WO2024005082A1

WO2024005082A1 - Anti-viral decorative sheet, and anti-viral adhesive processed sheet and anti-viral decorative board each using same

Info

Publication number: WO2024005082A1
Application number: PCT/JP2023/024007
Authority: WO
Inventors: 智美中島; 陽亮住田; 梨紗良波; 雅貴和田; 利成茅原
Original assignee: 大日本印刷株式会社
Priority date: 2022-06-30
Filing date: 2023-06-28
Publication date: 2024-01-04

Abstract

The present invention provides an anti-viral decorative sheet that exhibits an anti-viral effect particularly against a non-enveloped virus while keeping the surface performance of a surface-protecting layer.　More specifically, the present invention provides an anti-viral decorative sheet having a crosslinking-cured resin layer as an outermost surface layer, the anti-viral decorative sheet being characterized in that (1) the crosslinking-cured resin layer comprises a cured product of a crosslinking-cured resin and an anti-viral agent and (2) the anti-viral agent has an anti-viral effect against a non-enveloped virus, contains a carboxylic acid derivative and a styrene polymer derivative, and contains, as at least constituent components for the carboxylic acid derivative, all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine and N,N,2,2-tetramethyl-1,3-propanediamine.

Description

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

The present invention relates to an antiviral decorative sheet, an antiviral adhesive processed sheet using the same, and an antiviral decorative board, and in particular an antiviral decorative sheet having antiviral properties against non-enveloped viruses, and an antiviral decorative sheet using the same. The present invention relates to an antiviral adhesive sheet and an antiviral decorative board.

Conventionally, various decorative sheets have been used for surface decoration of fittings, floors, walls, etc. used as interior materials of buildings. For example, decorative sheets are widely used that are composed of a laminate that has a base sheet, a transparent resin layer, and a surface protective layer in order in the thickness direction, and decorations can be applied on the base sheet as necessary. A primer layer may be provided between the transparent resin layer and the surface protection layer to improve adhesion, and an ionizing radiation curing type may be added to the resin component of the surface protection layer to increase the scratch resistance of the surface protection layer. It is known that it contains resin.

As an example of adding functionality to a decorative sheet, a decorative sheet with antiviral properties is known. As a specific example, for example, Patent Document 1 states that ``a surface protective layer formed of a single layer or a multilayer is provided on a base sheet, and an antiviral agent is provided on the outermost layer located on the outermost surface of the surface protective layer. "A decorative sheet to which is added." is disclosed.

Patent Document 1 discloses that the antiviral agent contains at least one of a carboxylic acid material, a sulfonic acid material, or a quaternary ammonium salt as an organic material, so that it is effective against both enveloped viruses and non-enveloped viruses. It is stated that an antiviral effect is exhibited (Claim 7 and paragraphs [0044] to [0047]). However, in the Examples of Patent Document 1, it is stated that antiviral properties against enveloped viruses were confirmed as an antiviral performance test, but antiviral properties against non-enveloped viruses were not specifically confirmed.

In general, enveloped viruses can be inactivated relatively easily by destroying the envelope (lipid layer), so it is easy to obtain an antiviral effect with a wide variety of known antiviral agents, and the effect can be expressed even with a small amount added. Since it is easy to use, it is possible to impart antiviral performance while maintaining the surface performance that the surface protective layer should originally have. On the other hand, non-enveloped viruses are relatively difficult to inactivate, and it is difficult to obtain the same effect with the same antiviral agent and the same additive amount as for enveloped viruses. In order to obtain the same effect with the same antiviral agent, it is necessary to increase the amount added, which poses a problem that the surface performance that the surface protective layer should originally have may be inhibited.

Therefore, there is a need to develop an antiviral decorative sheet that maintains the surface performance of the surface protective layer and exhibits antiviral effects, especially against non-enveloped viruses.

Japanese Patent Application Publication No. 2022-41101

An object of the present invention is to provide an antiviral decorative sheet that exhibits an antiviral effect particularly against non-enveloped viruses while maintaining the surface performance of the surface protective layer. Another object of the present invention is to provide an antiviral pressure-sensitive adhesive sheet and an antiviral decorative board using the decorative sheet.

As a result of extensive research, the present inventors have discovered that the above object can be achieved by containing a specific antiviral agent in the surface protective layer, and have completed the present invention.

That is, the present invention relates to the following antiviral decorative sheet, antiviral adhesive processed sheet and antiviral decorative board using the same.
1. A decorative sheet comprising a crosslinked curable resin layer on the outermost layer,
(1) The crosslinked curable resin layer contains a cured product of a crosslinked curable resin and an antiviral agent,
(2) The antiviral agent is an antiviral agent having antiviral properties against non-enveloped viruses, and contains a carboxylic acid derivative and a styrene polymer derivative, and at least triethylamine, N , N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine,
An antiviral cosmetic sheet characterized by:
2. The antiviral agent contains triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1, as constituent components of the styrene polymer derivative. The antiviral decorative sheet according to item 1 above, which contains all of 3-propanediamine.
3. 3. The antiviral decorative sheet according to

item

1 or 2, wherein the crosslinked curable resin layer has fine irregularities having an arithmetic mean roughness Ra of 0.1 μm or more on the outermost surface.
4. 4. The antiviral decorative sheet according to item 3, wherein the arithmetic mean roughness Ra of the fine irregularities is 40 μm or less.
5. 5. The antiviral decorative sheet according to any one of items 1 to 4 above, wherein the crosslinked curable resin layer further contains an antibacterial agent made of silver-containing inorganic particles.
6. 6. The antiviral decorative sheet according to any one of items 1 to 5 above, wherein the crosslinked curable resin layer further contains a triazine-based ultraviolet absorber and/or a light stabilizer.
7. The antiviral agent according to any one of items 1 to 6 above, wherein the antiviral agent contains the carboxylic acid derivative and the styrene polymer derivative in a mass ratio of 1:1 to 10:1. Cosmetic sheet.
8. When the thickness of the smooth part of the cross-linked curable resin layer is divided into thirds and divided into a lower layer, a middle layer, and an upper layer, the central point of the antiviral agent that accounts for 50% or more of the entire antiviral agent is the middle layer. or the antiviral decorative sheet according to any one of items 1 to 7 above, which is present in the upper layer.
9. The antiviral decorative sheet according to any one of items 1 to 8 above, which contains the antiviral agent in an amount of 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the crosslinked curable resin.
10. 10. The antiviral decorative sheet according to any one of items 1 to 9 above, wherein the average thickness of the smooth portion of the crosslinked curable resin layer is 2 μm or more and 35 μm or less.
11. The antiviral decorative sheet according to any one of items 1 to 10 above, wherein the antiviral agent has an average particle diameter of 2 μm or more and 15 μm or less.
12. 12. The antiviral decorative sheet according to any one of items 1 to 11 above, wherein the crosslinked curable resin contains an ionizing radiation curable resin.
13. 13. The antiviral decorative sheet according to any one of items 1 to 12 above, wherein the crosslinked curable resin layer has a Martens hardness of 30 N/mm ² or more and 180 N/mm ² or less.
14. Any one of items 1 to 13 above, which is composed of a laminate comprising at least a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and the crosslinked curable resin layer in order in the thickness direction. The antiviral cosmetic sheet described in section.
15. 15. The antiviral decorative sheet according to item 14, wherein the base sheet and/or the transparent thermoplastic resin layer has a Martens hardness of 30 N/mm ² or more and 80 N/mm ² or less.
16. An antiviral adhesive processed sheet comprising a laminate comprising at least an adhesive sheet and an antiviral decorative sheet according to any one of items 1 to 15 above, in order in the thickness direction.
17. An antiviral decorative board comprising a laminate comprising at least a decorative board base material and an antiviral decorative sheet according to any one of items 1 to 15 above, in order in the thickness direction.
18. An antiviral decorative board comprising a laminate including at least a decorative board base material and an antiviral pressure-sensitive adhesive sheet according to item 16 above, in order in the thickness direction.

The antiviral decorative sheet of the present invention contains a specific antiviral agent in the crosslinked curable resin layer (surface protective layer), which is the outermost layer, so that the surface performance of the surface protective layer (scratch resistance, impact resistance, It is possible to exhibit an antiviral effect particularly against non-enveloped viruses while maintaining arbitrary surface properties that a surface protective layer should originally have, such as chemical resistance. Moreover, the decorative sheet can be made into an antiviral adhesive processed sheet by being combined with an adhesive sheet, and the decorative sheet and the adhesive processed sheet can be made into an antiviral decorative board by being combined with a decorative laminate base material, respectively.

FIG. 1 is a schematic cross-sectional view showing an example of an antiviral decorative sheet of the present invention. FIG. 1 is a schematic cross-sectional view showing an example of an antiviral pressure-sensitive adhesive sheet of the present invention. FIG. 1 is a cross-sectional view schematically showing an example of the constituent members of the antiviral decorative board of the present invention. FIG. 2 is a schematic cross-sectional view for explaining the relationship between the thickness A of the smooth portion of the crosslinked curable 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. It is a figure which shows the diamond indenter (a) used for the measurement of Martens hardness in this specification, the schematic diagram (b) of indentation operation, and an example of indentation load and displacement (c).

1. Antiviral Decorative Sheet The antiviral decorative sheet of the present invention (hereinafter also referred to as "the decorative sheet of the present invention") is a decorative sheet comprising a crosslinked curable resin layer on the outermost layer,
(1) The crosslinked curable resin layer contains a cured product of a crosslinked curable resin and an antiviral agent,
(2) The antiviral agent is an antiviral agent having antiviral properties against non-enveloped viruses, and contains a carboxylic acid derivative and a styrene polymer derivative, and at least triethylamine, N , N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine,
It is characterized by

The decorative sheet of the present invention improves the surface performance (scratch resistance, impact resistance, chemical resistance) of the surface protection layer by containing a specific antiviral agent in the crosslinked curing resin layer (surface protection layer), which is the outermost layer. It is possible to exhibit an antiviral effect particularly against non-enveloped viruses while maintaining the arbitrary surface properties that a surface protective layer should originally have. Moreover, the decorative sheet can be made into an antiviral adhesive processed sheet by being combined with an adhesive sheet, and the decorative sheet and the adhesive processed sheet can be made into an antiviral decorative board by being combined with a decorative laminate base material, respectively.

The decorative sheet of the present invention includes a cross-linked curable resin layer on the outermost layer, and the cross-linked curable resin layer and the antiviral agent contained therein satisfy the predetermined requirements shown in (1) and (2) above. If so, the specific structure (layer structure) is not limited.

In a specific embodiment, the decorative sheet of the present invention is composed of a laminate including at least a base sheet, a transparent thermoplastic resin layer, and a crosslinked curable resin layer in this order in the thickness direction. It's okay. Further, the decorative sheet of the present invention is composed of a laminate including, in order in the thickness direction, for example, a base sheet, a pattern layer, a transparent thermoplastic resin layer, and a crosslinked curable resin layer. It's okay. In the decorative sheet of the present invention, the outermost crosslinked curable resin layer has a role as a so-called surface protective layer.

FIG. 1 is a schematic cross-sectional view showing an example of the decorative sheet of the present invention. In FIG. 1, a pattern layer 3, a transparent adhesive layer 4, a transparent thermoplastic resin layer 5, a primer layer 6, and a cross-linked curable resin layer 7 are laminated in this order on a base sheet 2. A back primer layer 8 is further provided on the back side of the sheet 2. Furthermore, an embossed uneven pattern is formed. Further, in the crosslinked curable resin layer 7, the presence mode of the antiviral agent 9 is schematically shown. The thickness of the cross-linked curable resin layer 7 (thickness of the smooth part excluding the bulges on the outermost surface) is the thickness shown by A in the figure. A bulge (convex portion) exceeding the thickness A of the smooth portion may be formed by being present on the surface side. Moreover, fine irregularities may be formed on the outermost surface of the crosslinked curable resin layer 7 in addition to the convex portions caused by the antiviral agent 9. Note that the convex portion shown in FIG. 1 is a bulge caused by the antiviral agent 9, but the antiviral agent 9 itself is not exposed, but is a bulge as a crosslinked curable resin layer.

Furthermore, the present invention provides an antiviral adhesive sheet (hereinafter also referred to as "adhesive sheet of the present invention") which is composed of a laminate that includes at least an adhesive sheet and a decorative sheet of the present invention in this order in the thickness direction. The present invention also includes the inventions (for example, the embodiment shown in FIG. 2). Note that although FIG. 2 illustrates the configuration of the adhesive processed sheet 11 that includes the adhesive sheet 10 on the back surface of the decorative sheet 1 shown in FIG. 1, the configuration of the decorative sheet 1 is not limited to this.

Furthermore, the present invention provides an antiviral decorative board (hereinafter referred to as " Also included is the invention (for example, the embodiment shown in FIG. 3) (also referred to as "the decorative laminate of the present invention"). In addition, in FIG. 3, the structure of the decorative board 13 which equipped the back surface of the decorative sheet 1 shown in FIG. 1 with the decorative board base material 12 is illustrated. Further, the decorative board 13 may have a configuration in which the decorative board base material 12 is provided on the back surface of the adhesive processed sheet 11 shown in FIG.

In this specification, the surface that is visually recognized after construction of the decorative sheet of the present invention, that is, the direction in which the crosslinked curable resin layer (surface protection layer) is laminated when viewed from the base sheet, is referred to as "top" or "front". The direction in which the back primer layer is laminated when viewed from the base sheet is called the "bottom" or "back surface." Such a relationship is the same in the case of the adhesive processed sheet of the present invention and the decorative board of the present invention. In addition, when referring to "the side of the cross-linked curable resin layer (surface protective layer)" in the laminate, it is also abbreviated as "the cross-linked curable resin layer (surface protective layer) side."

Hereinafter, each layer of the decorative sheet of the present invention will be explained using FIG. 1 as an example. However, the layer structure of the decorative sheet of the present invention is not limited to the embodiment shown in FIG. 1, and as described above, various layer structures can be adopted as a laminate. In the following description, the lower and upper limits of the numerical range represented by "~" mean "more than or equal to" (for example, if α to β, it is more than or equal to α and less than or equal to β).　

Base material sheet The base material sheet has picture pattern layers etc. laminated in sequence on its surface (front surface). Note that the outermost layer is a crosslinked curable resin layer (surface protection layer).

Examples of the base sheet include a variety of resin films, paper, resin-impregnated paper, etc. Among resin films, those containing thermoplastic resin as a resin component are preferred. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, methacrylic esters, and the like. In the present invention, at least one of polyvinyl chloride and polyolefin (polyethylene, polypropylene, etc.) can be suitably used.

The base sheet may be colored. For example, a coloring agent (pigment or dye) can be added to a thermoplastic resin to color it. As the coloring agent, for example, inorganic pigments such as titanium dioxide, carbon black, and iron oxide, and organic pigments such as phthalocyanine blue, as well as various dyes can be used. One type or two or more types can be selected from these. Further, the amount of the coloring agent added may be appropriately set depending on the desired color tone and the like.

The base sheet contains various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers as necessary. It may be

The thickness of the base sheet can be appropriately set depending on the purpose of the final product, how it is used, etc., but is generally preferably 50 to 250 μm.

If necessary, the surface (front surface) of the base sheet may be subjected to corona discharge treatment in order to improve the adhesion of the ink forming the picture pattern layer. The method and conditions for the corona discharge treatment may be carried out according to known methods. In addition, if necessary, the back side of the base sheet may be subjected to corona discharge treatment, a picture pattern layer (so-called back print), a back primer layer (described later), a backer layer (described later), etc. Good too.

Picture Pattern Layer The picture pattern layer is an arbitrary layer that imparts a desired picture (design) to the decorative sheet of the present invention, and the type of picture is not limited. Examples include wood grain patterns, leather patterns, stone grain patterns, sand grain patterns, tiling patterns, brickwork patterns, cloth grain patterns, geometric figures, letters, symbols, abstract patterns, flower patterns, landscapes, characters, and the like.

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

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

In addition to hydrophilically treated polyester urethane resins, binder resins include polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, and rosin derivatives. , alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, etc. can also be used in combination. More specifically, for example, polyacrylamide resin, poly(meth)acrylic acid resin, polyethylene oxide resin, polyN-vinylpyrrolidone resin, water-soluble polyester resin, water-soluble polyamide resin, water-soluble amino type resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, and polysaccharides; etc. can also be used. Furthermore, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth)acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, or modified products thereof, and other resins may also be used. can. The above binder resins can be used alone or in combination of two or more.

Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-acetic acid. - Ester organic solvents such as ethoxyethyl; alcohol organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Ether organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorinated organic solvents such as dichloromethane, carbon tetrachloride, trichlorethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

Examples of the printing method used to form the picture pattern layer include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. In addition, when forming a pattern layer that is solid on the entire surface, examples of methods include roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, dip coating, etc. Various coating methods such as a coating method can be mentioned. In addition, hand-drawing methods, suminagashi methods, photographic methods, transfer methods, laser beam drawing methods, electron beam drawing methods, partial vapor deposition of metals, etching methods, etc. may be used, or they may be used in combination with other forming methods. good.

The thickness of the picture pattern layer is not particularly limited and can be set as appropriate depending on the product characteristics, but the layer thickness is approximately 0.1 to 15 μm.

Transparent resin layer The transparent resin layer is a layer that can be provided arbitrarily, and is not particularly limited as long as it is transparent, and may be colorless and transparent, colored transparent, translucent, or the like. Although the material of the transparent resin layer is not limited, it is preferably made of thermoplastic resin. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, methacrylic esters, and the like. In the present invention, at least one of polyvinyl chloride and polyolefin (polyethylene, polypropylene, etc.) can be suitably used. In this specification, when the transparent resin layer contains a thermoplastic resin, the transparent resin layer is particularly referred to as a "transparent thermoplastic resin layer."

Note that the transparent resin layer may be colored as long as it has transparency.

In addition, as long as the transparent resin layer has transparency, it may contain various additives such as flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers as necessary. It's okay.

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

Transparent Adhesive Layer A transparent adhesive layer may be formed in order to improve the adhesion between the pattern layer and the transparent resin layer or the cross-linked curable resin layer (surface protection layer) described below. The transparent adhesive layer is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, translucent, or the like.

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

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.

Primer layer A primer layer for a crosslinked curable resin layer (surface protection layer) may be provided on the transparent resin layer. This primer layer has the effect of increasing the adhesion between the transparent resin layer and the cross-linked curable resin layer described below, and in combination with the cross-linked curable resin layer, it can improve the bending processability and scratch resistance of the decorative sheet. . The primer layer is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, translucent, or the like.

The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. Examples of primer agents include acrylic modified urethane resins (acrylic urethane copolymer resins), urethane resin primers made of polycarbonate-based acrylic urethane copolymer resins, and urethane-cellulose resins (for example, urethane and nitrified cotton). A resin-based primer agent made of a block copolymer of acrylic and urethane, etc. may be mentioned. Among these, a urethane resin-based primer agent containing a polycarbonate-based acrylic urethane copolymer resin can be preferably used from the viewpoint of scratch resistance and weather resistance.

Additives may be added to the primer agent if necessary. Examples of additives include weathering agents such as ultraviolet absorbers and light stabilizers; fillers such as silica, calcium carbonate, and clay; flame retardants such as magnesium hydroxide; antioxidants; lubricants; and blowing agents. The blending amount of the additive can be appropriately set depending on the product characteristics.

Among the above additives, examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and the like. As the light stabilizer, for example, hindered amine light stabilizer (HALS) is suitable. The content of these weathering agents is not limited, but may be approximately 1,000 to 100,000 ppm by mass for each of the ultraviolet absorber and light stabilizer. In particular, in the present invention, it is preferable to use a triazine-based ultraviolet absorber and/or a hindered amine-based light stabilizer.

The thickness of the primer layer is not limited, but is preferably 0.5 μm or more and 12 μm or less, more preferably 1 μm or more and 8 μm or less. By setting it within this range, the folding processability and scratch resistance of the decorative sheet can be easily improved by combining with the crosslinked curable resin layer. In addition, it becomes easier to contain additives such as weathering agents, and it becomes easier to impart weather resistance to the decorative sheet.

Cross-linked curing resin layer (surface protection layer)
The decorative sheet of the present invention includes a cross-linked curable resin layer (surface protective layer) on the outermost layer, and the cross-linked curable resin layer and the antiviral agent contained therein meet the predetermined conditions shown in (1) and (2) below. By satisfying the requirements, it is possible to maintain the surface performance of the surface protective layer while exhibiting an antiviral effect, especially against non-enveloped viruses.
(1) The crosslinked curable resin layer contains a cured product of a crosslinked curable resin and an antiviral agent,
(2) The antiviral agent is an antiviral agent having antiviral properties against non-enveloped viruses, and contains a carboxylic acid derivative and a styrene polymer derivative, and at least triethylamine, N , N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine.

The crosslinked curable resin is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, translucent, etc.

The resin component of the crosslinked curable resin is not limited, but preferably contains an ionizing radiation curable resin or a two-part curable urethane resin. Preferably, the material is substantially made of these resins. When the outermost layer is formed of an ionizing radiation curable resin or a two-component urethane resin, the abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, etc. of the decorative sheet can be easily improved. Among these, ionizing radiation curable resins are preferred. By using these resins, it becomes easier to adjust the Martens hardness of the cross-linked curable resin layer to 30 N/mm ² or more and 180 N/mm ² or less, thereby increasing the slip resistance value (C.S.) as an index of anti-slip property. R. value) can be easily adjusted to 0.25 or more.

In addition, the above C. S. R. As an index of anti-slip property for various uses in terms of value, if it is 0.25 or more (especially 0.25 or more and less than 0.30), it can be judged that it is suitable for fittings, and if it is 0.30 or more (especially 0.30 If the value is 0.38 or more (especially 0.38 or more and less than 0.50), it is considered suitable for use as a normal floor, and if it is 0.38 or more (particularly 0.38 or more and less than 0.50), it is suitable for use as an anti-slip floor that exhibits a high level of anti-slip properties. It can be determined that

Ionizing radiation-curable resins are not particularly limited, and include prepolymers (including oligomers) and/or monomers containing radically polymerizable double bonds in their molecules that can be polymerized and crosslinked by irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin whose main component is These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a crosslinking curing reaction.

Specifically, the prepolymer or monomer is a compound having a radically polymerizable unsaturated group such as a (meth)acryloyl group or a (meth)acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group in the molecule. can be mentioned. Also preferred is a polyene/thiol-based prepolymer made of a combination of polyene and polythiol. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

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

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

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy compounds, and vinyl ether-based resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include polyurethane made of diol and diisocyanate with allyl alcohol added to both ends.

In the present invention, as an ionizing radiation curable resin, a urethane (meth)acrylate oligomer (A) having a weight average molecular weight of 1,000 to 3,000 and having two radically polymerizable unsaturated groups in one molecule and a urethane (meth)acrylate oligomer (A) having two radically polymerizable unsaturated groups in one molecule, A mixed resin containing an aliphatic urethane (meth)acrylate oligomer (B) having 15 radically polymerizable unsaturated groups can be used. When using such a mixed resin, it is easy to obtain effects such as scratch resistance and stain resistance due to the high crosslinking density, and by appropriately adjusting the weight average molecular weight and/or blending amount, the crosslinked curable resin layer can be formed. It has the advantage that it is easy to adjust the surface performance according to the application, such as by making it into a form with excellent impact resistance or a form with excellent processing suitability such as V-cut.

The content ratio of the oligomer (A) and the oligomer (B) in the ionizing radiation curable resin is not limited, but when the total amount of the oligomer (A) and the oligomer (B) is 100% by mass, the oligomer It is preferable that (A) be in the range of 50 to 90% by mass and the oligomer (B) be in the range of 10 to 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 or more and 180 N/mm ² or less, and the anti-slip property of the cross-linked curable resin layer can be used for various purposes (slip resistance value (C.S.R. value) of 0.25 or more).

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

Resin A is an aliphatic urethane (meth)acrylate having an isocyanurate skeleton, and is not limited as long as it satisfies this requirement. ) Acrylates are preferred. Specific examples include a trimer of hexamethylene diisocyanate (particularly 1,6-hexamethylene diisocyanate), a trimer of tolylene diisocyanate, a trimer of metaxylene diisocyanate, and the like. In addition, since tolylene diisocyanate and metaxylene diisocyanate may have inferior weather resistance than hexamethylene diisocyanate in that they have a benzene ring, these diisocyanates are preferably hydrogenated. These resins A have the effect of improving the stain resistance, alkali resistance, etc. of the crosslinked curable resin layer.

Resin B is an aliphatic urethane (meth)acrylate that does not have an isocyanurate skeleton but has an alicyclic skeleton, and is not limited as long as it satisfies this requirement, but for example, at least one of isophorone and cyclohexane as the alicyclic skeleton. It is preferable to have. Specifically, examples include urethane oligomers, which are polymers containing isophorone diisocyanate and butanediol as monomers, with acrylate added to the ends, and PG-modified diacrylates of hydrogenated dicyclohexylmethane diisocyanate (hydrogenated MDI). It will be done. These resins B have the effect of imparting flexibility to the cross-linked curable resin layer, and when combined with resin A, the cross-linked curable resin layer has excellent stain resistance, alkali resistance, etc. over a long period of time, as well as impact resistance. It has the effect of suppressing the occurrence of cracks and cracks when applied or processed.

Ionizing radiation-curable resins are mainly composed of prepolymers (including oligomers) and/or monomers that contain radically polymerizable double bonds in their molecules that can be polymerized and crosslinked by irradiation with ionizing radiation such as ultraviolet rays and electron beams. The curing reaction is usually a crosslinking curing reaction. As the ionizing radiation used to cure the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of curing molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion beams, etc. may also be used. In addition, in the present invention, among ionizing radiation curable resins, the properties of the raw material resin can be directly reflected in the properties of the resin components of the crosslinked curable resin layer since it does not contain a photopolymerization initiator, and when a weathering agent is used in combination. It is preferable to use an electron beam curable resin from the viewpoint of widening the range of selection.

Two-component curable urethane resins are not particularly limited, but include polyol components (acrylic polyols, polyester polyols, polyether polyols, epoxy polyols, etc.) having an OH group as a main component, and isocyanate components (tolylene diethylene chloride) as a curing agent component. isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, etc.) can be used.

The crosslinked curable resins exemplified above can be used alone or in combination of two or more.

The crosslinked curable resin layer contains an antiviral agent in addition to the cured product of the crosslinked curable resin. Viruses are generally classified into enveloped viruses (having an envelope) and non-enveloped viruses (having no envelope), depending on the presence or absence of an envelope (lipid membrane). Enveloped viruses include, for example, influenza virus, herpes virus, AIDS virus, hepatitis B virus, and the like. Furthermore, non-enveloped viruses include, for example, norovirus, feline calicivirus, rhinovirus, adenovirus, and the like.

The antiviral agent used in the present invention (hereinafter also referred to as "the antiviral agent of the present invention") is an antiviral agent that has antiviral properties against non-enveloped viruses and contains carboxylic acid derivatives and styrene polymer derivatives. The carboxylic acid derivative contains at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3- It is characterized by containing all propanediamine. The antiviral agent of the present invention further contains triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2- as constituent components of the styrene polymer derivative. Preferably, all of the tetramethyl-1,3-propanediamine is contained. These compounds are detected as constituents when the organic structures of carboxylic acid derivatives and styrene polymer derivatives are analyzed.

The carboxylic acid derivative is not limited as long as the above-mentioned predetermined component is detected when the organic structure is analyzed, but examples of preparation methods include, for example, cyclohexanecarboxylic acid (manufactured by Shin Nippon Chemical Co., Ltd.), triethylamine, etc. (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- A carboxylic acid derivative can be prepared by mixing and reacting raw materials containing 1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

The styrene polymer derivative is preferably one in which the above-described predetermined constituent components are detected when the organic structure is analyzed, and examples of preparation methods include, for example, sodium p-styrene sulfonate (manufactured by Tosoh Corporation). ; trade name "Spinomer NaSS"), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.), and denatured ethanol (manufactured by Wako Pure Chemical Industries, Ltd.; trade name "86% Ethanol-ME") are mixed and reacted to form a styrene polymer. Derivatives can be prepared.

The antiviral agent of the present invention can be produced by mixing (kneading) the above carboxylic acid derivative and the above styrene polymer derivative at a desired mixing ratio, and pulverizing the mixture to a desired size using a known pulverizing means such as a jet mill. It can be prepared. Although the content ratio of the carboxylic acid derivative and the styrene polymer derivative is not limited, it is preferable that the mass ratio is 1:1 to 10:1, and 2:1 to 5:1. It is more preferable that there be. By setting such a content ratio (mixing ratio), it becomes easier to obtain an antiviral effect against non-enveloped viruses.

The shape of the antiviral agent (primary particles) of the present invention is not limited, but examples thereof include spheres, ellipsoids, polyhedrons, scales, and the like. Further, the average particle diameter of the antiviral agent of the present invention is not limited, but it is preferably 2 μm or more and 15 μm or less, and more preferably 3 μm or more and 12 μm or less. Note that the average particle diameter in this specification is a value specified as the mass average value D50 in particle size distribution measurement by laser light diffraction method.

The reason why the antiviral agent of the present invention has antiviral properties against viruses (particularly non-enveloped viruses) is presumed as follows, but is not limited to the mechanism presumed below. Various viruses bind to sugar chain receptors on the surface of host cells (the sugar chain end is neuraminic acid) and invade into host cells, but the antiviral agent of the present invention has an ionic group similar to neuraminic acid, so it By binding to and capturing the virus instead of cells, it is thought to prevent the virus from binding to host cell receptors and exert an antiviral effect. Specifically, the plurality of amino groups described above that are constituents of the carboxylic acid derivative bind (capture) to the spike protein of an enveloped virus and the capsid (protein shell) of a non-enveloped virus. At the same time or dependently, enveloped viruses are thought to be inactivated by the sulfonic acid groups of styrene polymer derivatives destroying their envelopes, and non-enveloped viruses are thought to be inactivated by the carboxyl groups of carboxylic acid derivative compounds oxidizing capsids. It will be done. Furthermore, as mentioned above, the sulfonic acid group is thought to mainly contribute to the destruction of the envelope, but since it has oxidizing power, it is also involved in the oxidation of the capsid of non-enveloped viruses, just like the carboxy group. Therefore, in order to efficiently inactivate non-enveloped viruses and also inactivate enveloped viruses, it is effective to use a carboxylic acid derivative and a styrene polymer derivative at the same time. The antiviral agent of the present invention has an advantage over conventional products in that it can inactivate non-enveloped viruses at a content that does not impede the surface performance of the surface protective layer, but there is also a presumed mechanism for inactivating enveloped viruses. As described above, the antiviral agent of the present invention has an antiviral effect not only against non-enveloped viruses but also against enveloped viruses.

The content of the antiviral agent of the present invention with respect to 100 parts by mass of the crosslinked curable resin is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 2 parts by mass or more and 6 parts by mass or less. Within this content range, a predetermined antiviral effect can generally be exhibited without affecting the surface performance of the surface protective layer.

The thickness of the cross-linked curable resin layer is preferably such that the average thickness of the smooth portion is 2 μm or more when the cross-linked curable resin layer does not have convex portions caused by the antiviral agent of the present invention. When it has convex portions caused by the antiviral agent of the invention, it is preferable that the average thickness of the smooth portion excluding the convex portions is 2 μm or more. The average thickness of the smooth portion is preferably 4 μm or more among 2 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 is determined by the thickness of the flat area (thickness A in FIG. In this specification, it means the average value of the thickness of arbitrary 10 points in the width of 1 cm of the cross-sectional observation image of the cross-linked curable resin layer. "Width" is a direction perpendicular to the thickness direction.

For example, the crosslinked curable resin layer is formed by applying a composition for forming a crosslinked curable resin layer containing a crosslinked curable resin and the antiviral agent of the present invention onto the primer layer by a known coating method such as gravure coating or roll coating. It can be formed by curing the resin after coating. Specifically, after coating the composition for forming a cross-linked curable resin layer, the antiviral agent of the present invention lifts up in the coating film before it is completely cured, so that it reaches the outermost surface of the cross-linked curable resin layer. Even if protrusions are formed due to the antiviral agent, or the antiviral agent partially aggregates in the coating film, and the particle size of the antiviral agent becomes larger in appearance, there is no problem with the expression of antiviral performance. None.

In the present invention, when the thickness of the smooth part of the cross-linked curable resin layer is divided into three equal parts and divided into a lower layer, a middle layer, and an upper layer, 50% or more of the entire antiviral agent of the present invention (the entire number) It is preferable that the central point of the antiviral agent exists in the middle layer or the upper layer (that is, the middle layer or above). FIG. 4 exemplarily shows the relationship between the thickness A of the smooth portion of the crosslinked curable resin layer and the position of the center point of the antiviral agent. Here, for antiviral agents 9-1 and 9-2, the position of the center point of the antiviral agent is the middle layer or upper layer of the thickness of the smooth part of the crosslinked curing resin layer (the middle layer includes the lower layer). The antiviral agent 9-3 is an example in which the central point of the antiviral agent exists in the lower layer. . The center point of the antiviral agent is determined by drawing a circle with the smallest diameter in the cross-sectional observation image of the cross-linked cured resin layer so that the antiviral agent of the present invention, which has various shapes that are not necessarily circular, can be completely accommodated. The center of is set as the center point. The proportion of the central point of the antiviral agent of the present invention in the middle layer or upper layer (that is, the middle layer or above) is preferably 50% or more, more preferably 67% or more, as described above. Within this range, the antiviral effect of the antiviral agent of the present invention can be easily obtained. In addition, even in such a preferable embodiment, as mentioned above, if the content of the antiviral agent of the present invention is 10 parts by mass or less with respect to 100 parts by mass of the crosslinked curable resin, it generally does not affect the surface performance of the surface protective layer. It is possible to exert the desired antiviral effect without any need for treatment. For cross-sectional observation, after cutting the cross-linked cured resin layer in the thickness direction with a sharp blade such as a single-edged trimming razor or microtome, the cut surface (width 200 μm) was observed using a digital microscope (manufactured by Keyence Corporation, model number: This is done by observing with a VHX-7000 (magnification: 200x).

In the present invention, it is preferable that the crosslinked curable resin layer has fine irregularities with an arithmetic mean roughness Ra of 0.1 μm or more on the outermost surface. Such fine irregularities may be formed due to the antiviral agent by lifting the antiviral agent, or may be formed by physical processing such as sandblasting or fine embossing. In addition, the arithmetic mean roughness Ra of the outermost surface is more preferably 1.0 μm or more, and the preferable upper limit of Ra is about 40 μm or less. Since the surface area of the outermost surface increases due to the formation of such fine irregularities, it becomes easier to obtain an antiviral effect compared to a case without fine irregularities. Note that the arithmetic mean roughness Ra in this specification is a value measured by a surface roughness measuring device (“SURFCOM-FLEX-50A”, manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with JIS B0601 (2001).

In the present invention, the Martens hardness of the crosslinked curable resin layer is preferably 30 N/mm ² or more and 180 N/mm ² or less, more preferably 60 N/mm ² or more and 180 N/mm ² or less.

Note that the Martens hardness in this specification is a value measured using a Martens hardness measuring device PICODENTOR HM-500 (manufactured by Fisher Instruments) in accordance with ISO14577. Specifically, the measurement is performed by using a diamond indenter (Vickers indenter) shown in FIG. 5(a) and pushing the diamond indenter into the measurement sample as shown in FIG. 5(b). The indentation conditions were as shown in Figure 5(c) at room temperature (laboratory environment temperature), first a load of 0 to 5 mN was applied for 10 seconds, then a load of 5 mN was held for 5 seconds, and finally a load of 5 mN was applied for 10 seconds. Unload to ~0 mN in 10 seconds. In this specification, the Martens hardness of the cross-section of the cross-linked curable resin layer was measured in order to avoid the influence of the hardness of layers other than the cross-linked curable resin layer. At this time, the decorative sheet is embedded in a resin (resin such as a cold-curing type epoxy two-component curing resin or UV-curing resin), and is left at room temperature (23 ± 5°C) for at least 24 hours to harden. , cut the cured embedding sample, mechanically polish it to expose the cross-section of the cross-linked cured resin layer, and place it on the cross-section (if fine particles such as fillers are included in the layer, avoid the fine particles). ) The Martens hardness of the cross section was measured by indenting it with a diamond indenter.

In the present invention, by setting the Martens hardness of the crosslinked curable resin layer to preferably 30 N/mm ² or more and 180 N/mm ² or less, the slip resistance value (C.S.R. value) is used as an index of anti-slip property. It becomes easier to adjust the value to 0.25 or more. Here, C. S. R. As an index of anti-slip property for various uses in terms of value, if it is 0.25 or more (especially 0.25 or more and less than 0.30), it can be judged that it is suitable for fittings, and if it is 0.30 or more (especially 0.30 If the value is 0.38 or more (especially 0.38 or more and less than 0.50), it is considered suitable for use as a normal floor, and if it is 0.38 or more (particularly 0.38 or more and less than 0.50), it is suitable for use as an anti-slip floor that exhibits a high level of anti-slip properties. It can be determined that In addition, the slip resistance value (C.S.R. value) in this specification is the slip resistance value (C.S.R. value) with socks using a Tokyo Institute of Technology slip tester (O-Y PSM). This is the value measured. When the Martens hardness of the cross-linked curable resin layer is 30 N/mm ² or more and 180 N/mm ² or less, the corresponding Martens hardness of the base sheet and/or transparent thermoplastic resin layer is, for example, 30 N/mm 2 or more and 180 N/mm 2 or less. /mm ² or more and 80 N/mm ² or less.

In the present invention, a phenyl ether derivative compound can be contained in the crosslinked curable resin layer in order to complement the antiviral performance of the crosslinked curable resin layer. Examples of phenyl ether derivative compounds include polyoxyethylene alkyl ether, which is known to exhibit antiviral performance as an ether type nonionic surfactant.

In addition, the cross-linked curable resin layer contains coloring agents such as dyes and pigments, fillers such as inorganic fillers, weathering agents, and antifoaming agents within the range that does not affect the surface performance of the surface protective layer and the specified antiviral properties. Various additives may be added, such as a leveling agent, a thixotropic agent, a flame retardant, an antibacterial agent different from the antiviral agent, and an antiallergen agent different from the antiviral agent. For example, in the present invention, an embodiment may be adopted in which, in addition to the antiviral agent, at least one selected from the group consisting of an antibacterial agent and an antiallergen agent is further included. In addition, inorganic fillers are often used mainly as matting agents, but by including an inorganic filler in the crosslinked curable resin layer, it can also be expected to have the effect of suppressing curing shrinkage of the surface protective layer.

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

The above anti-allergen agent contains either an inorganic compound or an organic compound, and each may be used alone, or two or more different types may be mixed. The inorganic compound is preferably a material supporting a metal.

As an anti-allergen agent, an agent similar or the same as an antibacterial agent may also be effective. In that case, the content of the antibacterial agent and antiallergen agent may be optimized so as to obtain the desired antibacterial property and the desired antiallergenic property.

The inorganic material of the inorganic compound is preferably at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate, and magnesium phosphate, among which titanium oxide and phosphorus are preferred. Acid zirconium etc. are preferred.

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

As the organic compound, at least one monomer component selected from the group consisting of water-insoluble polymers containing phenolic hydroxyl groups or polyphenol compounds supported on inorganic solid acids, styrene sulfonic acid and salts thereof; It is preferable that it is a polymer containing.

As water-insoluble polymers containing phenolic hydroxyl groups, commercially available products such as "Aller Buster (trade name)" manufactured by Sekisui Chemical Co., Ltd. and "Maruka Linker M (trade name)" manufactured by Maruzen Sekiyu Co., Ltd. are used. can do. Further, as a combination of a polyphenol compound and a zirconium compound, there is "Aleli Move (trade name)" manufactured by Toagosei Co., Ltd., and the like. These anti-allergen agents act effectively against various allergens such as dust mites and pollen.

As at least one monomer component selected from the group consisting of styrene sulfonic acid and its salts, materials such as those shown in Japanese Patent No. 6136433 can be used.

In addition, when an organic compound and an inorganic compound are mixed, for example, an anionic phenol-based material and a zinc-based material having anti-allergenic properties may be used.

Anionic phenolic materials include tannin, tannic acid tartarite, phenolsulfonic acid formaldehyde resin, sulfone compounds of novolac type resin, methanesulfonic acid of novolac type resin, methanesulfonic acid of resol type resin, and benzylated phenol sulfone. It is appropriately selected and used from acids, thiophenol compounds, dihydroxy, diphenylsulfone compounds, ligand compounds, metal chelate compounds thereof, and the like.

The zinc-based material is appropriately selected from water-soluble zinc compounds, water-insoluble zinc compounds, zinc/metal oxide composite materials, etc., and water-insoluble zinc compounds and/or water-insoluble zinc/metal oxide composite particles are used. It is preferable that the metal oxide is water-dispersed, has a particle size of 50 μm or less, and contains at least one of titania, silica, and alumina.

Embossing Embossing is performed to impart a desired texture such as a wood grain pattern to the decorative sheet, and may be performed on the transparent resin layer and/or on the crosslinked curable resin layer. For example, a cross-linked curable resin layer is heated and softened, then pressed and shaped with an embossing plate having a desired pattern of unevenness, and then cooled and fixed to give a texture. Embossing can be performed with a known single-fed or rotary embossing machine.

Examples of the embossed uneven pattern include wood grain conduit grooves, raised patterns (embossed annual ring uneven patterns), hairlines, sand grains, satin finishes, and the like.

When embossing is performed, the embossed recesses may be filled with ink by wiping, if necessary. For example, ink is filled into the embossed recesses while scraping the surface with a doctor blade. As the ink to be filled (wiping ink), it is usually possible to use an ink having a two-component curing type urethane resin as a binder. In particular, by performing a wiping process on the unevenness of the wood grain conduit groove, the product value can be increased by expressing a design that is closer to the actual wood grain.

A back primer layer may be provided on the back side of the back primer layer base sheet, if necessary. For example, it is effective when producing a decorative laminate by bonding a base sheet and a decorative laminate base material.

The back primer layer can be formed by applying a known primer agent to the base sheet. Examples of primer agents include acrylic modified urethane resins (acrylic urethane copolymer resins), urethane resin primers made of polycarbonate-based acrylic urethane copolymer resins, and urethane-cellulose resins (for example, urethane and nitrified cotton). A resin-based primer agent made of a block copolymer of acrylic and urethane, etc. may be mentioned.

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

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

Synthetic resin backer layer A synthetic resin backer layer may be provided on the back side of the base sheet, if necessary. By having the synthetic resin backer layer, the impact resistance of the decorative sheet is further improved. In addition, when the above-mentioned back primer layer is also provided, the synthetic resin backer layer and the back primer layer are provided on the back surface of the base sheet in this order from the base sheet side.

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

The thickness of the synthetic resin backer 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. When the lower limit of the thickness of the synthetic resin backer layer is within the above range, the impact resistance of the decorative sheet is further improved. Furthermore, by setting the upper limit of the thickness of the synthetic resin backer layer within the above range, warping of the decorative sheet is further suppressed.

Vesicleization of various additives contained in each layer of the decorative sheet The various additives added to the above-mentioned layers of the decorative sheet of the present invention (such as inorganic fillers added to the primer layer and the cross-linked hardening resin layer) are Preferably, the additive is vesiculated. The method for forming various additives into vesicles is not particularly limited, and may be formed by any known method, and among them, supercritical reverse phase evaporation is preferred.

In addition to the supercritical reverse phase evaporation method, examples of the vesicle formation treatment method include the Bangham method, the extrusion method, the hydration method, the reverse phase evaporation method, and the freeze-thaw method. To briefly explain such a vesiculation treatment method, in the Bangham method, chloroform or a mixed solvent of chloroform/methanol is placed in a container such as a flask, and then phospholipids are added and dissolved. Thereafter, the solvent is removed using an evaporator to form a thin film made of lipids, and after a dispersion of additives is added, vesicles are obtained by hydration and dispersion using a vortex mixer. The extrusion method is a method for obtaining vesicles by preparing a thin film of phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method. The hydration method is a preparation method that is almost the same as the Bangham method, but it is a method in which vesicles are obtained by gentle stirring and dispersion without using a mixer. In the reverse phase evaporation method, phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to create a W/O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and water is added. This method is used to obtain vesicles. The freeze-thaw method is a method that uses cooling and heating as external perturbations, and is a method that obtains vesicles by repeating this cooling and heating.

Hereinafter, the supercritical reverse phase evaporation method will be explained in detail. The supercritical reverse phase evaporation method is a method in which water-soluble or hydrophilic substances are uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure above the supercritical point. In this method, an aqueous phase containing various additives as an encapsulating substance is added to form a capsule-shaped vesicle containing various additives as an encapsulating substance in a single layer of membrane. In addition, carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773 ± 0.0030 MPa) or higher; Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition. By this method, unilamellar vesicles with a diameter of 50 to 800 nm can be obtained. In general, a vesicle is a general term for a vesicle that has a closed spherical membrane structure and contains a liquid phase inside. In particular, a vesicle whose outer membrane is composed of biological lipids such as phospholipids is called a liposome. .

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

As the substance constituting the outer membrane, a dispersant such as a nonionic surfactant or a mixture of this and cholesterol or triacylglycerol can be used.

Examples of the nonionic surfactants include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene. One or two types of polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. The above can be used.

The above-mentioned cholesterols include one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol, etc. Can be used.

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

2. Antiviral Adhesive Processed Sheet The antiviral adhesive processed sheet of the present invention (adhesive processed sheet of the present invention) is composed of a laminate comprising at least an adhesive sheet and a decorative sheet of the present invention in this order in the thickness direction. . The pressure-sensitive adhesive sheet is not particularly limited, and any pressure-sensitive adhesive sheet used in the field of decorative sheets and other functional sheets can be used as appropriate. By having an adhesive sheet on the back side, the adhesive processed sheet of the present invention can be applied to the surfaces of various articles for floors and adherends, and can optionally be imparted with antiviral properties.

FIG. 2 shows an example of an antiviral pressure-sensitive adhesive sheet 11 in which the decorative sheet 1 of the present invention (the surface opposite to the cross-linked curable resin layer and the pressure-sensitive adhesive sheet 10 are laminated in this order) on the pressure-sensitive adhesive sheet 10. shows.

3. Antiviral Decorative Board The antiviral decorative board of the present invention (the decorative board of the present invention) comprises at least, in order in the thickness direction, a decorative board base material, and a decorative sheet of the present invention or an adhesive processed sheet of the present invention. Composed of laminates.

FIG. 3 shows an antiviral decorative board in which the decorative sheet 1 of the present invention (the surface opposite to the cross-linked curing resin layer side and the decorative board base material 12 are laminated) on the decorative board base material 12 in this order. An example of No. 13 is shown below.

Decorative board base materials include, but are not limited to, medium-density wood fiberboard, high-density wood fiberboard, particle board, softwood plywood, hardwood plywood, early-wood plywood, cork sheet, cork-containing composite base material, thermoplastic At least one type of resin board (resin board whose main component is polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc., or a foamed version thereof) can be used. These decorative laminate base materials may be used alone or in combination and laminated together.

Here, examples of coniferous trees include Japanese pine, Japanese pine, Ezo pine, cedar, cypress, pine, sequoia, spruce, and the like. Examples of broad-leaved trees include lauan, china, birch, sen, beech, oak, and meranti. Moreover, examples of fast-growing trees include poplar, falcata, acacia, chameleon, eucalyptus, terminaria, and the like.

When using wood plywood such as softwood plywood, hardwood plywood, and early-maturity plywood, the number of laminated wood veneers (number of plies) is not limited, but is usually preferably 3 to 7, more preferably 5 to 7. Further, the adhesive used when producing the wood plywood is not limited, and a wide variety of known woodworking adhesives can be used. Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc. as active ingredients. Examples include adhesives that can be used. Further, examples of thermosetting adhesives include melamine-based, phenol-based, urea-based (vinyl acetate-urea, etc.) adhesives, and the like.

As the cork sheet, not only so-called natural cork, which is a highly elastic material made by exfoliating and processing the cork tissue of cork oak bark, but also so-called synthetic cork, which is made to resemble cork, can be used. Note that the cork sheet may be a single layer, or may be a laminate of a plurality of cork sheets having different elastic moduli and densities.

Examples of the cork-containing composite base material include a composite material formed by laminating and bonding a cork sheet and other materials (for example, medium-density wood fiberboard, high-density wood fiberboard).

The thickness of the decorative board base material is not limited, but is preferably about 2 to 15 mm, more preferably about 2 to 12 mm.

The lamination method for laminating the decorative sheet or adhesive processed sheet and the decorative laminate base material is not limited, and for example, a method of pasting each with an adhesive can be adopted. In addition, if the adhesive sheet has sufficient adhesion to the decorative laminate base material, it is possible to adopt a method of attaching the adhesive sheet and the decorative laminate base material without using an adhesive. can. The adhesive may be appropriately selected from known adhesives depending on the type of adherend. For example, in addition to urethane, acrylic, urethane-acrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural Examples include rubber. These adhesives may be used alone or in combination of two or more.

The present invention will be specifically described below with reference to Examples, Comparative Examples, and Test Examples. However, the present invention is not limited to the contents shown in the examples.

Example 1
A 60 μm thick colored polypropylene film was prepared as a base sheet.

A back primer layer (thickness: 2 μm) was formed on the back side of the base sheet. Further, a pattern layer was formed on the front surface of the base sheet by gravure printing using a two-component urethane ink (trade name "V180", manufactured by Toyo Ink Co., Ltd.) to a thickness of 2 μm.

A transparent adhesive layer was formed on the pattern layer using urethane resin to a thickness of 2 μm.

A sheet of transparent random polypropylene resin was laminated on the transparent adhesive layer by an extrusion lamination method to a thickness of 80 μm to form a transparent resin layer.

After corona discharge treatment was applied to the front surface of the transparent resin layer, a primer layer was formed by applying a primer agent containing a two-component curable urethane resin to a thickness of 2 μm.

After applying the following composition for forming a crosslinked curable resin layer to the front surface of the primer layer in a coating amount of 15 μm using a gravure coating method, using an electron beam irradiation device in an environment with an oxygen concentration of 200 ppm or less. A crosslinked curable resin layer was formed by irradiating the electron beam under the conditions of an acceleration voltage of 165 KeV and 5 Mrad to cure the electron beam curable resin, thereby producing a decorative sheet. Here, the following antiviral agent was set to be contained in an amount of 3 parts by mass based on 100 parts by mass of the crosslinked curable resin. In addition, in the cross-sectional observation of the crosslinked curable resin layer, the proportion of the central point of the antiviral agent present in the middle layer or upper layer (that is, the middle layer or above) was 60% of the total.

(Crosslinked curable resin layer forming composition)
- As a crosslinked curable resin, a total of 100 parts by mass of urethane acrylate resin consisting of 30 parts by mass of a polyfunctional urethane oligomer and 70 parts by mass of a bifunctional oligomer (the Martens hardness of the crosslinked curable resin layer after curing is 110 N/mm ² (prescription)
・Antiviral agent (3 parts by mass per 100 parts by mass of resin)
The carboxylic acid derivatives include cyclohexanecarboxylic acid (manufactured by New Japan Chemical Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N,N-dimethylallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.). It was prepared by mixing and reacting raw materials containing N,N,2,2-tetramethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and N,N,2,2-tetramethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

In addition, styrene polymer derivatives include sodium p-styrene sulfonate (manufactured by Tosoh Corporation; trade name "Spinomer NaSS"), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.), and denatured ethanol (manufactured by Wako Pure Chemical Industries, Ltd.; trade name "86"). % ethanol-ME") were mixed and reacted.

The antiviral agent was prepared by sequentially mixing the above carboxylic acid derivative and the above styrene polymer derivative at a mass ratio of 3:1, and then pulverizing the mixture with a jet mill (Nissin Engineering, trade name "SJ-100"). When the antiviral agent was measured using a laser diffraction particle size distribution analyzer (manufactured by HORIBA) in accordance with JIS Z8825-1, the average particle diameter was 10 μm.
- Antibacterial agent (content is 0.5 parts by mass per 100 parts by mass of resin)
Silver-supported zeolite particles (trade name "Zeomic", manufactured by Sinanen Zeomic Co., Ltd., average particle size 10 μm)
・Weather resistant agent: triazine-based ultraviolet absorber (UVA "LA-F70", manufactured by ADEKA) (content: 1 part by mass per 100 parts by mass of resin)
Light stabilizer (radical scavenger) (HALS "Tinuvin 152", manufactured by BASF) (content is 0.3 parts by mass per 100 parts by mass of resin)

Example 2
9 parts by mass of a photoreaction initiator (trade name "Irgacure 184", manufactured by BASF) was added to 100 parts by mass of the crosslinked curable resin, and the coating amount of the composition for forming a crosslinked curable resin layer was 5 μm. The average particle size of the virus agent is 4 μm, the average particle size of the antibacterial agent is 2.5 μm, and ultraviolet rays with a wavelength of 300 nm are irradiated using an ultraviolet irradiation device (the Martens hardness of the crosslinked resin layer after curing is 70 N/ ^mm2 ), the ultraviolet absorber was changed to a benzotriazole type (UVA "Tinuvin 329", manufactured by BASF) (content per 100 parts by mass of resin was 5 parts by mass), and the content of light stabilizer was A decorative sheet was produced in the same manner as in Example 1, except that 2 parts by mass was changed from 100 parts by mass of the resin to form a crosslinked curable resin layer. In addition, in the cross-sectional observation of the cross-linked curable resin layer, the proportion of the central point of the antiviral agent present in the middle layer or upper layer (ie, above the middle layer) was 65% of the total.

Comparative example 1
A decorative sheet was produced in the same manner as in Example 1, except that the antiviral agent was prepared by pulverizing only the styrene polymer derivative described in Example 1 using a jet mill. In addition, in the cross-sectional observation of the crosslinked curable resin layer, the proportion of the central point of the antiviral agent present in the middle layer or upper layer (that is, the middle layer or above) was 60% of the total.

Example 3
A colored polyethylene sheet with a thickness of 80 μm was prepared as a base sheet.

On the picture pattern layer, the following transparent resin layer was laminated by a dry laminating method using a dry laminating adhesive (trade name "Takelac A540", manufactured by Mitsui Chemicals, Co., Ltd.; coating amount: 2 g/m ² ). Furthermore, an embossed pattern was applied to the front surface of the bonded transparent resin layer.

The transparent resin layer contains 0.5 parts by mass of a hindered phenolic antioxidant (trade name "Irganox 1010", manufactured by BASF) and triazine-based ultraviolet absorber based on 100 parts by mass of highly crystalline homopolypropylene resin. A resin composition containing 0.5 parts by mass of an agent (trade name "CYASORBUV-1164", manufactured by SUNCEM) and 0.5 parts by mass of a NOR type light stabilizer (trade name "Tinuvin XT850FF", manufactured by BASF). It was obtained by melt-extruding using an extruder to form a transparent highly crystalline homopolypropylene sheet with a thickness of 100 μm. In addition, both surfaces of the transparent resin layer were subjected to corona treatment, and the wetting tension of the sheet surface was set to 40 dyn/cm or more.

A decorative sheet was obtained by applying the following composition for forming a crosslinked curable resin layer to a transparent resin layer provided with an embossed pattern and curing the coating film. In addition, in cross-sectional observation of the cross-linked curable resin layer, the proportion of the central point of the antiviral agent present in the middle layer or upper layer (ie, above the middle layer) was 80% of the total.
(Crosslinked curable resin layer forming composition)
The composition for forming a crosslinked curable resin layer (thermocurable type that crosslinks and cures with heat) is prepared by blending the following curing agent, gloss modifier, ultraviolet absorber, light stabilizer, and diluting solvent into the following polymer solution A. It was prepared by
・Polymer solution A
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, and 100 g of ethyl acetate was added and dissolved, and placed on an oil bath in a nitrogen atmosphere. Stir at the bottom. Next, polymerization was started by blending 0.2 g of α,α'-azobisisobutyronitrile, and heating and stirring was continued for 5 hours on an oil bath at 60°C to form a colorless and viscous polymer solution A. Obtained.
Compound: 80 parts by mass/hardening agent Product name: Duranate 24A-100 (manufactured by Asahi Kasei Corporation)
Formulation: 5 parts by mass/gloss modifier (inorganic particles)
Product name: Sunsphere H122 (manufactured by AGC SI Tech)
Properties: Spherical, average particle size 12μm, pore volume 2ml/g
Formula: 10 parts by mass/UV absorber Product name: TinuvinP, Tinuvin326, Tinuvin399 (all manufactured by BASF)
Formulation: 2.0 parts by mass each, light stabilizer Product name: Tinuvin765 (manufactured by BASF)
Blend: 2.0 parts by mass/diluent Solvent Name: Ethyl acetate Blend: 50 parts by mass

Example 4
A decorative sheet was obtained in the same manner as in Example 3, except that the composition for forming a crosslinked curable resin layer used in Example 3 was changed to the following composition. In addition, in the cross-sectional observation of the cross-linked curable resin layer, the proportion of the central point of the antiviral agent existing in the middle layer or upper layer (ie, the middle layer or above) was 58% of the total.
[Thermosetting/photocuring hybrid curable composition]
The thermosetting/photocuring hybrid curable composition is prepared by blending the following curing agent, photoinitiator, gloss modifier, ultraviolet absorber, light stabilizer, and diluting solvent with the following polymer solution A and monomer. did.
・Polymer solution A
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, and 100 g of ethyl acetate was added and dissolved, and the mixture was placed on an oil bath under a nitrogen atmosphere. It was stirred with Next, polymerization was started by blending 0.2 g of α,α'-azobisisobutyronitrile, and heating and stirring was continued for 5 hours on an oil bath at 60°C to form a colorless and viscous polymer solution A. Obtained.
Blending: 40 parts by mass, monomer Product name: Dipentaerythritol hexaacrylate Blending: 40 parts by mass, curing agent Product name: Duranate 24A-100 (manufactured by Asahi Kasei Corporation)
Formula: 10 parts by mass/photoinitiator Product name: Irgacure 184 (manufactured by BASF)
Blend: 10 parts by mass/Gloss modifier (inorganic particles)
Product name: Sunsphere H122 (manufactured by AGC SI Tech Co., Ltd.)
Properties: Spherical, average particle size 12μm, pore volume 2ml/g
Formula: 10 parts by mass/UV absorber Product name: Tinuvin400 (manufactured by BASF)
Formula: 5.0 parts by mass/light stabilizer Product name: Tinuvin123 (manufactured by BASF)
Blend: 2.0 parts by mass/diluent Solvent Name: Ethyl acetate Blend: 50 parts by mass

Test example 1
Regarding the decorative sheets produced in Examples and Comparative Examples, the proportion of the central point of the antiviral agent in the middle layer or upper layer (i.e., the middle layer or above) of the crosslinked curable resin layer, and the arithmetic mean roughness of the surface of the crosslinked curable resin layer. Ra and antiviral performance were evaluated. Each measurement method and evaluation method are as follows.

<Surface roughness>
Arithmetic mean roughness Ra defined in JIS B0601 (2001) was measured using a surface roughness measuring device (product number "SURFCOM-FLEX-50A", manufactured by Tokyo Seimitsu Co., Ltd.) under the following conditions. In addition, depending on the measured Ra, we decided to change the evaluation length and cutoff value to a suitable value and perform the measurement again.
(Measurement conditions) When Ra = more than 0.1 μm and less than 2 μm Number of measurements: n = 5 (5 arbitrary points)
Calculation standard: JIS'01
Measurement type: Roughness measurement evaluation length: 4.0mm
Cutoff value: 0.8mm
Measurement speed: 0.60mm/s
Filter type: Gaussian shape removal: Straight line (measurement conditions) When Ra = more than 2 μm and less than 10 μm Number of measurements: n = 5 (5 arbitrary points)
Calculation standard: JIS'01
Measurement type: Roughness measurement evaluation length: 12.5mm
Cutoff value: 2.5mm
Measurement speed: 0.60mm/s
Filter type: Gaussian shape removal: Straight line (measurement conditions) When Ra = more than 10 μm and less than 80 μm Number of measurements: n = 5 (5 arbitrary points)
Calculation standard: JIS'01
Measurement type: Roughness measurement evaluation length: 40mm
Cutoff value: 8mm
Measurement speed: 0.60mm/s
Filter type: Gaussian shape removal: Straight line

<Cross-sectional observation>
1) In order to observe the cross section of the produced decorative sheet, an arbitrarily selected area was cut in the thickness direction of the decorative sheet using a single-edged trimming razor.
2) A width of 200 μm was observed from the cross-sectional side of the cut decorative sheet using a digital microscope (manufactured by Keyence Corporation, model number: VHX-7000, magnification: 200x).
3) Confirm the position of the center point of the antiviral agent present in the entire area of the cross-sectional photograph observed, and calculate the proportion of the antiviral agent whose center point exists in the middle layer or upper layer (i.e., above the middle layer) of the crosslinked curing resin layer as shown below. Calculated using the formula.

(Number of antiviral agents whose center point is present in the middle layer or upper layer (i.e. above the middle layer)/Number of antiviral agents present in the entire area of the observed cross-sectional photograph) x 100 (%)

<Antiviral performance>
The decorative sheets produced in Examples and Comparative Examples were subjected to an antiviral performance test in accordance with the antiviral testing method (ISO21702), and the antiviral activity value against feline calicivirus as a non-enveloped virus was determined based on the following evaluation criteria. evaluated. The evaluation criteria are as follows.
Virus species: Non-enveloped virus (feline calicivirus)
+: Antiviral activity value after 24 hours is 2.0 or more,
-: Antiviral activity value after 24 hours is less than 2.0 The results are shown in Table 1 below.

As can be seen from the results in Table 1, the decorative sheets of Examples 1 to 4 containing the antiviral agent of the present invention have antiviral performance against non-enveloped viruses at a content that does not impair the surface performance of the surface protective layer. I can see that it is being done.

1. Antiviral decorative sheet 2. Base sheet 3. Picture pattern layer 4. Transparent adhesive layer5. Transparent resin layer 6. Primer layer7. Cross-linked curing resin layer (surface protection layer)
8. Back primer layer9. Antiviral agent 10. Adhesive sheet 11. Antiviral adhesive processed sheet 12. Decorative board base material 13. Antiviral decorative board A. Thickness of the smooth part of the crosslinked curable resin layer (surface protection layer) a. Upper layer b. middle layer c. Underlayer

Claims

A decorative sheet comprising a crosslinked curable resin layer on the outermost layer,
(1) The crosslinked curable resin layer contains a cured product of a crosslinked curable resin and an antiviral agent,
(2) The antiviral agent is an antiviral agent having antiviral properties against non-enveloped viruses, and contains a carboxylic acid derivative and a styrene polymer derivative, and at least triethylamine, N , N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine,
An antiviral cosmetic sheet characterized by:
The antiviral agent contains triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1, as constituent components of the styrene polymer derivative. The antiviral decorative sheet according to claim 1, which contains all of 3-propanediamine.
The antiviral decorative sheet according to claim 1 or 2, wherein the crosslinked curable resin layer has fine irregularities on the outermost surface with an arithmetic mean roughness Ra of 0.1 μm or more.
The antiviral decorative sheet according to claim 3, wherein the arithmetic mean roughness Ra of the fine irregularities is 40 μm or less.
The antiviral decorative sheet according to claim 1 or 2, wherein the crosslinked curable resin layer further contains an antibacterial agent made of silver-containing inorganic particles.
The antiviral decorative sheet according to claim 1 or 2, wherein the crosslinked curable resin layer further contains a triazine-based ultraviolet absorber and/or a light stabilizer.
The antiviral decorative sheet according to claim 1 or 2, wherein the antiviral agent contains the carboxylic acid derivative and the styrene polymer derivative in a mass ratio of 1:1 to 10:1.
When the thickness of the smooth part of the cross-linked curable resin layer is divided into thirds and divided into a lower layer, a middle layer, and an upper layer, the central point of the antiviral agent that accounts for 50% or more of the entire antiviral agent is the middle layer. or the antiviral decorative sheet according to claim 1 or 2, which is present in the upper layer.
The antiviral decorative sheet according to claim 1 or 2, wherein the antiviral agent is contained in a range of 1 part by mass to 10 parts by mass based on 100 parts by mass of the crosslinked curable resin.
The antiviral decorative sheet according to claim 1 or 2, wherein the average thickness of the smooth portion of the crosslinked curable resin layer is 2 μm or more and 35 μm or less.
The antiviral decorative sheet according to claim 1 or 2, wherein the antiviral agent has an average particle diameter of 2 μm or more and 15 μm or less.
The antiviral decorative sheet according to claim 1 or 2, wherein the crosslinked curable resin contains an ionizing radiation curable resin.
The antiviral decorative sheet according to claim 1 or 2, wherein the crosslinked curable resin layer has a Martens hardness of 30 N/mm 2 or more and 180 N/mm 2 or less.
The resistor according to claim 1 or 2, comprising a laminate comprising at least a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and the crosslinked curable resin layer in this order in the thickness direction. Viral makeup sheet.
The antiviral decorative sheet according to claim 14, wherein the base sheet and/or the transparent thermoplastic resin layer has a Martens hardness of 30 N/mm 2 or more and 80 N/mm 2 or less.
An antiviral adhesive processed sheet comprising a laminate comprising at least an adhesive sheet and the antiviral decorative sheet according to claim 1 or 2 in this order in the thickness direction.
An antiviral decorative board comprising a laminate comprising at least a decorative board base material and the antiviral decorative sheet according to claim 1 or 2 in order in the thickness direction.
An antiviral decorative laminate comprising a laminate comprising at least a decorative laminate base material and the antiviral pressure-sensitive adhesive sheet according to claim 16 in this order in the thickness direction.