agent was prepared by pulverizing the aforementioned carboxylic acid derivative and the aforementioned styrene polymer derivative in a mass ratio of 3:1 using a jet mill (manufactured by Nisshin Engineering Co., Ltd., trade name "SJ-100"). The antiviral agent was measured using a laser diffraction particle size distribution analyzer (manufactured by HORIBA Co., Ltd.) according to JIS Z8825-1, and its average particle size was found to be 10 μm.

[0182] • Antibacterial agent (0.5 parts by weight relative to 100 parts by weight of resin)

[0183] Silver-supported zeolite particles (trade name "Zeomic", manufactured by Sinanen Zeomic, average particle size 10 μm)

[0184] • Weather resistant agent

[0185] Triazine-based ultraviolet absorber (UVA "LA-F70", manufactured by ADEKA) (content is 1 part by weight relative to 100 parts by weight of resin)

[0186] Light stabilizer (free radical scavenger) (HALS "Tinuvin 152", manufactured by BASF) (0.3 parts by weight relative to 100 parts by weight of resin)

[0187] Example 2

[0188] Compared to 100 parts by weight of cross-linking curable resin, 9 parts by weight of photoinitiator (trade name "IRGACURE 184", manufactured by BASF) were added to make the coating thickness of the cross-linking curable resin layer forming composition 5 μm, the average particle size of the antiviral agent 4 μm, and the average particle size of the antibacterial agent 2.5 μm. The cross-linking curable resin layer was then irradiated with ultraviolet light at a wavelength of 300 nm using an ultraviolet irradiation device (resulting in a Marlowen hardness of 70 N / mm²). 2 Under the same conditions as in Example 1, the ultraviolet absorber was changed to a benzotriazole-based UVA absorber (UVA "Tinuvin 329", manufactured by BASF) (5 parts by weight relative to 100 parts by weight of resin), and the light stabilizer content was changed to 2 parts by weight relative to 100 parts by weight of resin to form a cross-linked curable resin layer. Otherwise, the same procedure was followed to produce the decorative sheet. Furthermore, when observing the cross-section of the cross-linked curable resin layer, the proportion where the center point of the antiviral agent was located in the middle or upper layer (i.e., above the middle layer) was 65% of the total.

[0189] Comparative Example 1

[0190] The antiviral agent was prepared by pulverizing only the styrene polymer derivative described in Example 1 using a jet mill. Otherwise, decorative sheets were fabricated using the same procedure as in Example 1. Furthermore, when observing the cross-section of the cross-linked cured resin layer, the proportion of the antiviral agent's center point located in the middle or upper layer (i.e., above the middle layer) was 60% of the total.

[0191] Example 3

[0192] Prepare an 80μm thick colored polyethylene sheet as the substrate.

[0193] A back undercoat (2μm thick) is formed on the back side of the substrate sheet. Then, on the front side of the substrate sheet, a pattern layer with a thickness of 2μm is formed by gravure printing using a two-component polyurethane ink (trade name "V180", manufactured by Toyo Ink Co., Ltd.).

[0194] Using a dry lamination adhesive (trade name "TAKELAC A540", manufactured by Mitsui Chemicals Co., Ltd., coating amount 2 g / m²) 2 The transparent resin layer is then laminated onto the patterned layer using a dry lamination method. An embossed pattern is then applied to the front side of the laminated transparent resin layer.

[0195] Using an extruder, a resin composition containing 0.5 parts by weight of hindered phenolic antioxidant (trade name "IRGANOX 1010", manufactured by BASF), 0.5 parts by weight of triazine UV absorber (trade name "CYASORBUV-1164", manufactured by SUNCHEM), and 0.5 parts by weight of NOR light stabilizer (trade name "Tinuvin XT850FF", manufactured by BASF) was melt-extruded to produce a transparent, highly crystalline homopolymer polypropylene sheet with a thickness of 100 μm, thereby obtaining a transparent resin layer. Furthermore, both sides of the transparent resin layer were subjected to corona treatment to achieve a wetting tension of 40 dyn / cm or higher on the sheet surface.

[0196] A cross-linking curable resin layer forming composition is applied to a transparent resin layer after embossing, and the coating is cured to obtain a decorative sheet. Furthermore, when observing the cross-section of the cross-linking curable resin layer, the proportion of the antiviral agent's center point located in the middle or upper layer (i.e., above the middle layer) is 80% of the total.

[0197] (Composition for forming cross-linking cured resin layers)

[0198] The cross-linking curable resin layer forming composition (thermally curable type that cross-links and cures due to heat) is prepared by combining the following curing agent, gloss modifier, ultraviolet absorber, light stabilizer and diluent in a polymer solution A.

[0199] Polymer solution A

[0200] 80 g of methyl methacrylate and 20 g of 2-hydroxyethyl methacrylate were introduced into a four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a reflux condenser. 100 g of ethyl acetate was added to dissolve them, and the mixture was stirred in an oil bath under a nitrogen atmosphere. Then, 0.2 g of α,α'-azobisisobutyronitrile was added to initiate polymerization. The mixture was heated and stirred in an oil bath at 60°C for 5 hours to obtain a colorless, viscous polymer solution A.

[0201] Mixture: 80 parts by weight

[0202] Hardener

[0203] Trade name: Duranate 24A-100 (manufactured by Asahi Kasei Co., Ltd.)

[0204] Mixture: 5 parts by weight

[0205] Gloss modifier (inorganic particles)

[0206] Product Name: Sunsphere H122 (Manufactured by AGC Si-Tech Co., Ltd.)

[0207] Characteristics: Spherical, average particle size 12μm, pore volume 2ml / g

[0208] Mixture: 10 parts by weight

[0209] • Ultraviolet absorbers

[0210] Product Names: Tinuvin P, Tinuvin 326, Tinuvin 399 (all manufactured by BASF)

[0211] Mixture: 2.0 parts by weight each

[0212] Light stabilizers

[0213] Product Name: Tinuvin 765 (Manufactured by BASF)

[0214] Mixture: 2.0 parts by weight

[0215] • Diluent

[0216] Product Name: Ethyl Acetate

[0217] Mixture: 50 parts by weight

[0218] Example 4

[0219] Except for changing the cross-linking curable resin layer forming composition used in Example 3 to the composition described below, the same procedure as in Example 3 was followed to obtain the decorative sheet. Furthermore, when observing the cross-section of the cross-linking curable resin layer, the proportion of the antiviral agent's center point located in the middle or upper layer (i.e., above the middle layer) was 58% of the total.

[0220] [Thermosetting / Photocuring Hybrid Composition]

[0221] The thermosetting / photosetting hybrid curing composition is prepared by combining the following curing agent, photoinitiator, gloss modifier, UV absorber, light stabilizer and diluent in a polymer solution A and a monomer as described below.

[0222] Polymer solution A

[0223] 80 g of methyl methacrylate and 20 g of 2-hydroxyethyl methacrylate were introduced into a four-necked flask equipped with a stirrer, a nitrogen inlet tube, and a reflux condenser. 100 g of ethyl acetate was added to dissolve them, and the mixture was stirred in an oil bath under a nitrogen atmosphere. Then, 0.2 g of α,α'-azobisisobutyronitrile was added to initiate polymerization. The mixture was heated and stirred in an oil bath at 60°C for 5 hours to obtain a colorless, viscous polymer solution A.

[0224] Formula: 40 parts by weight

[0225] ·monomer

[0226] Product Name: Dipentaerythritol Hexaacrylate

[0227] Formula: 40 parts by weight

[0228] Hardener

[0229] Product name: Duranate24A-100 (manufactured by Asahi Kasei Co., Ltd.)

[0230] Mixture: 10 parts by weight

[0231] Photoinitiator

[0232] Product Name: IRGACURE 184 (Manufactured by BASF)

[0233] Mixture: 10 parts by weight

[0234] Gloss modifier (inorganic particles)

[0235] Product Name: Sunsphere H122 (Manufactured by AGC Si-Tech Co., Ltd.)

[0236] Characteristics: Spherical, average particle size 12μm, pore volume 2ml / g

[0237] Mixture: 10 parts by weight

[0238] • Ultraviolet absorbers

[0239] Product Name: Tinuvin 400 (Manufactured by BASF)

[0240] Mixture: 5.0 parts by weight

[0241] Light stabilizers

[0242] Product Name: Tinuvin 123 (Manufactured by BASF)

[0243] Mixture: 2.0 parts by weight

[0244] • Diluent

[0245] Product Name: Ethyl Acetate

[0246] Mixture: 50 parts by weight

[0247] Experimental Example 1

[0248] For the decorative sheets prepared in the examples and comparative examples, the proportion of the antiviral agent's center point located in the middle or upper layer (i.e., above the middle layer) of the cross-linked cured resin layer, the arithmetic mean roughness Ra of the surface of the cross-linked cured resin layer, and the antiviral performance were evaluated. The measurement and evaluation methods are as follows.

[0249] <Surface Roughness>

[0250] Using a surface roughness measuring instrument (product number "SURFCOM-FLEX-50A", manufactured by Tokyo Seimitsu Co., Ltd.), the arithmetic mean roughness Ra as defined in JIS B0601 (2001) was measured under the following conditions. Furthermore, based on the measured Ra, the appropriate evaluation length and cutoff value were changed, and the measurement was repeated.

[0251] (Measurement conditions) Ra is greater than 0.1 μm and less than 2 μm.

[0252] Number of measurements: n = 5 (any 5 points)

[0253] Calculation standard: JIS'01

[0254] Type of measurement: Roughness measurement

[0255] Evaluation length: 4.0mm

[0256] Cutoff value: 0.8mm

[0257] Measurement speed: 0.60 mm / s

[0258] Filter type: Gaussian

[0259] Shape Removal: Straight Lines

[0260] (Measurement conditions) Ra is greater than 2 μm and less than 10 μm.

[0261] Number of measurements: n = 5 (any 5 points)

[0262] Calculation standard: JIS'01

[0263] Type of measurement: Roughness measurement

[0264] Evaluation length: 12.5mm

[0265] Cutoff value: 2.5mm

[0266] Measurement speed: 0.60 mm / s

[0267] Filter type: Gaussian

[0268] Shape Removal: Straight Lines

[0269] (Measurement conditions) Ra is greater than 10 μm and less than 80 μm.

[0270] Number of measurements: n = 5 (any 5 points)

[0271] Calculation standard: JIS'01

[0272] Type of measurement: Roughness measurement

[0273] Evaluation length: 40mm

[0274] Cutoff value: 8mm

[0275] Measurement speed: 0.60 mm / s

[0276] Filter type: Gaussian

[0277] Shape Removal: Straight Lines

[0278] <Cross-section observation>

[0279] 1) To observe the cross-section of the prepared decorative piece, a selected area is cut along the thickness direction of the decorative piece using a single-edged trimming razor.

[0280] 2) The width of 200 μm was observed from the cross-section of the cut decorative piece using a digital microscope (manufactured by Keyence, model: VHX-7000, magnification: 200x).

[0281] 3) In the entire area of ​​the observed cross-sectional photograph, identify the location of the center point of the antiviral agent, and use the following formula to calculate the proportion of antiviral agent whose center point exists in the middle or upper layer (i.e. above the middle layer) of the cross-linked cured resin layer.

[0282] (Number of antiviral agents present at the center point in the middle or upper layer (i.e., above the middle layer) / Number of antiviral agents present in the entire area of ​​the observed cross-sectional photograph) × 100 (%)

[0283] <Antiviral properties>

[0284] For the decorative sheets prepared in the examples and comparative examples, antiviral performance tests were conducted according to the method based on antiviral testing method (ISO 21702), and the antiviral activity against feline calicivirus, a non-enveloped virus, was evaluated based on the following evaluation criteria. The evaluation criteria are as follows.

[0285] Virus type: Non-enveloped virus (feline calicivirus)

[0286] +: The antiviral activity value is above 2.0 after 24 hours.

[0287] -: The antiviral activity value is less than 2.0 after 24 hours.

[0288] The results are shown in Table 1 below.

[0289] [Table 1]

[0290]

[0291] According to the results in Table 1, the decorative sheets of Examples 1 to 4 containing the antiviral agent of the present invention can obtain antiviral properties against non-enveloped viruses with an amount that does not damage the surface properties of the surface protective layer.

[0292] Explanation of reference numerals in the attached figures

[0293] 1: Antiviral decorative sheet; 2: Substrate sheet; 3: Pattern layer; 4: Transparent adhesive layer; 5: Transparent resin layer; 6: Primer layer; 7: Cross-linked curing resin layer (surface protective layer); 8: Back primer layer; 9: Antiviral agent; 10: Adhesive sheet; 11: Antiviral adhesive processing sheet; 12: Decorative panel substrate; 13: Antiviral decorative panel; A: Thickness of the smooth portion of the cross-linked curing resin layer (surface protective layer); a: Upper layer; b: Middle layer; c: Lower layer.

Claims

1. An antiviral decorative sheet having a cross-linked cured resin layer on its outermost layer, characterized in that: (1) The cross-linked curing resin layer contains a cured product of the cross-linked curing resin and an antiviral agent. (2) The antiviral agent is an antiviral agent that is effective against non-enveloped viruses. The antiviral agent contains a carboxylic acid derivative and a styrene polymer derivative. At least as a component of the carboxylic acid derivative, it contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine.

2. The antiviral decorative sheet as described in claim 1, characterized in that: The antiviral agent, as a component of the styrene polymer derivative, contains all of the following: triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine.

3. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The cross-linked cured resin layer has fine irregularities on its outermost surface with an arithmetic mean roughness Ra of 0.1 μm or more.

4. The antiviral decorative sheet as described in claim 3, characterized in that: The arithmetic mean roughness Ra of the micro-uneven surface is less than 40 μm.

5. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The cross-linked cured resin layer also contains an antibacterial agent composed of silver-containing inorganic particles.

6. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The cross-linked cured resin layer also contains a triazine-based ultraviolet absorber and / or a light stabilizer.

7. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The ratio of the carboxylic acid derivative to the styrene polymer derivative in the antiviral agent is 1:1 to 10:1 by mass.

8. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: When the thickness of the smooth portion of the cross-linked cured resin layer is divided into three equal parts to form a lower layer, a middle layer, and an upper layer, the center point of more than 50% of the antiviral agent in the whole is located in the middle layer or the upper layer.

9. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The antiviral agent is present in 1 to 10 parts by weight relative to 100 parts by weight of the cross-linked cured resin.

10. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The average thickness of the smooth portion of the cross-linked cured resin layer is more than 2 μm and less than 35 μm.

11. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The antiviral agent has an average particle size of 2 μm to 15 μm.

12. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The cross-linking curing resin includes an ionizing radiation curing resin.

13. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: The Martens hardness of the cross-linked cured resin layer is 30 N / mm. 2 Above 180N / mm 2 the following.

14. The antiviral decorative sheet as described in claim 1 or 2, characterized in that: It is composed of a laminate having at least one substrate sheet, a patterned layer, a transparent thermoplastic resin layer and the cross-linked curable resin layer in the thickness direction in sequence.

15. The antiviral decorative sheet as described in claim 14, characterized in that: The substrate sheet and / or the transparent thermoplastic resin layer have a Marlowen hardness of 30 N / mm. 2 Above 80N / mm 2 the following.

16. An antiviral adhesive processing sheet, characterized in that: It is composed of a laminate having at least an adhesive sheet and an antiviral decorative sheet as described in claim 1 or 2 in sequence in the thickness direction.

17. An antiviral decorative panel, characterized in that: It is composed of a laminate having at least a decorative panel substrate and the antiviral decorative sheet as described in claim 1 or 2 in sequence in the thickness direction.

18. An antiviral decorative panel, characterized in that: It is composed of a laminate having at least a decorative panel substrate and the antiviral adhesive processing sheet as described in claim 16 in the thickness direction.

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