JP2023050182A - Antiviral decorative sheet and antiviral decorative plate - Google Patents

Abstract

To provide an antiviral decorative sheet which is excellent in antiviral property and suppresses discoloration of a surface protective layer.SOLUTION: An antiviral decorative sheet has at least a surface protective layer on a thermoplastic resin base material sheet, wherein the surface protective layer contains an antiviral agent, and the antiviral agent contains an inorganic metal-based antiviral agent and an organic antiviral agent.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an antiviral decorative sheet and an antiviral decorative board.

2. Description of the Related Art Conventionally, various kinds of decorative sheets have been used for surface decoration of fittings, floors, walls, etc. used as interior materials of buildings. For example, a decorative sheet composed of a laminate having a substrate sheet, a transparent resin layer, and a surface protective layer in order in the thickness direction is widely used, and a decorative layer is added on the substrate sheet as necessary. , a primer layer is provided between the transparent resin layer and the surface protective layer to improve adhesion, or an ionizing radiation curable resin is added to the resin component of the surface protective layer to improve the scratch resistance of the surface protective layer. It is known to contain

As an example of imparting functionality to a decorative sheet, it is known to use an antibacterial resin composition that can be used for building parts and the like (see Patent Document 1). However, when the antibacterial resin composition described in Patent Document 1 is used for a decorative sheet, it cannot sufficiently suppress the growth of viruses typified by influenza virus, that is, it has antiviral properties. The problem is that it's not enough.

An antiviral member using an antiviral resin composition exhibiting antiviral properties has been disclosed (see Patent Document 2). However, since the antiviral resin composition described in Patent Document 2 contains cuprous oxide particles and the like, it has a tint derived from the color of cuprous oxide (reddish brown), and has a problem that it is not suitable as a decorative sheet. be.

In addition, an interior decorative sheet having antiviral properties has been disclosed (see Patent Document 3). In the decorative sheet for interior decoration of Patent Document 3, a silver-based inorganic additive or a zinc-based inorganic additive is blended in the coating resin on the outermost surface of the decorative sheet. However, the antiviral property of the interior decorative sheet of Patent Document 3 has room for investigation, and the silver-based inorganic additive has the problem of being discolored brown by light (visible light, ultraviolet light). In particular, when the amount of the silver-based inorganic additive added is increased in order to improve antiviral properties, there is a problem that discoloration due to light becomes noticeable.

Therefore, there is a demand for the development of an antiviral decorative sheet having excellent antiviral properties and suppressing discoloration of the surface protective layer, and an antiviral decorative board using the same.

Japanese Patent No. 3551201 Japanese Patent No. 6145758 Japanese Patent No. 6229429

An object of the present invention is to provide an antiviral decorative sheet that is excellent in antiviral properties and that suppresses discoloration of the surface protective layer. Another object of the present invention is to provide an antiviral decorative board using the antiviral decorative sheet.

As a result of intensive research, the present inventors have found that in an antiviral decorative sheet comprising at least a surface protective layer on a thermoplastic resin base sheet, the surface protective layer contains an antiviral agent, and the antiviral agent is found that an antiviral decorative sheet containing an inorganic metal antiviral agent and an organic antiviral agent can achieve the above objects, and completed the present invention.

That is, the present invention relates to the following antiviral decorative sheet and antiviral decorative board using the same.
1. An antiviral decorative sheet comprising at least a surface protective layer on a thermoplastic resin base sheet,
The surface protective layer contains an antiviral agent,
The antiviral agent includes an inorganic metal antiviral agent and an organic antiviral agent.
An antiviral cosmetic sheet characterized by:
2. Item 2. The antiviral cosmetic according to Item 1, wherein the inorganic metal antiviral agent is at least one selected from the group consisting of a silver antiviral agent, a zinc antiviral agent, and a copper antiviral agent. sheet.
3. Item 3. The antiviral according to Item 1 or 2, wherein the organic antiviral agent is at least one selected from the group consisting of benzimidazole antiviral agents, anionic antiviral agents, and ether antiviral agents. sexual makeup sheet.
4. 4. Any one of Items 1 to 3, wherein the content of the antiviral agent in the surface protective layer is 2.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component in the surface protective layer. The described antiviral cosmetic sheet.
5. The mass ratio of the inorganic metal antiviral agent and the organic antiviral agent in the surface protective layer (mass of the inorganic metal antiviral agent: mass of the organic antiviral agent) is 1:5 to Item 5. The antiviral cosmetic sheet according to any one of Items 1 to 4, which is 1:20.
6. Items 1 to 1, wherein the content of the inorganic metal antiviral agent in the surface protective layer is 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin component in the surface protective layer. 6. The antiviral cosmetic sheet according to any one of 5.
7. Items 1 to 6, wherein the content of the organic antiviral agent in the surface protective layer is 2.0 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin component in the surface protective layer. The antiviral cosmetic sheet according to any one of 1.
8. Item 8. The antiviral decorative sheet according to any one of Items 1 to 7, wherein the antiviral agent has two different average particle size peaks.
9. Item 9. The antiviral cosmetic according to any one of Items 1 to 8, wherein the antiviral cosmetic sheet has a silver ion concentration of 0.018 μg/cm ² or more and 0.50 μg/cm ^{2 or} less as measured by ICP-OES measurement. sheet.
10. Item 10. The antiviral decorative sheet according to any one of Items 1 to 9, which has a patterned layer between the thermoplastic resin base sheet and the surface protective layer.
11. Item 11. The antiviral decorative sheet according to any one of items 1 to 10, comprising a transparent resin layer between the thermoplastic resin base sheet and the surface protective layer.
12. Item 12. The antiviral decorative sheet according to Item 11, wherein the thermoplastic resin base sheet and the transparent resin layer contain a polyolefin resin.
13. The surface protective layer contains 65% by mass or more and 95% by mass or less of a urethane (meth)acrylate oligomer (A) having a weight average molecular weight of 1000 to 3000 and having two radically polymerizable unsaturated groups in one molecule; Item 1, which is a cured product layer of a resin mixture containing 5% by mass or more and 35% by mass or less of an aliphatic urethane (meth)acrylate oligomer (B) having 3 to 15 radically polymerizable unsaturated groups in the molecule. 13. The antiviral cosmetic sheet according to any one of 12.
14. Item 14. The antiviral decorative sheet according to any one of Items 1 to 13, wherein the surface protective layer has a nanoindentation hardness of 100 MPa or more.
15. Item 15. The antiviral decorative sheet according to any one of Items 1 to 14, wherein the surface protective layer has a nanoindentation hardness of 450 MPa or less.
16. Item 16. The antiviral decorative sheet according to any one of Items 1 to 15, wherein the thermoplastic resin base sheet has a nanoindentation hardness of 30 MPa or more and 80 MPa or less.
17. Item 17. The antiviral decorative sheet according to any one of Items 11 to 16, wherein the transparent resin layer has a nanoindentation hardness of 30 MPa or more and 80 MPa or less.
18. Item 18. The antiviral decorative sheet according to any one of Items 1 to 17, wherein the surface protective layer has a thickness of 1 μm or more and 50 μm or less.
19. An antiviral decorative sheet comprising a laminate comprising a decorative sheet base material and the antiviral decorative sheet according to any one of items 1 to 18 in order in the thickness direction.

The antiviral decorative sheet of the present invention has excellent antiviral properties and suppresses discoloration of the surface protective layer. In addition, since the antiviral decorative sheet of the present invention uses the antiviral decorative sheet, it has excellent antiviral properties and suppresses discoloration of the surface protective layer.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the antiviral decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the antiviral decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the antiviral decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the antiviral decorative board of this invention. A schematic for explaining the Berkovich indenter (a) used for measuring nanoindentation hardness in the present specification, the relationship (b) between the direction of the load and the indentation depth h, and the relationship (c) between the indentation depth and the indentation load It is a diagram.

1. Antiviral Decorative Sheet The antiviral decorative sheet of the present invention is an antiviral decorative sheet comprising at least a surface protective layer on a thermoplastic resin base sheet, the surface protective layer containing an antiviral agent, The antiviral agent is characterized by including an inorganic metal antiviral agent and an organic antiviral agent. In the antiviral decorative sheet of the present invention (hereinafter also simply referred to as "decorative sheet"), the surface protective layer contains an antiviral agent, and the antiviral agent includes an inorganic metal antiviral agent and an organic antiviral agent. agent, the antiviral property of the inorganic metal antiviral agent and the antiviral property of the organic antiviral agent can be combined to exhibit sufficient antiviral property. Therefore, the content of the inorganic metal antiviral agent can be reduced, and discoloration of the surface protective layer, such as discoloration due to the inclusion of the inorganic metal antiviral agent and discoloration due to light, can be suppressed. That is, the antiviral decorative sheet of the present invention contains an antiviral agent, and the antiviral agent contains an inorganic metal antiviral agent and an organic antiviral agent. Discoloration of the protective layer is suppressed.

The layer structure of the decorative sheet of the present invention is not limited as long as it has a layer structure comprising at least a surface protective layer on a thermoplastic resin base sheet. 1 to 3 are cross-sectional schematic diagrams showing an example of the decorative sheet of the present invention.

In FIG. 1, the decorative sheet 1 of the present invention has a surface protective layer 6 on a thermoplastic resin base sheet 3 .

2, the decorative sheet 1 of the present invention comprises a back primer layer 2, a thermoplastic resin base sheet 3, a pattern layer 4, a transparent resin layer 5, and a surface protective layer 6 in this order from the bottom. It has an embossed uneven pattern on the outermost surface side.

Further, in FIG. 3, the decorative sheet 1 of the present invention comprises, from the bottom, a back primer layer 2, a synthetic resin backer layer 7, a thermoplastic resin base sheet 3, a pattern layer 4, a transparent resin layer 5, and, The surface protective layer 6 is provided in this order, and has an embossed uneven pattern on the outermost surface side.

Furthermore, the present invention also includes an antiviral decorative sheet (hereinafter simply referred to as "decorative sheet") composed of a laminate comprising a decorative sheet base material and the above-described decorative sheet in order in the thickness direction. ing.

In the present specification, the surface of the decorative sheet of the present invention that is visible after application, that is, the direction in which the surface protective layer is laminated when viewed from the thermoplastic resin base sheet is referred to as "upper" or "front surface." , the direction opposite to the direction in which the surface protective layer is laminated when viewed from the thermoplastic resin base sheet is referred to as "lower" or "back". Moreover, such a relationship is the same in the case of the decorative board of the present invention.

Hereinafter, each layer of the decorative sheet of the present invention will be described using FIG. 3 as an example. However, the layer structure of the decorative sheet of the present invention is not limited to the embodiment shown in FIG. 3, and various layer structures can be employed as described above. In the following description, the lower and upper limits of numerical ranges represented by "-" mean "more than or equal to" (for example, α to β means greater than or equal to α and less than or equal to β).

Thermoplastic Resin Base Sheet The thermoplastic base sheet (hereinafter also simply referred to as "base sheet") may have a pattern layer or the like sequentially laminated on its surface (front surface). In addition, the outermost layer is provided with a surface protective layer.

A thermoplastic resin film can be used as the base sheet. Specific examples of thermoplastic resins forming the base sheet include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene- Acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ionomers, acrylic acid esters, methacrylic acid esters and the like can be mentioned. In the present invention, at least one of polyvinyl chloride resin and polyolefin resin (polyethylene, polypropylene, etc.) can be preferably used, and polyolefin resin is more preferable. Further, in the present invention, the thermoplastic resin base sheet described above and/or the transparent resin layer described later preferably contains at least one selected from the group consisting of polyvinyl chloride-based resins and polyolefin-based resins. , more preferably contains a polyolefin resin. In addition, the thermoplastic resin base sheet and the transparent resin layer described later preferably contain at least one selected from the group consisting of polyvinyl chloride-based resins and polyolefin-based resins, and contain polyolefin-based resins. is more preferable.

The base sheet may be colored. For example, the thermoplastic resin can be colored by adding a coloring agent (pigment or dye). Examples of colorants that can be used include inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes. One or more of these can be selected. Also, the amount of the coloring agent to be added may be appropriately set according to 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, light stabilizers, etc., as required. may be

The nanoindentation hardness of the base sheet is preferably 30 MPa or more and 80 MPa or less, more preferably 40 MPa or more and 60 MPa or less.

In this specification, the “nanoindentation hardness” of the base sheet is measured using a micro-area mechanical property evaluation device Triboindenter (registered trademark) “TI-950” (manufactured by Bruker). Shown by indentation hardness. The method for measuring the indentation hardness (HIT) of the base sheet using Triboindenter (registered trademark) "TI-950" is as follows.
(1) As an indenter for the nanoindenter, a triangular pyramid-shaped Berkovich indenter (model number: TI0039) shown in FIG. 5(a) is used. As shown in FIG. 5(b), a Berkovich indenter was pushed into the measurement sample under the indentation conditions described later, and the indentation depth h (nm) with respect to the indentation load F (μN) was continuously measured. Construct the load-displacement curve as shown. A maximum indentation load Fmax (μN) is obtained from the created load-displacement curve. Next, the hardness is obtained by dividing the maximum indentation load Fmax (μN) by the projected contact area Ap (μm ² ) between the indenter and the sample at that time. Here, Ap is a projected contact area obtained by correcting the curvature of the tip of the indenter by a standard method using fused silica as a standard sample. That is, HIT=Fmax/Ap.
(2) The indentation conditions were as follows: at room temperature (23±5° C.), as shown in FIG. ) is held for 5 seconds, and finally the load is removed from 50 to 0 μN for 5 seconds.
(3) When measuring the hardness, the cross-sectional hardness of the layer to be measured is measured in order to avoid the influence of the hardness of layers other than the layer to be measured. That is, the decorative sheet is embedded in a resin (room temperature curing type epoxy two-liquid curing resin), left to stand at room temperature for 24 hours or more to cure, and then the cured embedded sample is cut with a sharp knife (for example, electron microscope section preparation). The sample is cut out so that the Berkovich indenter can be pushed in, exposing the cross section of the layer to be measured, and the cross section of the base sheet (if the layer contains fine particles such as fillers, the The hardness of the cross section is measured by pressing the Berkovich indenter into the position where fine particles are avoided. (4) For the base sheet, measure the indentation hardness at 10 or more points, and take the average value of the 10 points measured with good reproducibility as the measured value.

The thickness of the base sheet can be appropriately set according to the application of the final product, the method of use, etc., but is generally preferably 50 to 250 μm.

The surface (front surface) of the base material sheet is subjected to a corona discharge treatment, if necessary, in order to increase the adhesion to a layer such as a pattern layer formed on the surface (front surface). good too. The method and conditions for corona discharge treatment may be carried out according to known methods. In addition, if necessary, the back surface of the base sheet may be subjected to corona discharge treatment, or a synthetic resin backer layer or the like, which will be described later, may be formed.

Patterned Layer The patterned layer is an optional layer that imparts a desired pattern (design) to the decorative sheet of the present invention, and the type of pattern is not limited. Examples include wood grain patterns, leather patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, texture patterns, geometric figures, characters, symbols, abstract patterns, flower patterns, landscapes, and characters.

The method for forming the pattern layer is not particularly limited. 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) is used. It may be formed on the surface of the substrate sheet by a known printing method. As the ink, an aqueous composition can be used from the viewpoint of reducing the VOC of the decorative sheet. In the case of a laminate having a transparent resin layer without a base sheet, a pattern layer may be provided between the transparent resin layer and the surface protective layer.

Examples of coloring agents include inorganic pigments such as carbon black, titanium white, zinc oxide, red iron oxide, Prussian blue, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; 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, neutralizers, surfactants and the like.

As a binder resin, in addition to hydrophilic polyester-based urethane resin, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative , alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, and the like can also be used in combination. More specifically, for example, polyacrylamide-based resins, poly(meth)acrylic acid-based resins, polyethylene oxide-based resins, poly N-vinylpyrrolidone-based resins, water-soluble polyester-based resins, water-soluble polyamide-based resins, water-soluble amino resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides and polysaccharides; Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth)acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or mixtures of the above natural rubbers, etc. Resin can also be used. The binder resin can be used alone or in combination of two or more.

Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; - Ester-based organic solvents such as ethoxyethyl; Alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone organic solvents; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; chlorine organic solvents such as dichloromethane, carbon tetrachloride, trichlorethylene and tetrachlorethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

The printing method used for forming the pattern layer includes, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, and the like. Further, in the case of forming a solid picture pattern layer on the entire surface, for example, roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, dipping, etc. Various coating methods such as a coating method can be used. In addition, a hand-drawn method, a suminagashi method, a photographic method, a transfer method, a laser beam drawing method, an electron beam drawing method, a partial vapor deposition method of a metal or the like, an etching method, or the like may be used, or may be used in combination with other forming methods. good.

The thickness of the pattern layer is not particularly limited, and can be appropriately set according to product characteristics, but the layer thickness is about 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 transparent, colored transparent, translucent, or the like. Although the material of the transparent resin layer is not limited, it is preferably made of a thermoplastic resin. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer Polymers, ionomers, acrylic acid esters, methacrylic acid esters and the like can be mentioned. In the present invention, at least one of polyvinyl chloride resin and polyolefin resin (polyethylene, polypropylene, etc.) can be preferably used, and polyolefin resin is more preferable.

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

In addition, the transparent resin layer may contain various additives such as flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, etc., as necessary, as long as it has transparency. good too.

A compound having a hydroxyphenyltriazine skeleton represented by the following formula (1) is preferably used as the ultraviolet absorber. Among these, compounds having maximum absorption in the range from 270 nm to 400 nm are preferred.

As shown by the following formula (2), the compound having the hydroxyphenyltriazine skeleton is excited by absorbing light, and hydrogen atoms move within the molecule according to the skeleton. Heat can be released back to the ground state.

Examples of compounds having a hydroxyphenyltriazine skeleton include 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2- hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-dimethylphenyl)- s-triazine, 2-[2-hydroxy-4-(3-dodecyloxy-2-hydroxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-[2 -hydroxy-4-(3-tridecyloxy-2-hydroxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-[2-hydroxy-4-[3 -(2-ethylhexyloxy)-2-hydroxypropyloxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4 ,6-dibiphenyl-s-triazine, 2-[2-hydroxy-4-[1-(i-octyloxycarbonyl)ethyloxy]phenyl]-4,6-dibiphenyl-s-triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-butoxy-2-hydroxyphenyl)-6-(2,4- dibutoxyphenyl)-s-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2 -hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine (trade name: CYASORB (registered trademark) UV-1164), 2,4,6-tris(2-hydroxy-4-hexyloxy- 3-methylphenyl)-1,3,5-triazine (trade name: LA-F70), 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(octyloxy)phenyl ]-s-triazine (trade name: SIASORB102) and the like.

The light stabilizer is not particularly limited, and a hindered amine light stabilizer containing a hindered amine compound (3) represented by the following formula (3) can be preferably used.

In formula (3) above, R, R ₁ and R ₂ are the same or different and represent a group which may contain a hydrogen atom, a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom.

The hindered amine-based compound can scavenge radicals by the reaction represented by the following formula (4).

Examples of the hindered amine light stabilizer include bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate; (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1, 2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl 4-hydroxybenzylmalonate; 1-(2-hydroxyethyl)-2,2,6, Condensates of 6-tetramethyl-4-hydroxypiperidine and succinic acid; 2,2,6,6-tetramethylpiperidin-4-yl stearate; 2,2,6,6-tetramethylpiperidin-4-yl dodeca 1,2,2,6,6-pentamethylpiperidin-4-yl stearate; 1,2,2,6,6-pentamethylpiperidin-4-yl dodecanoate; N,N'-bis(2 ,2,6,6-tetramethylpiperidin-4-yl)condensation product of hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tris(2,2,6 ,6-tetramethylpiperidin-4-yl)nitrilotriacetate; tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; 4-benzoyl- 2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(1,2,2,6,6-pentamethylpiperidyl)-2-n- Butyl 2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonic acid; 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5 ] Decane-2,4-dione; Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate; Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate a condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine;2- Chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis- Condensates of (3-aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-dodecyl-1-(1-ethanoyl-2,2,6,6 -tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; A mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexa Condensates of methylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; 1,2-bis-(3-aminopropylamino)ethane, 2,4,6-trichloro-1, Condensates of 3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza -4-oxospiro[4.5]decane; oxo-piperandinyl-triazine; 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4. 5] Reaction products of decane and epichlorohydrin, polymers of butanedioic acid dimethyl ester-4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, and the like.

As the hindered amine light stabilizer, an N-alkoxy hindered amine light stabilizer can be used. N-alkoxy hindered amine light stabilizers include tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate; Butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4- piperidinyl tridecyl ester; 1,2,3,4-butanetetracarboxylic acid 2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester; 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl- of the polymer of 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane 3,9-diethanol 4-piperidinyl ester; 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane3, 2,2,6,6-tetramethyl-4-piperidinyl ester of a polymer of 9-diethanol; bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate; mentioned.

Hydroxyl-substituted N-alkoxy HALS can also be used as the hindered amine light stabilizer. Hydroxyl-substituted N-alkoxy HALS include 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-piperidinol; 1-(2-hydroxy-2-methylpropoxy)- 4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; 1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadeca noyloxy-2-methylpropane; 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; 1-(2-hydroxyethyl)-2,2,6,6-tetra and reaction products of methyl-4-piperidinol and dimethylsuccinate.

A commercially available product may be used as the hindered amine light stabilizer. Examples of such commercially available products include BASF Japan Ltd. Tinuvin 123, Tinuvin 152, Tinuvin NOR 371 FF, Tinuvin XT850 FF, Tinuvin XT855 FF, Tinuvin 5100, Tinuvin 622SF, Flamestab NOR 116 ADEF, FKA ( ADEKA STAB LA-81 manufactured by ADEKA CORPORATION. These may be used alone or in combination of two or more.

The nanoindentation hardness of the transparent resin layer is preferably 30 MPa or more and 80 MPa or less, more preferably 40 MPa or more and 60 MPa or less.

In this specification, the method for measuring the nanoindentation hardness of the transparent resin layer is the same as the method for measuring the nanoindentation hardness of the substrate sheet described above.

Although the thickness of the transparent resin layer is not limited, it 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, it is possible to form deep embossing, and it is easy to obtain the effect of suppressing the generation of scratches and scraping (picture removal) due to wear of the picture pattern layer. .

Transparent Adhesive Layer A transparent adhesive layer may be formed in order to enhance the adhesion between the picture pattern layer and the transparent resin layer or surface protective layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and may be colorless transparent, colored 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 individually by 1 type or in combination of 2 or more types. In addition, a two-component curing type polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

Although the thickness of the transparent adhesive layer is not particularly limited, the thickness is about 0.1 to 30 μm, preferably about 1 to 20 μm.

Primer layer A primer 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 surface protective layer, and in combination with the surface protective layer, can improve the bending workability and scratch resistance of the decorative sheet. Further, a primer layer may be provided on the base sheet in order to enhance the adhesion between the base sheet and the layer laminated on the base sheet. The primer layer is not particularly limited as long as it is transparent, and may be colorless transparent, colored 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, etc., urethane-cellulose resins (for example, urethane and nitrocellulose resin obtained by adding hexamethylene diisocyanate to a mixture of ), and a resin-based primer made of a block copolymer of acrylic and urethane. Among these, a urethane resin-based primer 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; The blending amount of the additive can be appropriately set according to the product characteristics.

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

Although the thickness of the primer layer is not limited, it 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 the thickness within such a range, the combination with the surface protective layer facilitates enhancing the bending workability and scratch resistance of the decorative sheet. In addition, it becomes easy to contain additives such as weather resistance agents, and it becomes easy to impart weather resistance to the decorative sheet.

Surface Protective Layer The decorative sheet of the present invention comprises at least a surface protective layer on the thermoplastic resin base sheet. The decorative sheet of the present invention preferably has a surface protective layer on the outermost surface side.

The surface protective layer contains an antiviral agent in addition to the resin component. The resin component is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, or translucent.

Although the resin component forming the surface protective layer is not limited, it is preferably a cross-linking curable resin, and more preferably contains an ionizing radiation curable resin or a two-liquid curable urethane resin. Substantially, those formed from these resins are preferred. When the outermost layer is formed from an ionizing radiation-curable resin or a two-component curable 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.

Ionizing radiation-curable resins are not particularly limited, and are prepolymers (including oligomers) and/or monomers containing radically polymerizable double bonds capable of polymerizing and cross-linking in the molecule upon exposure to ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used singly or in combination. The curing reaction is typically a cross-linking 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, a cationically polymerizable functional group such as an epoxy group, or the like in the molecule. is mentioned. A polyene/thiol prepolymer obtained by combining a polyene and a polythiol is also preferable. Here, a (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 molecular weight of these compounds is generally preferably about 250 to 100,000.

Examples of monomers having radically polymerizable unsaturated groups include monofunctional monomers such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate. 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( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

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

In the present invention, the surface protective layer contains 65% by weight or more and 95% by weight or less of a urethane (meth)acrylate oligomer (A) having a weight average molecular weight of 1000 to 3000 and having two radically polymerizable unsaturated groups in one molecule. and a cured product layer of a resin mixture containing 5% by weight or more and 35% by weight or less of an aliphatic urethane (meth)acrylate oligomer (B) having 3 to 15 radically polymerizable unsaturated groups in one molecule. is preferred. When the surface protective layer has such a structure, the crosslink density is high, so effects such as scratch resistance and stain resistance can be easily obtained. There is an advantage that it is easy to adjust the surface properties according to the application, such as by making the resin layer in a mode excellent in impact resistance or in a mode excellent in workability such as V-cut.
Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the present invention, a mixed resin containing two types of aliphatic urethane acrylate, resin A and resin B described below, can also be used as the ionizing radiation-curable resin.

Resin A is an aliphatic urethane acrylate having an isocyanurate skeleton, and is not limited as long as this requirement is satisfied. Specific examples include a trimer of hexamethylene diisocyanate (especially 1,6-hexamethylene diisocyanate), a trimer of tolylene diisocyanate, a trimer of meta-xylene diisocyanate, and the like. Note that tolylene diisocyanate and meta-xylene diisocyanate may be inferior to hexamethylene diisocyanate in weather resistance due to the fact that they have a benzene ring, so these diisocyanates are preferably hydrogenated. These resins A are effective in improving stain resistance, alkali resistance, etc. of the surface protective layer.

Resin B is an aliphatic urethane acrylate that does not have an isocyanurate skeleton and has an alicyclic skeleton, and is not limited as long as it satisfies this requirement. is preferred. Specifically, PG-modified diacrylate of hydrogenated dicyclohexylmethane diisocyanate (hydrogenated MDI), and the like, which is obtained by adding an acrylate to the end of a urethane oligomer, which is a polymer of isophorone diisocyanate and butanediol as monomers, can be mentioned. be done. These resins B have the effect of imparting flexibility to the surface protective layer, and when combined with the resin A, the surface protective layer has excellent stain resistance, alkali resistance, etc. over a long period of time, and when an impact is applied, Gives the effect of suppressing the occurrence of cracks and cracks during processing.

The content ratio of resin A and resin B in the ionizing radiation curable resin is not limited, but when the total amount of resin A and resin B is 100% by mass, resin A is 10 to 50% by mass and resin B is 10 to 50% by mass. is preferably in the range of 50 to 90% by mass, more preferably in the range of 20 to 40% by mass for Resin A and 60 to 80% by mass for Resin B.

Ionizing radiation-curable resins are mainly composed of prepolymers (including oligomers) and/or monomers containing radically polymerizable double bonds capable of polymerizing and cross-linking by irradiation with ionizing radiation such as ultraviolet rays and electron beams. The curing reaction is usually a cross-linking curing reaction. As the ionizing radiation used for curing the ionizing radiation-curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation-curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible rays, X-rays, ion beams, etc. may also be used. In the present invention, among the ionizing radiation-curable resins, the properties of the raw material resin can be directly reflected in the properties of the resin component of the surface protective layer because it does not contain a photopolymerization initiator. It is preferable to use an electron beam-curing resin because the width of the resin is widened.

Although it is not particularly limited as a two-liquid curing type urethane resin, among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) having an OH group as a main agent and an isocyanate component (tolylene isocyanate, hexamethylene diisocyanate, meta-xylene diisocyanate, etc.) can be used.

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

The surface protective layer contains an antiviral agent. The antiviral agents include inorganic metal antiviral agents and organic antiviral agents.

The content of the antiviral agent in the surface protective layer (the total content of the inorganic metal antiviral agent and the organic antiviral agent) was 2.1 parts by mass based on 100 parts by mass of the resin component in the surface protective layer. 10 parts by mass or less is preferable, 2.5 parts by mass or more and 7 parts by mass or less is more preferable, and 3 parts by mass or more and 5 parts by mass or less is even more preferable. When the lower limit of the content of the antiviral agent is within the above range, the antiviral properties of the decorative sheet are further improved. Moreover, discoloration of the surface protective layer is further suppressed by setting the upper limit of the content of the antiviral agent within the above range.

Since the antiviral agent includes an inorganic metal antiviral agent and an organic antiviral agent, it may have two different average particle size peaks.

The inorganic metal-based antiviral agent is not particularly limited, and examples thereof include silver-based antiviral agents, zinc-based antiviral agents, and copper-based antiviral agents. Specifically, an inorganic metal-based antiviral agent in which metal ions such as silver, copper, and zinc are supported on zeolite, apatite, zirconia, glass, or the like can be used. Among these, silver-containing inorganic particles containing silver can be preferably used.

As silver-containing inorganic particles, composite materials formed by incorporating silver ions into substances such as zeolite, apatite, zirconia, and molybdenum oxide, which are inorganic particles, can be used. Silver-supported glass particles can also be used, and phosphoric acid is a typical example of the glass component. Silver-supported glass particles contain silver as one of the glass components and are positioned as soluble glass, and by adjusting the glass composition, the solubility when in contact with water can be adjusted. It is thought that even if the amount of silver-supported glass particles added is relatively small, antiviral performance and further antibacterial performance are likely to be exhibited. Here, silver-supported glass particles are thought to inactivate viruses and bacteria by dissolving the glass and eluting silver ions upon contact with water. In addition, since silver-supported molybdenum oxide particles can support a large amount of silver ions, even if the amount of silver-supported molybdenum oxide particles used is small, it is possible to express antiviral performance and antibacterial performance. There is an advantage that it hardly affects the surface performance of the protective layer.

Commercially available products for various applications may be used as these silver-containing inorganic particles.

The inorganic metal-based antiviral agents may be used singly or in combination of two or more.

Although the average particle size of the inorganic metal antiviral agent is not limited, it is preferably 1 μm or more and 12 μm or less, more preferably 2 μm or more and 10 μm or less. In addition, the lower limit of the average particle size can also be set to 1 μm “exceed”.
Here, the average particle size in the present specification is a value that can be obtained as a mass average value D50 in particle size distribution measurement by a laser beam diffraction method.

The content of the inorganic metal-based antiviral agent in the surface protective layer is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, and 0.1 parts by mass or more based on 100 parts by mass of the resin component in the surface protective layer. 2.5 parts by mass or less is more preferable, and 0.2 parts by mass or more and 1.0 parts by mass or less is even more preferable. When the lower limit of the content of the inorganic metal antiviral agent is within the above range, the antiviral properties of the decorative sheet are further improved. Moreover, discoloration of the surface protective layer is further suppressed when the upper limit of the content of the inorganic metal antiviral agent is within the above range.

When the inorganic metal antiviral agent is silver-containing inorganic particles, the content of the silver-containing inorganic particles in the surface protective layer is 0.01 μg/cm when the silver ion concentration measured by ICP-OES measurement on the decorative sheet of the present invention is 0.01 μg/cm. ² or more and 0.50 μg/cm ² or less is preferable, 0.018 μg/cm ² or more and 0.30 μg/cm ² or less is more preferable, and 0.05 μg/cm ² or more and 0.30 μg/cm ² or less is more preferable. In addition, in the ICP-OES measurement in this specification, after cutting the decorative sheet into 10 cm × 10 cm, put it in a polypropylene bag containing 50 ml of ultrapure water, heat it in a 40 ° C. constant temperature bath for 1 hour, and add ultrapure water. This was done by measuring the silver ion concentration with an extraction ICP-OES measurement.

The organic antiviral agent is not particularly limited, and examples include quaternary ammonium salts, quaternary phosphonium salts, pyridines, pyrithiones, benzimidazoles, organic iodine, isothiazolines, anionics, and ethers. Antiviral agents such as

Among the above organic antiviral agents, benzimidazole antiviral agents, anionic antiviral agents, and ether antiviral agents, which are antiviral agents that maintain particle shape, are preferably used. When the antiviral agent maintains its particle shape, it means that the antiviral agent does not dissolve in the composition for forming the surface protective layer (resin composition for forming the surface protective layer) and remains in the surface protective layer after curing. It means that it exists in the state of particles. Therefore, in the process of forming the surface protective layer, the particles of the antiviral agent tend to float in the resin composition for forming the surface protective layer applied on the layer such as the base material sheet, and the surface protective layer is formed. It is possible to make it easier to unevenly distribute the particles of the antiviral agent on the surface side (the side opposite to the base sheet). Then, by unevenly distributing the particles of the antiviral agent on the front surface side of the surface protective layer (the side opposite to the base sheet), the amount of the antiviral agent required to obtain a predetermined antiviral property can be adjusted. can be suppressed, and the antiviral properties of the surface protective layer are further improved.

The anionic antiviral agent preferably contains, for example, a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound. In addition, the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably contain at least one structure among the structures of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and may contain all structures. more preferred.

In general, enveloped viruses can be inactivated relatively easily by destroying the envelope (lipid layer). Therefore, if only the effect on enveloped viruses is expected, only the styrene polymer derivative compound should be contained. If only the styrene resin alone is included, sufficient effects may be obtained in some cases.

On the other hand, for non-enveloped viruses whose activity is difficult to inhibit, it may be necessary to increase the amount of the styrene polymer derivative compound and/or styrene resin in combination, thereby improving the surface performance that the surface protective layer should originally possess. It may impede. Therefore, in order to obtain a sufficient inhibition of activity against non-enveloped viruses, it is preferable to use the carboxylic acid derivative compound as a mixture. Use a compound containing all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as constituents of the compound is more preferred.

The reason why the anionic antiviral agent exhibits antiviral properties is presumed as follows, but is not limited to the following. That is, various viruses bind to sugar chain receptors (sugar chain ends are neuraminic acid) on the surface of host cells and invade host cells. It is thought that by binding to the virus instead of the host cell and capturing the virus, it suppresses the binding of the virus to the host cell receptor and exerts an antiviral effect. Specifically, functional groups having shared electron pairs, such as multiple types of amino groups described above, are bound to the spike protein of enveloped viruses and the capsid (protein shell) of non-enveloped viruses as constituents of carboxylic acid derivatives. (Capture). At the same time or subordinately, the sulfonic acid group of the styrene polymer derivative destroys the envelope to inactivate the enveloped virus, and the carboxyl group of the carboxylic acid derivative compound oxidizes the capsid to inactivate the non-enveloped virus. be done. In addition, as described above, the sulfonic acid group mainly contributes to the destruction of the envelope, and since it has oxidizing power, it can also contribute to the oxidation of the capsid of the non-enveloped virus in the same way as the carboxy group. Therefore, simultaneous use of a carboxylic acid derivative and a styrene polymer derivative is effective in inactivating enveloped viruses while efficiently inactivating non-enveloped viruses.

Examples of the benzimidazole-based antiviral agents include benzimidazole-based compounds such as methyl-benzimidazol-2-ylcarbamate (carbendazim); and polymerized imidazole-based compounds.

As the ether-based antiviral agent, for example, a phenyl ether derivative compound is preferable. Examples of the phenyl ether derivative compounds include polyoxyethylene alkylphenyl ethers. In addition, polyoxyethylene alkyl ether can be used as an ether-based antiviral agent when considering biodegradability, cost, etc., and these can express antiviral performance as ether-type nonionic surfactants. It is known.

Commercially available products for various purposes may be used as these organic antiviral agents.

The above organic antiviral agents may be used singly or in combination of two or more.

The organic antiviral agent may be in any form, such as a solid such as particles, or a liquid. Moreover, when the organic antiviral agent is solid, the shape is not particularly limited, and examples thereof include spheres, ellipsoids, polyhedrons, scales, and the like.

When the organic antiviral agent is particulate, the average particle size of the organic antiviral agent is not limited, but is preferably 1 μm or more and 12 μm or less, more preferably 2 μm or more and 10 μm or less.

Regardless of whether it is an inorganic antiviral agent or an organic antiviral agent, the particulate antiviral agent (antiviral particles) added to the ink for forming the surface protective layer (resin composition for forming the surface protective layer) Even if the surface protective layer is aggregated until the surface protective layer is completely cured and the particle size exceeds the preferred range of the average particle size, it has little effect on the expression of antiviral performance.

In addition, in order to achieve both the predetermined antiviral performance and various performances such as scratch resistance, stain resistance, and anti-slip properties of the surface protective layer, cross-sectional observation of the surface protective layer (observation from the direction perpendicular to the thickness direction) ), it is preferable to set the cross-sectional area ratio (occupancy) of the antiviral agent to 1% or more and 10% or less with respect to 100% of the cross-sectional area of the surface protective layer. When the lower limit of the cross-sectional area ratio of the antiviral agent is in the above range, the antiviral performance of the surface protective layer is further improved. Various performances (scratch resistance, stain resistance, slip resistance, etc.) are further improved. The cross-sectional area ratio is a value calculated by observing a cross section in the thickness direction (an arbitrary width of 200 μm; “width” is a direction perpendicular to the thickness direction) with a digital microscope.

Furthermore, in order to achieve both the predetermined antiviral performance and the performance of the surface protective layer, when observing the surface of the surface protective layer (observation in the thickness direction from above), the amount of the antiviral agent with respect to 100% of the surface area of the surface protective layer It is preferable to set the surface area ratio (occupancy) to 6% or more and 20% or less. By setting the surface area ratio of the antiviral agent to 6% or more, a predetermined antiviral performance can be easily obtained, and by setting the surface area ratio of the antiviral agent to 20% or less, the above-mentioned various performances of the surface protective layer (scratch resistance , stain resistance, slip resistance, etc.) are further improved. The surface area ratio is a value calculated by measuring an arbitrary 2 mm long×3 mm wide area of 100% using a laser microscope and calculating the average value of n=5.

The content of the organic antiviral agent in the surface protective layer is preferably 2.0 parts by mass or more and 5.0 parts by mass or less, and 2.5 parts by mass or more4 based on 100 parts by mass of the resin component in the surface protective layer. 0 mass part or less is more preferable. When the lower limit of the content of the organic antiviral agent is within the above range, the antiviral properties of the decorative sheet are further improved. In addition, when the upper limit of the content of the organic antiviral agent is within the above range, it is possible to suppress deterioration of the physical properties of the coating film such as scratch resistance of the surface protective layer.

The mass ratio of the inorganic metal antiviral agent to the organic antiviral agent (inorganic metal antiviral agent:organic antiviral agent) in the surface protective layer is preferably 1:5 to 1:20, more preferably 1:7. ~1:15 is more preferred. When the mass ratio is within the above range, the antiviral properties of the decorative sheet are further improved, and discoloration of the surface protective layer is further suppressed.

The nanoindentation hardness of the surface protective layer is preferably 100 MPa or higher, more preferably 250 MPa or higher. When the lower limit of the indentation hardness of the surface protective layer is within the above range, the scratch resistance of the decorative sheet of the present invention is further improved. Moreover, the nanoindentation hardness of the surface protective layer is preferably 450 MPa or less, more preferably 400 MPa or less, and even more preferably 350 MPa or less. When the upper limit of the indentation hardness of the surface protective layer is within the above range, the processability of the decorative sheet of the present invention is further improved.

In this specification, the method for measuring the nanoindentation hardness of the surface protective layer is the same as the method for measuring the nanoindentation hardness of the substrate sheet described above.

Although the thickness of the surface protective layer is not limited, it is preferably 1 μm or more and 50 μm or less, more preferably 5 μm or more and 35 μm or less. In addition, the thickness of the surface protective layer means a measured value at a flat portion where the embossed uneven pattern is not formed.

The surface protective layer is formed by, for example, applying a resin composition for forming a surface protective layer containing a crosslinked curable resin and an antiviral agent on the primer layer by a known coating method such as gravure coating or roll coating, and then removing the resin. It can be formed by curing.

In addition, the surface protective layer may contain coloring agents such as dyes and pigments, fillers such as inorganic fillers, weather resistance agents, antifoaming agents, leveling agents, thixotropy imparting agents, Additives such as flame retardants, antioxidants, lubricants, ultraviolet absorbers and light stabilizers may be added. The blending amount of the additive can be appropriately set according to the product characteristics.

In the case of imparting a low-gloss design to the decorative sheet, this can be achieved by adding matte silica as a filler such as the above-mentioned inorganic filler and increasing the blending amount.

However, when an anionic antiviral agent is selected as the antiviral agent to be added to the surface protective layer, it is preferable to use hydrophobized silica as the matte silica. Since ordinary matte silica is hydrophilic and has a hydrophilic group, it is positively charged in the resin composition for forming a surface protective layer and can react with the negatively charged functional group of the anionic antiviral agent. It may reduce the antiviral performance of anionic antiviral agents. Even in such a case, the antiviral performance of the anionic antiviral agent can be prevented from deteriorating by using hydrophobized silica as the matte silica.

Embossing Embossing is performed to impart a desired texture (embossed uneven pattern) such as a wood grain pattern to the decorative sheet. good too. For example, after the surface protective layer is heated and softened, it is pressurized and shaped with an embossed plate having an uneven pattern of a desired shape, and is cooled and fixed to impart a texture. Embossing can be carried out on a known sheet-fed or rotary embossing machine.

Examples of embossed uneven patterns include wood grain conduit grooves, embossed patterns (uneven patterns of embossed annual rings), hairlines, sand grains, and satin finish.

If embossing is applied, the embossed recesses may be filled with ink by wiping, if necessary. For example, the embossed recesses are filled with ink while scraping the surface with a doctor blade. As the filling ink (wiping ink), an ink containing a two-liquid curable urethane resin as a binder can be used. In particular, by performing wiping processing on the unevenness of the wood grain conduit groove, the product value can be enhanced by expressing a design that is closer to the actual wood grain.

Back surface primer layer A back surface primer layer may be provided on the back surface of the base sheet, if necessary. For example, it is effective when a base material sheet and a decorative board base material are adhered to produce a decorative board.

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, etc., urethane-cellulose resins (for example, urethane and nitrocellulose resin obtained by adding hexamethylene diisocyanate to a mixture of ), and a resin-based primer made of a block copolymer of acrylic and urethane.

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 according to the product characteristics.

Although the thickness of the back primer layer is not particularly limited, it is usually about 0.01 to 10 μm, preferably about 0.1 to 5 μm.

If necessary, a synthetic resin backer layer may be provided on the back surface of the synthetic resin backer layer substrate sheet. By having a synthetic resin backer layer, the impact resistance of the decorative sheet is further improved. When the back primer layer described above is also provided, the synthetic resin backer layer and the back primer layer are provided in this order from the base sheet side on the back surface of the base sheet.

Examples of the resin constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, polyalkylene terephthalate with high heat resistance [e.g. So-called PET-G (manufactured by Eastman Chemical Company), which is polyethylene terephthalate substituted with ,4-cyclohexanedimethanol, diethylene glycol, etc.], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, Polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, diene rubber such as styrene butadiene rubber, isoprene rubber, chloroprene rubber, non-diene rubber such as butyl rubber, ethylene propylene rubber, natural rubber, thermoplastic elastomer, etc. . These resins can be used singly 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, even more preferably 0.20 to 0.40 mm. By setting the lower limit of the thickness of the synthetic resin backer layer within the above range, the impact resistance of the decorative sheet is further improved. Moreover, since the upper limit of the thickness of the synthetic resin backer layer is within the above range, warping of the decorative sheet is further suppressed.

Vesicle Formation of Various Additives Contained in Each Layer of the Decorative Sheet Various additives (such as inorganic fillers added to the surface protective layer) added to the above-described layers of the decorative sheet of the present invention are converted into vesicles. It is preferable that The method for forming various additives into vesicles is not particularly limited, and vesicle formation can be performed by a known method, and among them, the supercritical reverse phase evaporation method is preferred.

Examples of the vesicle treatment method include supercritical reverse phase evaporation method, Bangham method, extrusion method, hydration method, reverse phase evaporation method, freeze-thaw method, and the like. Briefly describing such a vesicle treatment method, in the Bangham method, chloroform or a mixed solvent of chloroform/methanol is put into a container such as a flask, and then phospholipid is added and dissolved. Thereafter, the solvent is removed using an evaporator to form a lipid thin film, a dispersion of additives is added, and vesicles are obtained by hydrating and dispersing with a vortex mixer. The extrusion method is a method of obtaining vesicles by preparing a thin film phospholipid solution and passing it through a filter instead of the mixer used as the external perturbation in the Bangham method. The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining vesicles by gently stirring and dispersing 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 make a W/O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and water is added. This is a method for obtaining vesicles by The freeze-thaw method is a method of using cooling and heating as external perturbation, and is a method of obtaining vesicles by repeating this cooling and heating.

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

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, and sphingomyelin. , ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

Nonionic surfactants and dispersing agents such as mixtures of nonionic surfactants with cholesterols or triacylglycerols can also be used as the substance constituting the outer membrane.

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

Examples of the cholesterols include one or more of cholesterol, α-cholestanol, β-cholestanol, cholesterol, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol, and the like. can be used.

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

2. Antiviral Decorative Sheet The antiviral decorative sheet of the present invention is composed of a laminate comprising a decorative sheet base material and the decorative sheet of the present invention in this order in the thickness direction.

FIG. 4 shows an example of an antiviral decorative board in which the decorative sheet of the present invention (the side of the base sheet 3 and the decorative board base 8 are bonded together) is laminated in this order on the base board 8 of the decorative board.

Examples of non-limiting decorative board substrates include medium-density wood fiberboards, high-density wood fiberboards, particle boards, softwood plywood, hardwood plywood, fast-growing plywood, cork sheets, cork-containing composite substrates, and thermoplastics. At least one resin plate (a resin plate containing polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc. as a main component, or a foamed product thereof) may be used. You may use these decorative board base materials by laminating|stacking them individually or in combination of 2 or more types.

Here, conifers include, for example, Japanese pine, Japanese larch, Ezo pine, Japanese cedar, Japanese cypress, pine, sequoia, and spruce. Broad-leaved trees include, for example, lauan, cinnamon, birch, sen, beech, oak, and meranti. In addition, early-growing trees include poplar, falcata, acacia, chamelele, eucalyptus, terminalaria, and the like.

When woody plywood such as coniferous plywood, hardwood plywood, and fast-growing plywood is used, the number of laminated wooden veneers (number of plies) is not limited, but usually 3 to 7 is preferable, and 5 to 7 is more preferable. Moreover, the adhesive used in producing wood plywood is not limited, and a wide range of known adhesives for woodworking can be used. Examples of adhesives 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. and adhesives. Further, the thermosetting adhesives include melamine-based, phenol-based, urea-based (vinyl acetate-urea-based, etc.) adhesives.

As the cork sheet, it is possible to use not only so-called natural cork, which is a highly elastic material obtained by exfoliating and processing the cork tissue of cork oak bark, but also so-called synthetic cork made to resemble cork. 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 substrate include a composite material obtained by laminating and bonding a cork sheet and another material (for example, a medium-density wood fiber board or a high-density wood fiber board).

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

The lamination method for laminating the decorative sheet and the decorative plate substrate is not limited, and for example, a method of sticking them together with an adhesive can be employed. The adhesive may be appropriately selected from known adhesives depending on the type of adherend. Examples include urethane, acrylic, urethane-acrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural Rubber etc. are mentioned. These adhesives are used individually or in combination of 2 or more types.

EXAMPLES 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 transparent polypropylene film having a thickness of 60 μm was prepared as a thermoplastic resin base sheet. The nanoindentation hardness of the thermoplastic resin base sheet was 60 MPa.

A back primer agent was prepared from a two-liquid curing type urethane resin using isocyanate as a curing agent. A back surface primer agent was applied to the back surface of the thermoplastic resin base sheet to form a back surface primer layer having a thickness of 2 μm.

After corona discharge treatment was applied to the front surface of the base material sheet, a primer agent was applied to form a primer layer having a thickness of 2 μm.

After coating the front surface of the primer layer with the following resin composition for forming a surface protective layer by a gravure coating method, in an environment with an oxygen concentration of 200 ppm or less, an electron beam irradiation apparatus was used at an acceleration voltage of 165 KeV and 5 Mrad. A decorative sheet was produced by irradiating electron beams under the above conditions to cure and form a surface protective layer having a thickness of 15 μm. The nanoindentation hardness of the surface protective layer was 120 MPa.
(Resin composition for forming surface protective layer)
・Electron beam curable resin: Urethane acrylate resin of 100 parts by mass in total consisting of 30 parts by mass of polyfunctional urethane oligomer and 70 parts by mass of bifunctional oligomer ・Antiviral agent:
A: Inorganic metal-based antiviral agent; silver-supported compound (manufactured by Sumika Environmental Science, trade name “Neosinthol AV-18F” (average particle size 3 μm)
B: Organic antiviral agent (styrene resin manufactured by Polysciences, trade name “Microsphere” (particle size 4.5 μm) and polyoxyethylene alkyl ether manufactured by Kao Chemicals, trade name “Emulgen 707” mixed at a mass ratio of 1:1 )
・ Antiviral agent content: A: 0.3 parts by mass, B: 3.0 parts by mass with respect to 100 parts by mass of electron beam curable resin

A decorative board was produced by laminating the decorative sheet produced as described above so that the back primer layer side of the decorative sheet was in contact with the decorative surface (pattern layer) of the directly printed wood base material.

Example 2
A colored polypropylene film having a thickness of 60 μm was prepared as a thermoplastic resin base sheet. The nanoindentation hardness of the thermoplastic resin base sheet was 60 MPa.

A back primer agent was prepared from a two-liquid curing type urethane resin using isocyanate as a curing agent. A back surface primer agent was applied to the back surface of the thermoplastic resin base sheet to form a back surface primer layer having a thickness of 2 μm.

After corona discharge treatment was applied to the front surface of the base material sheet, a primer agent was applied to form a primer layer having a thickness of 2 μm.

A pattern layer was formed on the front surface of the base sheet by gravure printing so as to have a thickness of 2 μm. A transparent adhesive layer was formed on the pattern layer using a urethane-based resin so as to have a thickness of 2 μm. On the transparent adhesive layer, a sheet of transparent polypropylene resin was laminated by an extrusion lamination method so as to have a thickness of 80 μm to form a transparent resin layer. The nanoindentation hardness of the transparent resin layer was 60 MPa. Next, the front surface of the transparent resin layer was subjected to a corona discharge treatment, and then a primer layer was formed by applying a primer agent to a thickness of 2 μm.

After applying the resin composition for forming a surface protective layer having the same composition as in Example 1 to the front surface of the primer layer by gravure coating, in an environment with an oxygen concentration of 200 ppm or less, using an electron beam irradiation device. It was cured by irradiation with an electron beam under conditions of an acceleration voltage of 165 KeV and 5 Mrad to form a surface protective layer having a thickness of 15 μm. The nanoindentation hardness of the surface protective layer was 120 MPa. Next, after heating the surface protective layer side with an infrared non-contact type heater, embossing was immediately performed by hot pressing to form an uneven shape, thereby producing a decorative sheet.

A decorative board was manufactured in the same manner as in Example 1 using the decorative sheet manufactured as described above.

Example 3
Same as Example 1, except that 20 parts by mass of hydrophobized silica (average particle size: 11 µm) was added as an inorganic filler to 100 parts by mass of the electron beam curable resin in the resin composition for forming the surface protective layer. Then, a decorative sheet and a decorative board were manufactured.

Comparative example 1
A decorative sheet was produced in the same manner as in Example 2, except that the following antiviral agent was used as the antiviral agent to be added to the resin composition for forming a surface protective layer. The nanoindentation hardness of the surface protective layer was 170 MPa.
・ Antiviral agent: Silver-supported phosphate glass particles manufactured by Koa Glass Co., Ltd. Product name “PG711” (average particle size 3 μm)
・ Antiviral agent content: 5.0 parts by mass with respect to 100 parts by mass of electron beam curable resin

A decorative board was manufactured in the same manner as in Example 1 using the decorative sheet manufactured as described above.

Comparative example 2
Per 100 parts by mass of highly crystalline homopolypropylene resin, 0.5 parts by mass of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF) and a triazine-based ultraviolet absorber (CYASORB UV-1164; manufactured by SUNCHEM). 0.5 parts by mass and 0.5 parts by mass of a NOR-type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) are melt-extruded using an extruder to form a transparent high A sheet-like transparent resin layer was formed from a crystalline polypropylene sheet. The nanoindentation hardness was set to 90 MPa by controlling the temperature during extrusion. Both surfaces of the obtained transparent resin layer were subjected to corona treatment to adjust the wetting tension of the sheet surface to 40 dyn/cm or more.

On the other hand, on one side of an 80 μm thick polyethylene sheet (colored layer) having a concealing property, a pattern is printed by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to form a pattern layer. was provided, and a primer coat was applied to the other surface of the colored layer. Next, a transparent resin layer is laminated on the pattern layer surface of the colored layer via a dry lamination adhesive (Takelac A540; manufactured by Mitsui Chemicals, Inc.; coating amount: 2 g/m ² ) by a dry lamination method. rice field. An embossed pattern was applied to the surface of the transparent resin layer of this laminated sheet.

The following resin composition for forming a surface protective layer was used on a transparent resin layer having an embossed pattern, and a thermosetting composition (coating amount after drying (denoted by film thickness after drying; the same shall apply hereinafter) 5 μm), By sequentially laminating the photocurable composition (5 μm coating amount after drying), the surface protective layer 5 consisting of two layers, a thermosetting layer (lower layer) and a photocurable layer (upper layer), is formed, and the total thickness is 195 μm Comparison. A decorative sheet of Example 2 was obtained.

[Thermosetting composition]
The thermosetting composition was prepared by blending the following polyol solution A with the following curing agent, gloss modifier, ultraviolet absorber, and light stabilizer.
・ Polyol 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 to dissolve, followed by nitrogen atmosphere on an oil bath. Stir on the bottom. Polymerization was initiated by adding 0.2 g of α,α'-azobisisobutyronitrile thereto, and the mixture was heated and stirred on an oil bath at 60°C for 5 hours to give a colorless, viscous polyol solution A. got
Composition: 80 parts by mass

・ Curing agent Product name: Duranate TPA-100 (manufactured by Asahi Kasei Corporation)
Compounding: 5 parts by mass Gloss adjuster (inorganic particles)
Product name: Silophobic 702 (manufactured by Fuji Silysia Chemical Co., Ltd.)
Properties: amorphous, average particle size 4 μm, oil absorption 170 mL/100 g
Composition: 10 parts by mass, UV absorber Product name: Tinuvin 400 (manufactured by BASF)
Composition: 5.0 parts by mass Light stabilizer Product name: Tinuvin 123 (manufactured by BASF)
Composition: 2.0 parts by mass/Dilution solvent Product name: Ethyl acetate Composition: 50 parts by mass

[Photocurable composition]
The photocurable composition was prepared by blending the following UV resin with the following antiviral agent, photoinitiator, gloss modifier, and light stabilizer.
・UV resin Product name: UA-33H
Properties: molecular weight 1400, number of functional groups 9
Composition: 90 parts by mass Antiviral agent A silver-based inorganic antibacterial agent (TB-B100, manufactured by Taisho Technos Co., Ltd.) was used. 0.1 part by mass of a silver-based inorganic antibacterial agent having an average particle size of 5 μm was added to the acrylic resin composition. In addition, the active ingredient of the antiviral agent is supported by an inorganic material. At this time, the first peak of the particle size of the antiviral agent was 3 μm, and the second peak was 7 μm.
・Photoinitiator Product name: Irgacure 184
Compounding: 8 parts by mass, gloss modifier (inorganic particles)
Product name: Silophobic 702 (manufactured by Fuji Silysia Chemical Co., Ltd.)
Properties: amorphous, average particle size 4 μm, oil absorption 170 mL/100 g
Composition: 10 parts by mass Light stabilizer Product name: Tinuvin 123 (manufactured by BASF)
Composition: 2.0 parts by mass/Dilution solvent Product name: Ethyl acetate Composition: 60 parts by mass

A decorative board was manufactured in the same manner as in Example 1 using the decorative sheet manufactured as described above.

Using the decorative sheets and boards produced in Examples 1 to 3 and Comparative Examples 1 and 2, the properties were evaluated by the following tests. For Example 3, only antiviral performance-1 of Test Example 1 (evaluation of antiviral property) was evaluated among the following tests.

Test Example 1 (antiviral evaluation)
For the decorative sheets produced in Examples and Comparative Examples, the silver ion concentration was measured by ICP-OES measurement and the antiviral performance was evaluated. Each measurement method and evaluation method are as follows.

<ICP-OES measurement>
After cutting the decorative sheet prepared in Examples and Comparative Examples into 10 cm × 10 cm pieces, put it in a polypropylene bag containing 50 ml of ultrapure water, heat it in a 40 ° C. constant temperature bath for 1 hour, remove the ultrapure water, and ICP- The silver ion concentration was measured by OES measurement.

<Antiviral performance-1>
The surface protective layer side of the decorative sheets produced in Examples and Comparative Examples was subjected to an antiviral performance test in accordance with the antiviral test method (ISO21702), and the antiviral activity value against influenza virus was obtained according to the following evaluation criteria. evaluated.
++: Antiviral activity value after 6 hours is 2.0 or more +: Antiviral activity value after 6 hours is less than 2.0, but antiviral activity value after 24 hours is 2.0 or more Yes-: Antiviral activity value after 24 hours is less than 2.0

Test Example 2 (Evaluation of discoloration suppression (design property))
Twenty adult males and females (10 males and 10 females) observed the decorative boards produced in Examples and Comparative Examples from the outermost surface side to check whether the visibility of the pattern was reduced due to discoloration of the surface protective layer. , was evaluated according to the following evaluation criteria.
+: More than 80% of adult men and women judged that the visibility of the pattern was clear -: Less than 80% of adult men and women judged that the visibility of the pattern was clear

Test Example 3 (Evaluation of nanoindentation hardness)
For the decorative sheets produced in Examples and Comparative Examples, the nanoindentation hardness of the surface protective layer, the transparent resin layer, and the base sheet was measured as described above as the method for measuring the nanoindentation hardness of the base sheet. method.

The results are shown in Tables 1 and 2 below.

Example 4
A decorative sheet and a decorative board were produced in the same manner as in Example 1, except that the following antiviral agent was used as the antiviral agent to be added to the surface protective layer-forming resin composition in the following content.

• Antiviral agent The following inorganic metal antiviral agent and organic antiviral agent were mixed at a mass ratio of 1:6 and used.
A: Inorganic metal-based antiviral agent; silver-supported compound (trade name “Zeomic” manufactured by Sinanen Zeomic Co., Ltd. (average particle size 10 μm)
B: Organic antiviral agent: An anionic antiviral agent prepared as follows was used. <Preparation of anionic antiviral agent>
As carboxylic acid derivatives, cyclohexanecarboxylic acid (manufactured by Shin Nippon Rika Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N,N-dimethylallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dimethylpyrrole (Tokyo Kasei Kogyo Co., Ltd.) and N,N,2,2-tetramethyl-1,3-propanediamine (Tokyo Kasei Kogyo Co., Ltd.) are prepared, mixed and reacted to form a mixture of carboxylic acid derivative compounds. was prepared. In addition, as styrene polymer derivatives, sodium p-styrenesulfonate (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 " A mixture of styrene polymer derivative compounds was prepared by preparing 86% ethanol-ME"), mixing and reacting. Next, the mixture of the carboxylic acid derivative compound and the mixture of the styrene polymer derivative compound are mixed at a mass ratio of 3:1, and pulverized with a jet mill (manufactured by Nisshin Engineering Co., Ltd., trade name “SJ-100”). An organic antiviral agent was prepared by The average particle size of the organic antiviral agent was measured according to JIS Z8825-1 using a laser diffraction particle size distribution analyzer (manufactured by HORIBA) and found to be 9 μm.
・ Antiviral agent content: A: 0.5 parts by mass, B: 3.0 parts by mass with respect to 100 parts by mass of electron beam curable resin

Regarding the film produced in Example 4, the above-described Test Example 1 (evaluation of antiviral properties), Test Example 2 (evaluation of discoloration suppression (design property)), and Test Example 3 (evaluation of nanoindentation hardness). The characteristics were evaluated by each test method. However, in Test Example 1, in addition to <antiviral performance-1>, the following <antiviral performance-2> was also performed to evaluate the antiviral performance.

<Antiviral performance-2>
An antiviral performance test was performed on the surface protective layer side of the decorative sheet produced in Example 4 by a method based on the antiviral test method (ISO21702), and the antiviral activity value against feline calicivirus was evaluated according to the following evaluation criteria. evaluated.
++: Antiviral activity value after 6 hours is 2.0 or more +: Antiviral activity value after 6 hours is less than 2.0, but antiviral activity value after 24 hours is 2.0 or more Yes-: Antiviral activity value after 24 hours is less than 2.0

The results are shown in Table 3 below.

1. Antiviral cosmetic sheet2. back primer layer3. Thermoplastic resin base sheet4. pattern layer5. transparent resin layer6. surface protective layer 7 . Synthetic resin backer layer8. Decorative board base material

Claims (19)

An antiviral decorative sheet comprising at least a surface protective layer on a thermoplastic resin base sheet,
The surface protective layer contains an antiviral agent,
The antiviral agent includes an inorganic metal antiviral agent and an organic antiviral agent.
An antiviral cosmetic sheet characterized by: The antiviral property according to claim 1, wherein the inorganic metal-based antiviral agent is at least one selected from the group consisting of a silver-based antiviral agent, a zinc-based antiviral agent, and a copper-based antiviral agent. cosmetic sheet. The antiviral property according to claim 1, wherein the organic antiviral agent is at least one selected from the group consisting of benzimidazole antiviral agents, anionic antiviral agents, and ether antiviral agents. cosmetic sheet. The antiviral according to claim 1, wherein the content of the antiviral agent in the surface protective layer is 2.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component in the surface protective layer. sexual makeup sheet. The mass ratio of the inorganic metal antiviral agent and the organic antiviral agent in the surface protective layer (mass of the inorganic metal antiviral agent: mass of the organic antiviral agent) is 1:5 to The antiviral cosmetic sheet according to claim 1, which is 1:20. 2. The content of the inorganic metal antiviral agent in the surface protective layer is 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin component in the surface protective layer. The antiviral cosmetic sheet described in . 2. The method according to claim 1, wherein the content of the organic antiviral agent in the surface protective layer is 2.0 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin component in the surface protective layer. The described antiviral cosmetic sheet. The antiviral decorative sheet according to claim 1, wherein the antiviral agent has two different average particle size peaks. 2. The antiviral decorative sheet according to claim 1, wherein the antiviral decorative sheet has a silver ion concentration of 0.018 μg/cm ² or more and 0.50 μg/cm ² or less as measured by ICP-OES measurement. 2. The antiviral decorative sheet according to claim 1, which has a patterned layer between said thermoplastic resin base sheet and said surface protective layer. 2. The antiviral decorative sheet according to claim 1, comprising a transparent resin layer between said thermoplastic resin base sheet and said surface protective layer. 12. The antiviral decorative sheet according to claim 11, wherein said thermoplastic resin base sheet and said transparent resin layer contain a polyolefin resin. The surface protective layer contains 65% by mass or more and 95% by mass or less of a urethane (meth)acrylate oligomer (A) having a weight average molecular weight of 1000 to 3000 and having two radically polymerizable unsaturated groups in one molecule; A cured product layer of a resin mixture containing 5% by mass or more and 35% by mass or less of an aliphatic urethane (meth)acrylate oligomer (B) having 3 to 15 radically polymerizable unsaturated groups in the molecule. 2. The antiviral cosmetic sheet according to 1. The antiviral decorative sheet according to claim 1, wherein the surface protective layer has a nanoindentation hardness of 100 MPa or more. The antiviral decorative sheet according to claim 1, wherein the surface protective layer has a nanoindentation hardness of 450 MPa or less. The antiviral decorative sheet according to claim 1, wherein the thermoplastic resin base sheet has a nanoindentation hardness of 30 MPa or more and 80 MPa or less. The antiviral decorative sheet according to claim 11, wherein the transparent resin layer has a nanoindentation hardness of 30 MPa or more and 80 MPa or less. The antiviral decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 1 µm or more and 50 µm or less. An antiviral decorative sheet comprising a laminate comprising a decorative sheet base material and the antiviral decorative sheet according to any one of claims 1 to 18 in order in the thickness direction.

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