Decorative sheet with allergen reducing performance, adhesion processing sheet with allergen reducing performance using the same, and decorative plate with allergen reducing performance

Abstract

To provide a decorative sheet having an allergen reducing performance exhibiting an allergen reducing effect to mite and cedar, while maintaining surface performance of a surface protective layer.SOLUTION: A decorative sheet comprises a crosslink-cured resin layer on the outermost surface. (1) The crosslink-cured resin layer contains a cured product of a crosslink-cured resin and an allergen-reducing agent. (2) The allergen-reducing agent is an allergen-reducing agent having an allergen-reducing performance on mites and cedar, contains a carboxylic acid derivative and a styrene polymer derivative, and contains all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of at least the carboxylic acid derivative. (3) The crosslink-cured resin layer further contains two different types of fine particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet having allergen-reducing properties, an adhesive-processed sheet having allergen-reducing properties using the same, and a decorative board having allergen-reducing properties, and relates to a decorative sheet having allergen-reducing properties that has allergen-reducing properties against dust mites and cedar, an adhesive-processed sheet having allergen-reducing properties using the same, and a decorative board having allergen-reducing properties. [Background technology]

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

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

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

[0044] to

[0047] ). However, while the examples in Patent Document 1 describe that antiviral activity against enveloped viruses was confirmed in an antiviral performance test, they do not specifically confirm whether the agent has allergen-reducing ability, which is a similar functionality, or what the performance is if it does have allergen-reducing ability.

[0005] Incidentally, as another prior art document related to the present application, Patent Document 2 specifically discloses a decorative sheet in which an anti-allergen function is imparted to a curable resin layer, as follows: "A decorative sheet in which a curable resin layer is formed on a thermoplastic resin substrate sheet and the curable resin layer is imparted with an anti-allergen function, the curable resin layer being formed by crosslinking and curing a curable resin composition containing a urethane (meth)acrylate oligomer composition in which 50% by mass or more of a urethane (meth)acrylate oligomer having 6 or more functionalities is contained, and an allergen reducing agent composed of a phenolic polymer, the amount of the allergen reducing agent being blended in an amount of 10 to 30 parts by mass per 100 parts by mass of the urethane (meth)acrylate oligomer composition."

[0006] Generally, both allergen-reducing agents and antiviral agents exert their allergen and virus-reducing effects by denaturing the proteins of the target substance, and therefore, it is thought that agents with similar structures will exert their allergen and virus-reducing effects. However, because viruses can be inactivated relatively more easily than allergens, antiviral effects can be easily obtained using a wide variety of known antiviral agents, and the effects are easily exhibited even with a relatively small amount added, making it possible to impart antiviral performance while maintaining the surface performance that the surface protective layer should originally have. In contrast, because allergens are relatively difficult to inactivate, even if an antiviral agent with sufficient antiviral performance is used in the same amount, it is difficult to obtain the effect of allergen-reducing performance. In order to obtain the effect with the same antiviral agent, the amount added must be increased, which may result in the problem of inhibiting the surface performance that the surface protective layer should originally have.

[0007] Therefore, there is a need for the development of a decorative sheet that has allergen-reducing properties that exhibit allergen-reducing effects against dust mites and cedars while maintaining the surface performance of the surface protective layer. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-41101 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-171195 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to provide a decorative sheet having allergen-reducing properties that exhibits allergen-reducing effects against dust mites and cedars while maintaining the surface performance of a surface protective layer. It is also an object of the present invention to provide an adhesive-processed sheet having allergen-reducing properties and a decorative board having allergen-reducing properties that use the decorative sheet. [Means for solving the problem]

[0010] As a result of extensive research, the present inventors have discovered that the above object can be achieved by incorporating a specific allergen-reducing agent into the surface protective layer, and have thus completed the present invention.

[0011] That is, the present invention relates to the following decorative sheet having allergen-reducing properties, an adhesive-processed sheet having allergen-reducing properties using the same, and a decorative board having allergen-reducing properties. 1. A decorative sheet having a cross-linked cured resin layer on the outermost layer, (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an allergen reducing agent, (2) The allergen reducing agent has allergen reducing properties against dust mites and cedars, and contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative; (3) The cross-linked cured resin layer further contains two different types of fine particles. A decorative sheet having allergen-reducing properties, characterized by: 2. A decorative sheet having allergen-reducing properties as described in item 1 above, wherein the allergen-reducing agent contains all of triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the styrene polymer derivative. 3. A decorative sheet having allergen-reducing properties according to item 1 or 2 above, wherein the cross-linked curable resin layer has fine irregularities on the outermost surface with an arithmetic mean roughness Ra of 0.1 μm or more. 4. A decorative sheet having allergen-reducing properties according to item 3 above, wherein the arithmetic mean roughness Ra of the fine irregularities is 40 μm or less. 5. A decorative sheet having allergen-reducing properties according to any one of items 1 to 4 above, wherein the fine particles consist of first fine particles having an average particle diameter of less than 4 μm and second fine particles having an average particle diameter of 4 μm or more and 30 μm or less. 6. A decorative sheet having allergen reduction properties as described in item 5 above, containing 0.1 to 10 parts by mass of the first microparticles and 0.1 to 30 parts by mass of the second microparticles per 100 parts by mass of the cross-linked curable resin. 7. The decorative sheet having allergen-reducing properties according to any one of items 1 to 6 above, wherein the cross-linked cured resin layer further contains an antibacterial agent consisting of silver-containing inorganic particles in addition to the fine particles. 8. The decorative sheet having allergen-reducing properties according to any one of items 1 to 7 above, wherein the cross-linked curable resin layer further contains a triazine-based ultraviolet absorber and / or a light stabilizer. 9. A decorative sheet having allergen-reducing properties described in any one of items 1 to 8 above, wherein the allergen-reducing agent contains the carboxylic acid derivative and the styrene polymer derivative in a mass ratio of 1:1 to 10:1, in that order. 10. A decorative sheet having allergen-reducing properties according to any one of items 1 to 9 above, wherein, when the thickness of the smooth portion of the cross-linked cured resin layer is divided into thirds into a lower layer, a middle layer, and an upper layer, the center points of 50% or more of the allergen-reducing agents are present in the middle layer or the upper layer. 11. A decorative sheet having allergen-reducing properties according to any one of items 1 to 10, which contains 1 part by mass or more and 10 parts by mass or less of the allergen-reducing agent per 100 parts by mass of the cross-linking curable resin. 12. The decorative sheet having allergen-reducing properties according to any one of items 1 to 11 above, wherein the average thickness of the smooth portion of the cross-linked curable resin layer is 2 μm or more and 35 μm or less. 13. The decorative sheet having allergen-reducing properties according to any one of items 1 to 12 above, wherein the average particle size of the allergen-reducing agent is 2 μm or more and 15 μm or less. 14. The decorative sheet having allergen-reducing properties according to any one of items 1 to 13, wherein the cross-linking curable resin contains an ionizing radiation curable resin. 15. The cross-linked cured resin layer has a Martens hardness of 30 N / mm 2 More than 180N / mm 2 15. A decorative sheet having allergen-reducing properties according to any one of items 1 to 14 above, which is as follows: 16. A decorative sheet having allergen reduction properties according to any one of items 1 to 15 above, which is composed of a laminate having at least a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and the cross-linked cured resin layer in that order in the thickness direction. 17. The Martens hardness of the base sheet and / or the transparent thermoplastic resin layer is 30 N / mm 2 More than 80N / mm 2 Item 17. A decorative sheet having allergen-reducing properties according to item 16, which is as follows: 18. An adhesive-processed sheet having allergen-reducing properties, which is composed of a laminate having, in order in the thickness direction, at least an adhesive sheet and a decorative sheet having allergen-reducing properties described in any one of items 1 to 17 above. 19. A decorative board having allergen-reducing properties, which is composed of a laminate having, in order in the thickness direction, at least a decorative board substrate and a decorative sheet having allergen-reducing properties described in any one of items 1 to 17 above. 20. A decorative board having allergen-reducing properties, which is composed of a laminate having, in order in the thickness direction, at least a decorative board substrate and the adhesive-processed sheet having allergen-reducing properties described in item 18 above. [Effects of the Invention]

[0012] The decorative sheet with allergen-reducing properties of the present invention contains a specific allergen-reducing agent in the outermost cross-linked curable resin layer (surface protective layer), which allows it to exhibit allergen-reducing effects against dust mites and cedar while maintaining the surface properties of the surface protective layer (any surface properties that a surface protective layer should originally have, such as scratch resistance, impact resistance, chemical resistance, etc.) Furthermore, when combined with a pressure-sensitive adhesive sheet, this decorative sheet can be made into an adhesive-treated sheet with allergen-reducing properties, and when combined with a decorative board substrate, each of the decorative sheet and the adhesive-treated sheet can be made into a decorative board with allergen-reducing properties. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a cross-sectional view showing an example of a decorative sheet having allergen-reducing properties according to the present invention. FIG. [Figure 2] 1 is a cross-sectional view showing an example of an adhesive sheet having allergen-reducing properties according to the present invention. [Figure 3] 1 is a cross-sectional view schematically showing an example of a constituent member of a decorative board having allergen-reducing properties according to the present invention. [Figure 4] FIG. 2 is a cross-sectional view illustrating the relationship between the thickness A of the smooth portion of the cross-linked cured resin layer (surface protective layer) of the decorative sheet having allergen-reducing properties of the present invention and the position of the center point of the allergen-reducing agent. [Figure 5] FIG. 1 shows (a) a diamond indenter used in measuring Martens hardness in this specification, (b) a schematic diagram of the indentation operation, and (c) an example of the indentation load and displacement. DETAILED DESCRIPTION OF THE INVENTION

[0014] 1. Decorative sheet with allergen reduction properties The decorative sheet having allergen-reducing properties of the present invention (hereinafter also referred to as "the decorative sheet of the present invention") is a decorative sheet having a cross-linked cured resin layer as the outermost layer, (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an allergen reducing agent, (2) The allergen reducing agent has allergen reducing properties against dust mites and cedars, and contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative; (3) The cross-linked cured resin layer further contains two different types of fine particles. It is characterized by:

[0015] The decorative sheet of the present invention contains a specific allergen-reducing agent in the outermost cross-linked curable resin layer (surface protective layer), and is therefore able to exert an allergen-reducing effect against dust mites and cedar while maintaining the surface performance of the surface protective layer (any surface performance that a surface protective layer should originally have, such as scratch resistance, impact resistance, chemical resistance, etc.) Furthermore, the decorative sheet can be combined with a pressure-sensitive adhesive sheet to form an adhesive-processed sheet with allergen-reducing properties, and the decorative sheet and the adhesive-processed sheet can each be combined with a decorative board substrate to form a decorative board with allergen-reducing properties.

[0016] The decorative sheet of the present invention has a cross-linked curable resin layer as the outermost layer, and there are no restrictions on its specific configuration (layer configuration) as long as the cross-linked curable resin layer and the allergen reducing agent contained therein satisfy the specified requirements shown in (1) to (3) above.

[0017] In a specific embodiment, the decorative sheet of the present invention may be composed of a laminate comprising, in order in the thickness direction, for example, a base sheet, a transparent thermoplastic resin layer, and a cross-linked cured resin layer. The decorative sheet of the present invention may also be composed of a laminate comprising, in order in the thickness direction, for example, a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and a cross-linked cured resin layer. In the decorative sheet of the present invention, the outermost cross-linked cured resin layer serves as a so-called surface protective layer.

[0018] FIG. 1 is a cross-sectional schematic diagram showing an example of the decorative sheet of the present invention. In FIG. 1, a picture pattern layer 3, a transparent adhesive layer 4, a transparent resin layer 5, a primer layer 6, and a cross-linked curable resin layer (surface protective layer) 7 are laminated in this order on a base sheet 2, and a back primer layer 8 is further provided on the back surface of the base sheet 2. An embossed uneven pattern is also formed. Furthermore, the presence of an allergen reducing agent 9 in the cross-linked curable resin layer (surface protective layer) 7 is schematically shown. The thickness of the cross-linked curable resin layer (surface protective layer) 7 (the thickness of the smooth portion excluding the protrusions on the outermost surface) is indicated by A in the figure, but protrusions (protrusions) exceeding the thickness A of the smooth portion may be formed due to the presence of the allergen reducing agent 9 on the front surface side of the cross-linked curable resin layer (surface protective layer) 7. Furthermore, the outermost surface of the cross-linked curable resin layer (surface protective layer) 7 may have fine irregularities in addition to the protrusions caused by the allergen reducing agent 9. The convex portions shown in FIG. 1 are protrusions caused by the allergen reducing agent 9, but the allergen reducing agent 9 itself is not exposed, but is a protrusion of a cross-linked cured resin layer.

[0019] Furthermore, the present invention also encompasses an invention (for example, an embodiment shown in Figure 2) of an adhesive sheet (hereinafter also referred to as "the adhesive sheet of the present invention") having allergen-reducing properties, which is composed of a laminate comprising, in order in the thickness direction, at least an adhesive sheet and a decorative sheet of the present invention. Note that Figure 2 illustrates the configuration of an adhesive sheet 11 having an adhesive sheet 10 on the back surface of the decorative sheet 1 shown in Figure 1, but the configuration of the decorative sheet 1 is not limited to this.

[0020] Furthermore, the present invention also encompasses an invention (for example, an embodiment shown in FIG. 3) of a decorative board (hereinafter also referred to as "the decorative board of the present invention") having allergen-reducing properties, which is composed of a laminate comprising, in order in the thickness direction, at least a decorative board substrate and the decorative sheet of the present invention or the adhesive sheet of the present invention. Note that FIG. 3 illustrates the configuration of a decorative board 13 having a decorative board substrate 12 on the back surface of the decorative sheet 1 shown in FIG. 1. Alternatively, the decorative board 13 may have a configuration in which the decorative board substrate 12 is on the back surface of the adhesive sheet 11 shown in FIG. 2.

[0021] In this specification, the surface visible after application of the decorative sheet of the present invention, i.e., the direction in which the cross-linked curable resin layer (surface protective layer) is laminated as viewed from the base sheet, is referred to as the "upper" or "front side," and the direction in which the back primer layer is laminated as viewed from the base sheet is referred to as the "lower" or "back side." This relationship is the same for the pressure-sensitive adhesive sheet of the present invention and the decorative board of the present invention. Note that when referring to the "side of the cross-linked curable resin layer (surface protective layer)" in the laminate, it is also abbreviated to "the side of the cross-linked curable resin layer (surface protective layer)."

[0022] Hereinafter, each layer of the decorative sheet of the present invention will be described using Figure 1 as an example. However, the layer structure of the decorative sheet of the present invention is not limited to the embodiment of Figure 1, and various layer structures can be adopted as a laminate, as mentioned above. In the following description, the lower and upper limits of numerical ranges expressed by "to" mean "greater than or equal to" (for example, if α to β, it means greater than or equal to α and less than or equal to β).

[0023] Base sheet The substrate sheet has a surface (front surface) on which a pattern layer and the like are sequentially laminated, with the outermost layer being a cross-linked cured resin layer (surface protection layer).

[0024] Examples of the substrate sheet include various materials such as resin films, paper, and resin-impregnated paper, but among resin films, those containing a thermoplastic resin as a resin component are preferred. Specific examples include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, and the like. In the present invention, at least one of polyvinyl chloride and polyolefins (polyethylene, polypropylene, etc.) can be preferably used.

[0025] The substrate sheet may be colored. For example, the thermoplastic resin can be colored by adding a colorant (pigment or dye). As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black, iron oxide, etc., organic pigments such as phthalocyanine blue, and various dyes can be used. One or more of these can be selected. The amount of colorant added can also be appropriately determined depending on the desired color tone, etc.

[0026] The substrate sheet may contain various additives, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers, as required.

[0027] The thickness of the substrate sheet can be appropriately set depending on the application and method of use of the final product, but is generally preferably 50 to 250 μm.

[0028] If necessary, the surface (front surface) of the substrate sheet may be subjected to a corona discharge treatment to improve adhesion of the ink that forms the picture pattern layer. The corona discharge treatment may be carried out according to known methods and conditions. If necessary, the back surface of the substrate sheet may be subjected to a corona discharge treatment, a picture pattern layer (so-called back print) may be formed, or a back primer layer (described later), a backer layer (described later), etc. may be formed.

[0029] Pattern layer The picture pattern layer is an optional layer that imparts a desired pattern (design) to the decorative sheet of the present invention, and the type of pattern is not limited. Examples include wood grain patterns, leather patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, geometric shapes, letters, symbols, abstract patterns, floral patterns, landscapes, characters, etc.

[0030] The method for forming the picture pattern layer is not particularly limited, and for example, the picture pattern layer may be formed on the surface of the substrate sheet by a known printing method using an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) together with a binder resin in a solvent (or dispersion medium). From the viewpoint of reducing VOCs in the decorative sheet, an aqueous composition can also be used as the ink.

[0031] Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, iron blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; and luminous pigments. These colorants can be used alone or in combination. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizers, surfactants, and the like.

[0032] As binder resins, in addition to hydrophilically treated polyester-based urethane resins, polyesters, polyacrylates, polyvinyl acetates, polybutadiene, polyvinyl chloride, chlorinated polypropylenes, polyethylene, polystyrene, polystyrene-acrylate copolymers, rosin derivatives, alcohol adducts of styrene-maleic anhydride copolymers, cellulose-based resins, etc. can also be used. 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-based resins, water-soluble phenol-based resins, other water-soluble synthetic resins, water-soluble natural polymers such as polynucleotides, polypeptides, and polysaccharides can also be used. Other examples include natural rubber, synthetic rubber, polyvinyl acetate-based resins, (meth)acrylic resins, polyvinyl chloride-based resins, polyurethane-polyacrylic resins, and modified versions thereof, as well as other resins. The above binder resins can be used alone or in combination of two or more.

[0033] Examples of solvents (or dispersion media) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

[0034] Examples of printing methods used to form the picture pattern layer include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. When forming a solid picture pattern layer over the entire surface, examples of coating methods include roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating. Other methods that may be used include hand-drawing, ink-flowing, photography, transfer printing, laser beam writing, electron beam writing, partial vapor deposition of metals or the like, and etching, or may be used in combination with other forming methods.

[0035] The thickness of the picture pattern layer is not particularly limited and can be set appropriately depending on the product characteristics, but the layer thickness is about 0.1 to 15 μm.

[0036] transparent resin layer The transparent resin layer can be provided arbitrarily and is not particularly limited as long as it is transparent. It may be colorless and transparent, colored and transparent, translucent, or the like. The material of the transparent resin layer is not particularly limited, but one formed from a thermoplastic resin is preferred. Specific examples include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, and the like. In the present invention, at least one of polyvinyl chloride and polyolefin (polyethylene, polypropylene, etc.) can be preferably used. In this specification, when the transparent resin layer contains a thermoplastic resin, the transparent resin layer is specifically referred to as a "transparent thermoplastic resin layer."

[0037] The transparent resin layer may be colored as long as it has transparency.

[0038] Furthermore, the transparent resin layer may contain various additives such as a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer, as needed, so long as it has transparency.

[0039] The thickness of the transparent resin layer is not limited, but is preferably 40 μm to 300 μm, more preferably 60 μm to 200 μm, and most preferably 60 μm to 100 μm. By setting the thickness of the transparent resin layer within the above range, it is possible to form a deep embossment and to easily obtain the effect of suppressing the occurrence of scratches and scraping (removal of the pattern) due to wear of the pattern layer.

[0040] transparent adhesive layer A transparent adhesive layer may be formed to enhance adhesion between the picture pattern layer and the transparent resin layer or the cross-linked cured resin layer (surface protective layer) described later. The transparent adhesive layer is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, translucent, etc.

[0041] The adhesive is not particularly limited, and adhesives known in the field of decorative sheets can be used. Examples of adhesives known in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins, and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives can be used alone or in combination of two or more. Two-component curing polyurethane resins or polyester resins using isocyanate as a curing agent can also be used.

[0042] The thickness of the transparent adhesive layer is not particularly limited, but is about 0.1 to 30 μm, preferably about 1 to 20 μm.

[0043] Primer layer A primer layer for the cross-linked curable resin layer (surface protective layer) may be provided on the transparent resin layer. This primer layer not only improves adhesion between the transparent resin layer and the cross-linked curable resin layer described below, but also improves the folding processability and scratch resistance of the decorative sheet when combined with the cross-linked curable resin layer. The primer layer is not particularly limited as long as it is transparent, and may be colorless and transparent, colored and transparent, translucent, etc.

[0044] 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 urethane resin-based primer agents made of acrylic-modified urethane resin (acrylic urethane copolymer resin), polycarbonate-based acrylic urethane copolymer resin, etc., primer agents made of urethane-cellulose resin (e.g., a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and soluble cellulose), and resin-based primer agents made of acrylic and urethane block copolymers. Among these, urethane resin-based primer agents containing polycarbonate-based acrylic urethane copolymer resins are preferred from the viewpoint of scratch resistance and weather resistance.

[0045] The primer agent may contain additives as needed. Examples of additives include weathering agents such as ultraviolet absorbers and light stabilizers; fillers such as silica, calcium carbonate, and clay; flame retardants such as magnesium hydroxide; antioxidants; lubricants; and foaming agents. The amount of additives added can be appropriately determined depending on the product characteristics.

[0046] Among the above additives, examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Examples of light stabilizers include hindered amine-based light stabilizers (HALS). The content of these weathering agents is not limited, but may be approximately 1,000 to 100,000 ppm by mass for each of the ultraviolet absorber and light stabilizer. In particular, in the present invention, it is preferable to use a triazine-based ultraviolet absorber and / or a hindered amine-based light stabilizer.

[0047] The thickness of the primer layer is not limited, but is preferably 0.5 μm to 12 μm, more preferably 1 μm to 8 μm. By setting the thickness within this range, the combination with the cross-linked cured resin layer makes it easier to improve the folding processability and scratch resistance of the decorative sheet. It also makes it easier to incorporate additives such as weathering agents, making it easier to impart weather resistance to the decorative sheet.

[0048] Cross-linked curing resin layer (surface protection layer) The decorative sheet of the present invention comprises a cross-linked curable resin layer (surface protective layer) as the outermost layer, and the cross-linked curable resin layer and the allergen reducing agent contained therein satisfy the specified requirements shown in (1) to (3) below, thereby being able to exhibit an allergen reducing effect against dust mites and cedar while maintaining the surface performance of the surface protective layer. (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an allergen reducing agent, (2) The allergen reducing agent has allergen reducing properties against dust mites and cedars, contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative; (3) The cross-linked cured resin layer further contains two different types of fine particles.

[0049] The cross-linking curable resin is not particularly limited as long as it is transparent, and may be colorless transparent, colored transparent, translucent, or the like.

[0050] In one embodiment, the resin component of the crosslinking curable resin preferably contains an ionizing radiation curable resin or a two-component curable urethane resin. The crosslinking curable resin is preferably formed from an ionizing radiation curable resin or a two-component curable urethane resin. When the outermost layer is formed from an ionizing radiation curable resin or a two-component curable urethane resin, the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet are easily improved. In one embodiment, it is particularly preferable that the resin component of the crosslinking curable resin is an ionizing radiation curable resin. In the present invention, by using an ionizing radiation curable resin or a two-component curable urethane resin as the resin component of the crosslinking curable resin, the Martens hardness of the crosslinking curable resin layer can be increased to 30 N / mm 2 More than 180N / mm 2 This makes it easier to adjust the slip resistance value (CSR value) as an index of slip resistance to 0.25 or more.

[0051] As an index of slip resistance for various uses based on the above CSR values, a value of 0.25 or higher (especially 0.25 or higher but less than 0.30) indicates that the material is suitable for use in building materials, a value of 0.30 or higher (especially 0.30 or higher but less than 0.38) indicates that the material is suitable for use in ordinary flooring, and a value of 0.38 or higher (especially 0.38 or higher but less than 0.50) indicates that the material is suitable for use as an anti-slip floor, exhibiting a high level of slip resistance.

[0052] The ionizing radiation curable resin is not particularly limited, and a transparent resin mainly composed of a prepolymer (including oligomer) and / or monomer containing a radically polymerizable double bond in the molecule that can undergo a polymerization / crosslinking reaction when irradiated with ionizing radiation such as ultraviolet light or an electron beam can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a crosslinking curing reaction.

[0053] Specifically, the prepolymer or monomer may be a compound having a radically polymerizable unsaturated group such as a (meth)acryloyl group or a (meth)acryloyloxy group, or a cationic polymerizable functional group such as an epoxy group in the molecule. Polyene / thiol-based prepolymers, which are a combination of polyene and polythiol, are also preferred. Here, the (meth)acryloyl group refers to an acryloyl group or a methacryloyl group.

[0054] Examples of prepolymers having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, and silicone (meth)acrylate. The weight-average molecular weight of these prepolymers is preferably about 250 to 100,000. The weight-average molecular weight in this specification is the average molecular weight measured by GPC analysis (gel permeation chromatography) and converted into standard polystyrene.

[0055] Examples of the monomer having a radically polymerizable unsaturated group include monofunctional monomers such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and phenoxyethyl(meth)acrylate. Examples of the polyfunctional monomers include glycerin tri(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0056] Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolac 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 in which allyl alcohol is added to both ends of a polyurethane made from a diol and a diisocyanate.

[0057] In the present invention, the ionizing radiation-curable resin (preferably an electron beam-curable resin) can be a mixed resin containing a urethane (meth)acrylate oligomer (A) having two radically polymerizable unsaturated groups per molecule and a weight-average molecular weight of 1,000 to 3,000, and an aliphatic urethane (meth)acrylate oligomer (B) having three to 15 radically polymerizable unsaturated groups per molecule. When using such a mixed resin, the high crosslinking density makes it easy to achieve effects such as scratch resistance and stain resistance. Furthermore, by appropriately adjusting the weight-average molecular weight and / or blending amount, it is possible to easily adjust the surface performance according to the application, for example, to provide the crosslinked curable resin layer with excellent impact resistance or excellent processability such as V-cutting.

[0058] The content ratio of the oligomer (A) and the oligomer (B) in the ionizing radiation curable resin (preferably an electron beam curable resin) is not limited, but it is preferable that the oligomer (A) is in the range of 50 to 90 mass % and the oligomer (B) is in the range of 10 to 50 mass % when the total amount of the oligomer (A) and the oligomer (B) is 100 mass %. In this range, the Martens hardness of the crosslinked curable resin layer (after curing) is 30 N / mm 2 More than 180N / mm 2 The slip resistance of the cross-linked cured resin layer can be easily adjusted to suit various applications (slip resistance value (CSR value) of 0.25 or more).

[0059] In the present invention, the ionizing radiation curable resin (preferably an electron beam curable resin) may be a mixed resin containing two types of aliphatic urethane (meth)acrylate, Resin A and Resin B, as shown below. Here, (meth)acrylate means acrylate or methacrylate.

[0060] Resin A is an aliphatic urethane (meth)acrylate having an isocyanurate skeleton. While not limited as long as it satisfies this requirement, for example, an aliphatic urethane (meth)acrylate having an isocyanurate skeleton formed by a diisocyanate trimer is preferred. Specific examples include a trimer of hexamethylene diisocyanate (particularly 1,6-hexamethylene diisocyanate), a trimer of tolylene diisocyanate, and a trimer of meta-xylene diisocyanate. Because tolylene diisocyanate and meta-xylene diisocyanate have a benzene ring, they may have poorer weather resistance than hexamethylene diisocyanate, so it is preferable that these diisocyanates are hydrogenated. These resins A have the effect of improving the contamination resistance, alkali resistance, etc. of the cross-linked cured resin layer.

[0061] Resin B is an aliphatic urethane (meth)acrylate that does not have an isocyanurate skeleton but has an alicyclic skeleton. While not limited as long as this requirement is met, it is preferable that the alicyclic skeleton contains at least one of isophorone and cyclohexane. Specific examples include a urethane oligomer, which is a polymer formed from isophorone diisocyanate and butanediol as monomers, to which an acrylate is added at the end, and a PG-modified diacrylate of hydrogenated dicyclohexylmethane diisocyanate (hydrogenated MDI). These resins B have the effect of imparting flexibility to the crosslinked cured resin layer, and in combination with resin A, they provide the crosslinked cured resin layer with excellent stain resistance, alkali resistance, etc. over a long period of time, as well as the effect of suppressing the occurrence of cracks or breakage when subjected to impact or during processing.

[0062] The ionizing radiation curable resin is a transparent resin primarily composed of a prepolymer (including oligomer) and / or monomer containing a radically polymerizable double bond in the molecule that can undergo a polymerization / crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet light or an electron beam, and the curing reaction is typically a crosslinking reaction. The ionizing radiation used to cure the ionizing radiation curable resin is electromagnetic waves or charged particles having enough energy to cause a curing reaction of the molecules in the ionizing radiation curable resin (composition). While ultraviolet light or an electron beam is usually used, visible light, X-rays, ion beams, etc. may also be used. In the present invention, the use of an electron beam curable resin is preferred as the ionizing radiation curable resin because it does not contain a photopolymerization initiator, allowing the properties of the raw material resin to be directly reflected in the properties of the resin component of the crosslinking / curable resin layer, and also broadening the range of options when a weathering agent is used in combination.

[0063] As a two-component curing urethane-based resin, for example, one containing, as a main component, a polyol component having an OH group (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) and, as a curing agent component, an isocyanate component (tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, etc.) can be used.

[0064] The above-exemplified cross-linked curable resins can be used alone or in combination of two or more.

[0065] The cross-linking curable resin layer contains an allergen reducing agent in addition to a cured product of the cross-linking curable resin.

[0066] The allergen-reducing agent used in the present invention (hereinafter also referred to as "the allergen-reducing agent of the present invention") is an allergen-reducing agent that has allergen-reducing properties against dust mites and cedars, and is characterized by containing a carboxylic acid derivative and a styrene polymer derivative, and containing at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative. It is preferable that the allergen-reducing agent of the present invention further contains triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the styrene polymer derivative. These compounds are positioned as compounds that are detected as components when the carboxylic acid derivative and the styrene polymer derivative are subjected to organic structural analysis, respectively.

[0067] The carboxylic acid derivative is not limited as long as the above-mentioned predetermined constituent component is detected when an organic structure analysis is performed. As an example of a preparation method, for example, a carboxylic acid derivative can be prepared by mixing and reacting raw materials including cyclohexanecarboxylic acid (manufactured by New Japan Chemical Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N,N-dimethylallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.), and N,N,2,2-tetramethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0068] In one embodiment, it is more preferable that the allergen reducing agent contains all of cyclohexanecarboxylic acid, triethylamine, N,N-dimethylallylamine, 2,4-dimethylpyrrole, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative.

[0069] In one particularly preferred embodiment, the allergen denaturing agent contains all of triethylamine, N,N-dimethylallylamine, 2,4-dimethylpyrrole, and N,N,2,2-tetramethyl-1,3-propanediamine as carboxylic acid derivative components.

[0070] Furthermore, the styrene polymer derivative is preferably one in which the above-mentioned specified constituent components are detected upon organic structure analysis, and as an example of a preparation method, the styrene polymer derivative can be prepared by mixing and reacting raw materials including 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 "86% Ethanol-ME").

[0071] In one embodiment, the allergen denaturing agent preferably contains sodium p-styrenesulfonate and a styrene monomer as components of the styrene polymer derivative.

[0072] The allergen reducing agent of the present invention can be prepared by mixing (kneading) the carboxylic acid derivative and the styrene polymer derivative at a desired mixing ratio and pulverizing them to a desired size using a known pulverizing means such as a jet mill. The content ratio of the carboxylic acid derivative and the styrene polymer derivative is not limited, but is preferably 1:1 to 10:1 by mass, and more preferably 2:1 to 5:1 by mass. By using such a content ratio (mixing ratio), it becomes easier to obtain the allergen reducing effect against dust mites and cedars.

[0073] The shape of the allergen-reducing agent (primary particles) of the present invention is not limited, but examples include spheres, ellipsoids, polyhedrons, and scales. The average particle size of the allergen-reducing agent of the present invention is not limited, but is preferably 2 μm to 15 μm, more preferably 3 μm to 12 μm, and even more preferably 4 μm to 11 μm. The average particle size in this specification is the value specified as the mass average value D50 in particle size distribution measurement by laser diffraction.

[0074] The reason why the allergen-reducing agent of the present invention has the ability to reduce allergens (allergens) is speculated as follows, but the present invention is not limited to this speculated mechanism. When various allergens derived from dust mites, cedar, etc., enter the body, they bind to specific antibodies, causing an allergic reaction by secreting chemicals such as histamine from mast cells. It is believed that the allergen-reducing agent binds to the allergen protein to capture the allergen, thereby preventing the allergen from binding to the specific antibody and thereby exerting its allergen-reducing effect. Specifically, it is believed that the aforementioned multiple amino groups, sulfonic acid groups of the styrene polymer derivative, and carboxyl groups of the carboxylic acid derivative compound, which are components of the carboxylic acid derivative, bind to proteins contained in dust mite- and cedar-derived allergens, thereby inactivating the allergens. The allergen-reducing agent of the present invention is superior to conventional products in that it can inactivate dust mite- and cedar-derived allergens at a concentration that does not inhibit the surface performance of the surface protective layer.

[0075] The content of the allergen reducing agent of the present invention relative to 100 parts by mass of the cross-linking curable resin is preferably from 1 to 10 parts by mass, more preferably from 2 to 6 parts by mass. Within this content range, a predetermined allergen reducing effect can generally be achieved without affecting the surface performance of the surface protective layer.

[0076] Regarding the thickness of the cross-linked curable resin layer, if the cross-linked curable resin layer does not have any convex portions due to the allergen reducing agent of the present invention, the average thickness of the smooth portions excluding the convex portions is preferably 2 μm or more. If the cross-linked curable resin layer has convex portions due to the allergen reducing agent of the present invention, the average thickness of the smooth portions excluding the convex portions is preferably 2 μm or more. The average thickness of the smooth portions is preferably 2 μm or more, and more preferably 4 μm or more, with the upper limit of the average thickness being, for example, 35 μm. The average thickness of the cross-linked curable resin layer is the average value measured at a flat area (see thickness A in Figure 1) where there is no embossed uneven pattern or convex portions due to the allergen reducing agent of the present invention (protrusions of the cross-linked curable resin layer). In this specification, it means the average thickness of 10 arbitrary points within a 1 cm width of an observed cross-sectional image of the cross-linked curable resin layer. "Width" refers to the direction perpendicular to the thickness direction.

[0077] The crosslinking-curable resin layer can be formed, for example, by applying a crosslinking-curable resin layer-forming composition containing a crosslinking-curable resin and the allergen-reducing agent of the present invention onto a primer layer by a known coating method such as gravure coating or roll coating, and then curing the resin. Specifically, after applying the crosslinking-curable resin layer-forming composition, the allergen-reducing agent of the present invention may lift up in the coating film before it is completely cured, forming convex portions due to the allergen-reducing agent on the outermost surface of the crosslinking-curable resin layer, or the allergen-reducing agent may partially aggregate in the coating film, causing the particle size of the allergen-reducing agent to appear larger, but this does not affect the expression of allergen-reducing performance.

[0078] In the present invention, when the thickness of the smooth portion of the cross-linked cured resin layer is divided into thirds and divided into a lower layer, a middle layer, and an upper layer, it is preferable that the center points of 50% or more of the allergen-reducing agents of the present invention (total in number) are located in the middle layer or the upper layer (i.e., the middle layer or higher). Figure 4 shows an example of the relationship between the thickness A of the smooth portion of the cross-linked cured resin layer and the position of the center point of the allergen-reducing agent. Here, allergen-reducing agents 9-1 and 9-2 are examples in which the center point of the allergen-reducing agent is located in the middle or upper layer (the middle layer includes the boundary between the lower layer and the middle layer, and the upper layer includes the boundary between the middle and the upper layer) of the thickness of the smooth portion of the cross-linked cured resin layer, and allergen-reducing agent 9-3 is an example in which the center point of the allergen-reducing agent is located in the lower layer. The center point of the allergen-reducing agent is determined by drawing a circle with the smallest diameter so that the allergen-reducing agent of the present invention, which may have any shape (not necessarily circular), can be completely contained in the cross-sectional observation image of the cross-linked cured resin layer, and the center of the circle is determined as the center point. As described above, the proportion of the center points of the allergen-reducing agent of the present invention located in the middle or upper layer (i.e., the middle layer or higher) is preferably 50% or more, more preferably 67% or more. By keeping the proportion within this range, the allergen-reducing effect of the allergen-reducing agent of the present invention can be easily achieved. Even in such a preferred embodiment, as described above, as long as the content of the allergen-reducing agent of the present invention is 10 parts by mass or less per 100 parts by mass of the cross-linked cured resin, the desired allergen-reducing effect can generally be achieved without affecting the surface performance of the surface protective layer. It should be noted that when an allergen-reducing agent different from the allergen-reducing agent of the present invention (referred to as a "different allergen-reducing agent" to distinguish it from the allergen-reducing agent of the present invention) is contained as one or more of the two different types of fine particles described below, the relationship between the position of the center point of the allergen-reducing agent and allergen-reducing performance described above may not apply to some different allergen-reducing agents (e.g., inorganic allergen-reducing agents). In particular, inorganic allergen-reducing agents that exhibit allergen-reducing performance through metal ions may exhibit allergen-reducing performance even if they are not necessarily present in the middle or higher layers of the cross-linked cured resin layer.The cross-sectional observation is performed by cutting the cross-linked curable resin layer in the thickness direction with a sharp blade such as a single-edged trimming razor or a microtome, and then observing the cut surface (200 μm wide) with a digital microscope (Keyence Corporation, model number: VHX-7000, magnification: 200x).

[0079] In the present invention, the cross-linked curable resin layer preferably has fine irregularities on its outermost surface with an arithmetic mean roughness Ra of 0.1 μm or more. Such fine irregularities may be formed by the allergen-reducing agent as a result of lifting of the allergen-reducing agent, or may be formed by physical processing such as sandblasting or fine embossing. The arithmetic mean roughness Ra of the outermost surface is more preferably 1.0 μm or more, with a preferred upper limit of Ra being 40 μm or less. The formation of such fine irregularities increases the surface area of ​​the outermost surface, making it easier to achieve an allergen-reducing effect compared to a surface without fine irregularities. The arithmetic mean roughness Ra in this specification is a value measured in accordance with JIS B0601 (2001) using a surface roughness measuring instrument ("SURFCOM-FLEX-50A", manufactured by Tokyo Seimitsu Co., Ltd.).

[0080] In the present invention, the Martens hardness of the cross-linked cured resin layer is 30 N / mm 2 More than 180N / mm 2 Less than 60N / mm is preferable 2 More than 180N / mm 2 The following is more preferred:

[0081] The Martens hardness values ​​used herein were measured using a PICODENTOR HM-500 Martens hardness tester (manufactured by Fischer Instruments) conforming to ISO 14577. Specifically, measurements were performed by pressing the diamond indenter (Vickers indenter) shown in Figure 5(a) into the test sample as shown in Figure 5(b). The indentation conditions were as follows: at room temperature (laboratory ambient temperature), a load of 0 to 5 mN was applied for 10 seconds, followed by a 5 mN load hold for 5 seconds, and finally, the load was removed from 5 to 0 mN for 10 seconds, as shown in Figure 5(c). In this specification, the Martens hardness was measured on the cross-section of the cross-linked cured resin layer to avoid the influence of the hardness of layers other than the cross-linked cured resin layer. In this case, the decorative sheet was embedded in resin (such as a cold-setting type two-component epoxy resin or a UV-curable resin), and left to harden at room temperature (23±5°C) for 24 hours or more. The hardened embedded sample was then cut and mechanically polished to expose the cross section of the cross-linked cured resin layer, and the Martens hardness of the cross section was measured by pressing a diamond indenter into the cross section (in cases where fine particles such as fillers were contained in the layer, a position avoiding the fine particles). The average value of measurements taken at five different points was taken as the Martens hardness.

[0082] In the present invention, the Martens hardness of the crosslinked cured resin layer is preferably 30 N / mm 2 More than 180N / mm 2 By setting the value below, it becomes easier to adjust the slip resistance value (CSR value) as an index of slip resistance to 0.25 or more. Here, as an index of slip resistance for various applications based on the CSR value, a value of 0.25 or more (particularly 0.25 or more but less than 0.30) is judged to be suitable for building materials, a value of 0.30 or more (particularly 0.30 or more but less than 0.38) is judged to be suitable for normal flooring, and a value of 0.38 or more (particularly 0.38 or more but less than 0.50) is judged to be suitable for slip-resistant flooring, exhibiting high levels of slip resistance. The slip resistance value (CSR value) in this specification is the value measured using a Tokyo Institute of Technology slip resistance tester (OY-PSM) with socks.

[0083] In one embodiment, the Martens hardness of the substrate sheet and / or the transparent thermoplastic resin layer is 30 N / mm 2 More than 80N / mm 2 It is preferable that:

[0084] In the present invention, the cross-linked cured resin layer may contain a phenyl ether derivative compound to complement the allergen-reducing performance of the cross-linked cured resin layer. Examples of the phenyl ether derivative compound include polyoxyethylene alkyl ether, which is known to be capable of exhibiting allergen-reducing performance as an ether-type nonionic surfactant.

[0085] In the present invention, the cross-linking curable resin layer contains two different types of fine particles in addition to the cured product of the cross-linking curable resin and the allergen reducing agent. The two different types of fine particles may be inorganic, organic, or a combination of inorganic and organic. Examples of inorganic fine particles include silica, alumina, and zirconia. Examples of organic fine particles include melamine, acrylic, and resin beads. If the two different types of fine particles are designated as first fine particles and second fine particles, respectively, their average particle diameters can be set, for example, to less than 4 μm for the first fine particles and 4 μm to 30 μm for the second fine particles. Furthermore, the amount of the first fine particles added per 100 parts by mass of the cross-linking curable resin can be set, for example, to 0.1 parts by mass to 10 parts by mass and 0.1 parts by mass to 30 parts by mass for the second fine particles. Setting the amounts within the above ranges allows the fine particles to be densely packed in the cross-linking curable resin layer, thereby facilitating the presence of the allergen reducing agent in the middle or higher layers of the cross-linking curable resin layer. For example, when silica is used as both the first fine particles and the second fine particles, one can be anti-settling silica and the other can be matte silica. When selecting two different types of fine particles, it is preferable to use fine particles with a larger specific gravity than the allergen reducing agent of the present invention (including the case of a different allergen reducing agent), because this makes it easier for the fine particles to fill the lower layer of the cross-linked cured resin layer and for the functional material to be lifted up more easily.

[0086] In one embodiment, the two different types of fine particles contained in the cross-linked curable resin layer are Silica fine particles having an average particle size of less than 4 μm and silica fine particles having an average particle size of 4 μm or more and 30 μm or less are preferred.

[0087] In one embodiment, the two different types of fine particles contained in the cross-linked curable resin layer are Silica fine particles having an average particle size of less than 4 μm and silica fine particles having an average particle size of 4 μm or more and 30 μm or less, The content of silica fine particles having an average particle diameter of less than 4 μm is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cross-linked curable resin, The content of silica fine particles having an average particle size of 4 μm or more and 30 μm or less is more preferably 0.1 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the cross-linking curable resin.

[0088] Furthermore, various additives may be added to the cross-linking curable resin layer, such as colorants (e.g., dyes, pigments), fillers (e.g., inorganic fillers), weathering agents, antifoaming agents, leveling agents, thixotropy-imparting agents, flame retardants, and antibacterial agents other than the allergen-reducing agents, as long as they do not affect the surface performance and predetermined allergen-reducing performance of the surface protective layer. Inorganic fillers are often used primarily as matting agents, but including an inorganic filler in the cross-linking curable resin layer can also be expected to have the effect of suppressing cure shrinkage of the surface protective layer. In the present invention, for example, silica may be used as the two different types of fine particles, and a material other than silica may be used as the additive made of an inorganic material, thereby distinguishing between the two different types of fine particles and other components such as additives.

[0089] The antibacterial agents include inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are desirable because they are generally safer than organic antibacterial agents and have excellent durability and heat resistance. In this specification, inorganic antibacterial agents are those in which antibacterial metals such as silver, copper, and zinc are supported on various inorganic carriers. In one embodiment, the inorganic antibacterial agent is preferably a silver-containing inorganic antibacterial agent (an antibacterial agent made of silver-containing inorganic particles). In one embodiment, the antibacterial agent made of silver-containing inorganic particles is preferably silver-supported zeolite particles.

[0090] Embossing Embossing is performed to impart a desired texture, such as a wood grain pattern, to the decorative sheet, and embossing may be performed on the transparent resin layer and / or the cross-linked curable resin layer. For example, the cross-linked curable resin layer is heated and softened, then pressed and shaped with an embossing plate having a desired concave-convex pattern, and then cooled and fixed to impart the texture. Embossing can be performed using a known sheet-fed or rotary embossing machine.

[0091] Examples of embossed uneven patterns include wood grain vessel grooves, raised patterns (raised annual ring patterns), hairlines, sand grain, and matte finish.

[0092] If embossing is performed, ink may be filled into the embossed recesses by wiping, if necessary. For example, ink is filled into the embossed recesses while scratching the surface with a doctor blade. The ink used to fill (wiping ink) is usually a two-component curing ink with a urethane resin binder. In particular, wiping the unevenness of the wood grain vessel grooves can enhance the product value by expressing a design that is closer to the actual wood grain.

[0093] Back primer layer A back primer layer may be provided on the back surface of the base sheet as needed, which is effective, for example, when a decorative board is produced by bonding the base sheet to a decorative board substrate.

[0094] The back primer layer can be formed by applying a known primer agent to the substrate sheet. Examples of primer agents include urethane resin-based primer agents made from acrylic-modified urethane resin (acrylic urethane copolymer resin), polycarbonate-based acrylic urethane copolymer resin, etc., urethane-cellulose resin-based primer agents (e.g., resins obtained by adding hexamethylene diisocyanate to a mixture of urethane and soluble nitrocellulose), and resin-based primer agents made from acrylic and urethane block copolymers.

[0095] The primer agent may contain additives as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The amount of additives added can be appropriately determined depending on the product characteristics.

[0096] The thickness of the back primer layer is not particularly limited, but is usually about 0.01 to 10 μm, and preferably about 0.1 to 1 μm.

[0097] Synthetic resin backing layer A synthetic resin backing layer may be provided on the back surface of the substrate sheet as needed. By providing a synthetic resin backing layer, the impact resistance of the decorative sheet is further improved. When the above-mentioned back surface primer layer is also provided, the synthetic resin backing layer and the back surface primer layer are provided on the back surface of the substrate sheet in this order from the substrate sheet side.

[0098] Examples of resins that can be used to form the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, highly heat-resistant polyalkylene terephthalate (e.g., polyethylene terephthalate in which part of the ethylene glycol has been replaced with 1,4-cyclohexanedimethanol or diethylene glycol, known as PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, diene rubbers such as styrene-butadiene rubber, isoprene rubber, and chloroprene rubber, non-diene rubbers such as butyl rubber and ethylene-propylene rubber, natural rubber, and thermoplastic elastomers. These resins can be used alone or in combination of two or more.

[0099] The thickness of the synthetic resin backer layer is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.45 mm, and even more preferably 0.20 to 0.40 mm. 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. Furthermore, by setting the upper limit of the thickness of the synthetic resin backer layer within the above range, warping of the decorative sheet is further suppressed.

[0100] Vesiculation of various additives contained in each layer of decorative sheets The various additives added to the above-mentioned layers of the decorative sheet of the present invention (such as inorganic fillers added to the primer layer and cross-linked curable resin layer) are preferably vesiculated. The method for vesiculating the various additives is not particularly limited, and they can be vesiculated by any known method, with supercritical reverse phase evaporation being preferred.

[0101] In addition to supercritical reverse-phase evaporation, other vesicle-forming methods include the Bangham method, extrusion, hydration, reverse-phase evaporation, and freeze-thaw. Briefly, the Bangham method involves dissolving phospholipids in chloroform or a chloroform / methanol mixture in a flask or other container. The solvent is then removed using an evaporator to form a thin lipid film. A dispersion of additives is then added, followed by hydration and dispersion in a vortex mixer to obtain vesicles. The extrusion method involves preparing a thin phospholipid solution and passing it through a filter, replacing the mixer used as an external perturbation in the Bangham method, to obtain vesicles. The hydration method is similar to the Bangham method, but does not require a mixer. Instead, vesicles are obtained by gentle agitation and dispersion. The reverse phase evaporation method involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing an additive, creating a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method uses cooling and heating as an external perturbation, and vesicles are obtained by repeating this cooling and heating process.

[0102] The supercritical reverse-phase evaporation method is described in detail below. Supercritical reverse-phase evaporation is a method in which a substance forming the outer membrane of a vesicle is uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure above the supercritical point. An aqueous phase containing various water-soluble or hydrophilic additives as encapsulated substances is added to the mixture to form a capsule-like vesicle encapsulating the various additives as encapsulated substances in a single layer. Note that "supercritical carbon dioxide" refers to carbon dioxide in a supercritical state above its critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa). "Carbon dioxide at a temperature or pressure above its critical point" refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition. This method can produce unilamellar vesicles with diameters of 50 to 800 nm. Generally, a vesicle is a collective term for a small vesicle with a spherical, closed membrane structure that contains a liquid phase inside. In particular, liposomes are those whose outer membrane is composed of biological lipids such as phospholipids.

[0103] Examples of the phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin; and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0104] The substance that can be used to form the outer membrane may also be a dispersant such as a nonionic surfactant or a mixture of a nonionic surfactant with cholesterol or triacylglycerol.

[0105] As the nonionic surfactant, one or more of polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. can be used.

[0106] As the cholesterols, one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol, and the like can be used.

[0107] The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet of the present invention, by using a liposome whose outer membrane is formed from a phospholipid, it is possible to improve the compatibility between the resin composition, which is the main component of each layer, and various additives.

[0108] 2. Adhesive-processed sheet with allergen reduction properties The pressure-sensitive adhesive sheet of the present invention having allergen-reducing properties (the pressure-sensitive adhesive sheet of the present invention) is composed of a laminate having, in order in the thickness direction, at least a pressure-sensitive adhesive sheet and the decorative sheet of the present invention. There are no particular limitations on the pressure-sensitive adhesive sheet, and pressure-sensitive adhesive sheets used in the fields of decorative sheets and other functional sheets can be used as appropriate. By having a pressure-sensitive adhesive sheet on its back surface, the pressure-sensitive adhesive sheet of the present invention can be attached to the surface of various flooring articles and adherends, and can be imparted with allergen-reducing properties as desired.

[0109] Figure 2 shows an example of an adhesive-processed sheet 11 having allergen reduction properties, in which a decorative sheet 1 of the present invention (the adhesive sheet 10 is bonded to the side opposite the cross-linked cured resin layer) is laminated in this order on an adhesive sheet 10.

[0110] 3. Decorative panels with allergen reduction properties The decorative board having allergen-reducing properties of the present invention (the decorative board of the present invention) is composed of a laminate having, in order in the thickness direction, at least a decorative board substrate and the decorative sheet of the present invention or the adhesive-processed sheet of the present invention.

[0111] Figure 3 shows an example of a decorative board 13 having allergen reduction properties, in which the decorative sheet 1 of the present invention (the side opposite the cross-linked cured resin layer side and the decorative board substrate 12 are bonded together) is laminated in this order on the decorative board substrate 12.

[0112] The decorative board substrate is not limited, and examples thereof include at least one of medium-density wood fiberboard, high-density wood fiberboard, particle board, softwood plywood, hardwood plywood, fast-growing tree plywood, cork sheet, cork-containing composite substrate, thermoplastic resin board (a resin board mainly composed of polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc., or a foamed version thereof), etc. These decorative board substrates may be used alone or in combination of two or more types, which may be laminated.

[0113] Here, examples of coniferous trees include linden pine, larch, Hokkaido pine, cedar, cypress, pine, sequoia, spruce, etc. Examples of broad-leaved trees include lauan, china, birch, sen, beech, oak, meranti, etc. Furthermore, examples of fast-growing trees include poplar, falcata, acacia, camellia, eucalyptus, terminalia, etc.

[0114] When using wood plywood such as softwood plywood, hardwood plywood, or fast-growing wood plywood, the number of layers of wood veneers (the number of plies) is not limited, but typically 3 to 7 plies is preferred, and 5 to 7 plies is more preferred. The adhesive used in producing the wood plywood is also not limited, and a wide variety of known woodworking adhesives can be used. Examples of adhesives include those containing polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, and natural rubber as active ingredients. Examples of thermosetting adhesives include melamine-based, phenol-based, and urea-based (e.g., vinyl acetate-urea-based) adhesives.

[0115] The cork sheet can be made of so-called natural cork, which is a highly elastic material made by peeling and processing the cork tissue from the bark of the cork oak, or a so-called synthetic cork made to resemble cork. The cork sheet can be a single layer or a laminate of multiple cork sheets with different elastic moduli and densities.

[0116] Examples of the cork-containing composite substrate include composite materials formed by laminating and bonding a cork sheet with another material (for example, a medium-density wood fiber board or a high-density wood fiber board).

[0117] The thickness of the decorative board substrate is not limited, but is preferably about 2 to 15 mm, and more preferably about 2 to 12 mm.

[0118] The lamination method for laminating the decorative sheet or pressure-sensitive adhesive sheet with the decorative board substrate is not limited, and can be, for example, a method of adhering them with an adhesive. Furthermore, if the pressure-sensitive adhesive sheet has sufficient adhesion to the decorative board substrate, a method of adhering the pressure-sensitive adhesive sheet to the decorative board substrate without using an adhesive can be adopted. The adhesive can be appropriately selected from known adhesives depending on the type of adherend, etc. 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. These adhesives can be used alone or in combination of two or more. [Example]

[0119] The present invention will be specifically explained below with reference to examples, comparative examples and test examples, but the present invention is not limited to the contents shown in the examples.

[0120] Example 1 The base sheet was a 60 μm thick colored polypropylene film (Martens hardness 70 N / mm 2 ) was prepared.

[0121] A back primer layer (2 μm thick) was formed on the back surface of the substrate sheet, and a picture pattern layer was formed on the front surface of the substrate sheet by gravure printing using a two-component urethane ink (product name "V180" manufactured by Toyo Ink Co., Ltd.) to a thickness of 2 μm.

[0122] A transparent adhesive layer was formed on the design layer using a urethane resin to a thickness of 2 μm.

[0123] A transparent random polypropylene resin sheet is extrusion laminated onto the transparent adhesive layer, and an 80 μm thick transparent thermoplastic resin layer (Martens hardness 60 N / mm 2 ) was formed.

[0124] After corona discharge treatment was performed on the front surface of the transparent thermoplastic resin layer, a primer agent containing a two-component curing urethane resin was applied to a thickness of 2 μm to form a primer layer.

[0125] The following composition for forming a cross-linking curable resin layer was applied to the front surface of the primer layer using a gravure coating method in a coating weight of 15 μm, and then the electron beam curable resin was cured by irradiating it with an electron beam using an electron beam irradiation device under conditions of an acceleration voltage of 165 KeV and 5 Mrad in an environment with an oxygen concentration of 200 ppm or less, thereby forming a cross-linking curable resin layer and producing a decorative sheet. Here, the content of the following allergen reducing agent was set to 3 parts by mass per 100 parts by mass of the cross-linking curable resin. In addition, when observing the cross-section of the cross-linking curable resin layer, the proportion of the center points of the allergen reducing agent present in the middle or upper layer (i.e., the middle layer or above) was 60% of the total.

[0126] (Crosslinked curable resin layer forming composition) The resin components of the cross-linking curing resin are 30 parts by mass of a multifunctional urethane oligomer and 70 parts by mass of a bifunctional urethane oligomer, totaling 100 parts by mass of urethane acrylate resin (the Martens hardness of the cured cross-linking curing resin layer is 110 N / mm 2 (Prescription) Allergen denaturing agent (3 parts by weight per 100 parts by weight of cross-linked curing resin) The carboxylic acid derivative was prepared by mixing and reacting raw materials including cyclohexanecarboxylic acid (manufactured by New Japan Chemical Co., Ltd.), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N,N-dimethylallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.), and N,N,2,2-tetramethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0127] The styrene polymer derivative was prepared by mixing and reacting raw materials including 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 "86% Ethanol-ME").

[0128] The allergen reducing agent was prepared by mixing the carboxylic acid derivative and the styrene polymer derivative in a mass ratio of 3:1, followed by pulverization in a jet mill (Nisshin Engineering, trade name "SJ-100"). The allergen reducing agent was measured using a laser diffraction particle size distribution analyzer (HORIBA) in accordance with JIS Z8825-1, and the average particle size was found to be 10 μm. Antibacterial agent (0.5 parts by mass per 100 parts by mass of cross-linked curing resin) Silver-loaded zeolite particles (product name "Zeomic", manufactured by Sinanen Zeomic Co., Ltd., average particle size 10 μm) Weatherproofing agent Triazine-based ultraviolet absorber (UVA "LA-F70", manufactured by ADEKA Corporation) (1 part by mass per 100 parts by mass of cross-linking curable resin) Light stabilizer (radical scavenger) (HALS "Tinuvin 152", manufactured by BASF) (0.3 parts by mass per 100 parts by mass of cross-linking curable resin) Two different types of particles First fine particles: Silica (average particle size 3 μm) 5 parts by mass per 100 parts by mass of cross-linked curing resin Secondary fine particles: Silica (average particle size 10 μm) 10 parts by mass per 100 parts by mass of cross-linked curing resin

[0129] Comparative Example 1 A decorative sheet was produced in the same manner as in Example 1, except that the allergen denaturing agent was changed to a silver ion-carrying compound (trade name "Million Guard", manufactured by Koa Glass Co., Ltd., average particle size 3 μm) and no antibacterial agent was used. In Comparative Example 1, the Martens hardness of the substrate sheet (a 60 μm thick colored polypropylene film) was 70 N / mm 2 The Martens hardness of the transparent thermoplastic resin layer (thickness 80 μm) is 60 N / mm 2In cross-sectional observation of the cross-linked cured resin layer, the proportion of the allergen reducing agent whose center was in the middle or upper layer (i.e., the middle layer or higher) accounted for 20% of the total. The silver ion-carrying compound (trade name "Million Guard", manufactured by Koa Glass Co., Ltd., average particle size 3 μm) does not contain a carboxylic acid derivative or a styrene polymer derivative.

[0130] Test Example 1 The decorative sheets produced in the examples and comparative examples were evaluated for the proportion of the central point of the allergen reducing agent present in the middle or upper layer (i.e., the middle layer or higher) of the cross-linked cured resin layer, the arithmetic mean roughness Ra of the surface of the cross-linked cured resin layer, and the allergen reducing performance. The measurement and evaluation methods are as follows.

[0131] <Surface roughness> The arithmetic mean roughness Ra defined in JIS B0601 (2001) was measured under the following conditions using a surface roughness measuring instrument (product number "SURFCOM-FLEX-50A", manufactured by Tokyo Seimitsu Co., Ltd.) In addition, depending on the measured Ra, the evaluation length and cutoff value were changed to appropriate values ​​and the measurement was carried out again. (Measurement conditions) Ra = over 0.1 μm and up to 2 μm Number of measurements: n = 5 (any 5 points) Calculation standard: JIS′01 Measurement type: Roughness measurement Evaluation length: 4.0 mm Cutoff value: 0.8 mm Measurement speed: 0.60mm / s Filter type: Gaussian Shape removal: straight line (Measurement conditions) Ra = Over 2 μm and up to 10 μm Number of measurements: n = 5 (any 5 points) Calculation standard: JIS′01 Measurement type: Roughness measurement Evaluation length: 12.5 mm Cutoff value: 2.5 mm Measurement speed: 0.60mm / s Filter type: Gaussian Shape removal: straight line (Measurement conditions) Ra = Over 10 μm and up to 80 μm Number of measurements: n = 5 (any 5 points) Calculation standard: JIS′01 Measurement type: Roughness measurement Evaluation length: 40 mm Cutoff value: 8mm Measurement speed: 0.60mm / s Filter type: Gaussian Shape removal: straight line

[0132] <Cross-section observation> 1) To observe the cross section of the prepared decorative sheet, an arbitrarily selected area was cut in the thickness direction of the decorative sheet with a single-edged trimming razor. 2) A 200 μm wide area was observed from the cross section of the cut decorative sheet using a digital microscope (Keyence Corporation, model number: VHX-7000, magnification: 200x). 3) The position of the center point of the allergen reducing agent present was confirmed throughout the entire cross-sectional photograph observed, and the percentage of allergen reducing agents whose center point was in the middle or upper layer (i.e., the middle layer or above) of the cross-linked cured resin layer was calculated using the following formula.

[0133] (Number of allergen denaturing agents with their center point in the middle or upper layer (i.e., middle layer or higher) / Number of allergen denaturing agents present in the entire area of ​​the observed cross-sectional photograph) x 100 (%)

[0134] <Allergen reduction performance> The decorative sheets produced in the Examples and Comparative Examples were evaluated for allergen reduction performance. For each decorative sheet, the inactivation rates of mite allergens and cedar pollen allergens were measured using an ITEA mite allergen (Derf1) ELISA kit (manufactured by ITEA Co., Ltd.) and an ITEA cedar pollen allergen (Cryj1) ELISA kit (manufactured by ITEA Co., Ltd.) Allergen solutions were prepared by adjusting the initial allergen concentration of each allergen standard solution included in each kit to 100 ng / ml using a diluent. 5cm 2400 μl of each prepared allergen solution was dropped onto the test piece cut into 5 cm 2 After covering the test specimens with PE film and leaving them for 24 hours, the mite allergens and cedar pollen allergens on each test specimen were collected, and the inactivation rates (%) of the mite allergens and cedar pollen allergens were measured using the ELISA method. The allergen reduction performance against mite and cedar pollen was evaluated according to the following criteria for allergen reduction performance. I(%)=(1-A1 / A0)×100 (Equation 1) (where I represents the inactivation rate of the allergen, A1 represents the absorbance measured based on the amount of remaining allergen, and A0 represents the absorbance measured based on the initial amount of allergen.) The allergen inactivation rate I (%) was calculated by applying the absorbance A0 measured based on the initial allergen amount and the absorbance A1 measured based on the remaining allergen amount after recovery to the above formula 1. <Criteria for determining allergen reduction performance> ++: The inactivation rate of the allergen from the initial concentration was 90% or more +: The inactivation rate of the allergen from the initial concentration was 70% or more but less than 90%. -: The inactivation rate of the allergen from the initial concentration was 30% or more but less than 70%. The results are shown in Table 1 below.

[0135] [Table 1]

[0136] Example 2 After forming a transparent resin layer in the same manner as in Example 1, the following surface protection layer-forming composition 1 (thermosetting resin) (coating amount after drying (described as film thickness after drying; the same applies below): 5 μm) and surface protection layer-forming composition 2 (ultraviolet curable resin) (coating amount after drying: 10 μm) were sequentially laminated, and ultraviolet light with a wavelength of 300 nm was irradiated using an ultraviolet irradiation device to form a crosslinked cured resin layer (surface protection layer) consisting of surface protection layer 1 (lower layer) formed from surface protection layer-forming composition 1 and surface protection layer 2 (upper layer) formed from surface protection layer-forming composition 2. In Example 2, the Martens hardness of the crosslinked cured resin layer (surface protection layer) was 160 N / mm 2 The Martens hardness of the base sheet (a 60 μm thick colored polypropylene film) is 70 N / mm 2 The Martens hardness of the transparent thermoplastic resin layer (thickness 80 μm) is 60 N / mm 2 It was.

[0137] [Composition 1 for forming surface protective layer] The following ultraviolet absorbers, light stabilizers, and additives were added in the amounts shown below to 100 parts by mass of the main component to prepare a surface protection layer-forming composition 1, which is a thermosetting resin. Base: Acrylic polyol with a glass transition temperature of approximately 100°C, a weight average molecular weight of approximately 40,000, and a hydroxyl value of 12, containing urethane bonds (can form urethane bonds when combined with a curing agent (isocyanate containing NH groups)). UV absorber: Tinuvin 399 (BASF Ltd.) 5 parts by weight Light stabilizer: Tinuvin 123 (BASF Ltd.) 3 parts by weight (additives) Dilution solvent: 50 parts by weight of ethyl acetate Gloss adjuster: Inorganic filler L-121 (AGC Si-Tech Co., Ltd.) 15 parts by weight Hardener: Duranate TPA-100 (manufactured by Asahi Kasei Corporation) 5 parts by weight

[0138] [Surface protective layer forming composition 2] A mixed resin was prepared by blending the following resins A, B, and C in a mass ratio of A:B:C = 60:30:10. To 100 parts by mass of this mixed resin, the same type and amount of allergen reducing agent (primary particle average particle size 10 μm) as in Example 1, two different types of fine particles (first fine particles and second fine particles) as in Example 1, and the same type and amount of antibacterial agent as in Example 1 were added. Furthermore, the following light stabilizer and two types of photopolymerization initiators were added in the following amounts to prepare a surface protection layer-forming composition 2, which is an ultraviolet-curable resin. Because the surface protection layer-forming composition 2 is an ultraviolet-curable resin, no ultraviolet absorber was added as a weather resistance agent, and only a light stabilizer was added. Resin A: Multifunctional urethane acrylate oligomer having 3 to 15 functional groups Resin B: Multifunctional urethane acrylate oligomer having 2 to 9 functional groups Resin C: 100 parts by mass of acrylic polyol having a glass transition temperature of about 100°C, a weight average molecular weight Mw of about 50,000, and a hydroxyl value of 15, and 5 parts by mass of Duranate TPA-100 (manufactured by Asahi Kasei Corporation) as a curing agent. Allergen denaturing agent (average primary particle size 10 μm): 3 parts by mass The same carboxylic acid derivative as in Example 1: the same styrene polymer derivative as in Example 1 (mass ratio 3:1) Light stabilizer: Sanol LS765 (BASF Ltd.) 3 parts by weight Photopolymerization initiator: Irgacure 907 (BASF Ltd.) 2.5 parts by weight Photopolymerization initiator: Irgacure 184 (BASF Ltd.) 2.5 parts by weight Two different types of particles First fine particles: Silica (average particle diameter 3 μm) 5 parts by mass Second fine particles: Silica (average particle size 10 μm) 10 parts by mass Antibacterial 0.5 parts by mass of silver-loaded zeolite particles (product name "Zeomic", manufactured by Sinanen Zeomic Co., Ltd., average particle size 10 μm)

[0139] Example 3 A mixed resin prepared by mixing the following resins A and B at a mass ratio of 70:30 (A:B) was used as the ionizing radiation curable resin for forming the cross-linked cured resin layer (surface protective layer). The mixed resin was a biomass-derived electron beam curable resin. To 100 parts by mass of the mixed resin, the same type and amount of allergen reducing agent (primary particle average particle size: 10 μm), the same type and amount of two different fine particles (first fine particles and second fine particles) as in Example 1, the same type and amount of weathering agent as in Example 1, and the same type and amount of antibacterial agent as in Example 1 were added to prepare a composition for forming a surface protective layer. Otherwise, a decorative sheet and a decorative board were produced in the same manner as in Example 1. In Example 3, the Martens hardness of the cross-linked cured resin layer (surface protective layer) was 130 N / mm 2 The Martens hardness of the base sheet (a 60 μm thick colored polypropylene film) is 70 N / mm 2 The Martens hardness of the transparent thermoplastic resin layer (thickness 80 μm) is 60 N / mm 2 It was. Resin A: Biomass-derived glycerin triacrylate (multifunctional monomer, molecular weight: 348, manufactured by Toagosei Co., Ltd., product name "Aronix M-930") Resin B: Hexafunctional urethane acrylate oligomer (Tg: 200°C or higher, molecular weight 1500, manufactured by Kyoeisha Chemical Co., Ltd., product name "UA306H") ·Mixing ratio (mass ratio) Resin A: Resin B=70:30 Allergen denaturing agent (average primary particle size 10 μm): 3 parts by mass The same carboxylic acid derivative as in Example 1: the same styrene polymer derivative as in Example 1 (mass ratio 3:1) Two different types of particles First fine particles: Silica (average particle diameter 3 μm) 5 parts by mass Second fine particles: Silica (average particle size 10 μm) 10 parts by mass Weatherproofing agent Triazine-based ultraviolet absorber (UVA "LA-F70", manufactured by ADEKA Corporation) 1 part by mass) Light stabilizer (radical scavenger) (HALS "Tinuvin 152", manufactured by BASF) 0.3 parts by mass Antibacterial 0.5 parts by mass of silver-loaded zeolite particles (product name "Zeomic", manufactured by Sinanen Zeomic Co., Ltd., average particle size 10 μm)

[0140] The results of Examples 2 and 3 are shown in Table 2 below.

[0141] [Table 2]

[0142] As can be seen from the results in Tables 1 and 2, it was confirmed that the decorative sheets of Examples 1 to 3, which contain an allergen reducing agent, exhibit allergen reducing properties against dust mites and cedar at a content that does not impair the surface performance of the surface protective layer. [Explanation of symbols]

[0143] 1. Decorative sheet with allergen reduction properties 2. Base sheet 3.Pattern layer 4.Transparent adhesive layer 5.Transparent resin layer 6. Primer layer 7.Crosslinked curing resin layer (surface protection layer) 8. Back primer layer 9. Allergen reducers 10. Adhesive sheet 11. Adhesive-processed sheet with allergen reduction properties 12. Decorative board base material 13. Decorative panels with allergen reduction properties A. Thickness of the smooth part of the cross-linked cured resin layer (surface protection layer) a. Upper layer b. Middle layer c. lower layer

Claims

1. A decorative sheet having a cross-linked curable resin layer on the outermost layer, (1) The cross-linked curable resin layer contains a cured product of a cross-linked curable resin and an allergen reducing agent, (2) The allergen reducing agent has allergen reducing properties against dust mites and cedars, and contains a carboxylic acid derivative and a styrene polymer derivative, and contains at least triethylamine, N,N-dimethylallylamine, dimethylpyrrole, tetramethyl-1,3-propanediamine, and N,N,2,2-tetramethyl-1,3-propanediamine as components of the carboxylic acid derivative; (3) The cross-linked cured resin layer further contains two different types of fine particles. A decorative sheet having allergen-reducing properties, characterized by:

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

3. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the cross-linked curable resin layer has fine irregularities on the outermost surface thereof with an arithmetic mean roughness Ra of 0.1 μm or more.

4. 4. The decorative sheet having allergen-reducing properties according to claim 3, wherein the arithmetic mean roughness Ra of the fine irregularities is 40 μm or less.

5. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the fine particles comprise first fine particles having an average particle size of less than 4 μm and second fine particles having an average particle size of 4 μm or more and 30 μm or less.

6. A decorative sheet having allergen reduction properties as described in claim 5, containing 0.1 to 10 parts by mass of the first microparticles and 0.1 to 30 parts by mass of the second microparticles relative to 100 parts by mass of the cross-linked curable resin.

7. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein said cross-linked cured resin layer further contains an antibacterial agent consisting of silver-containing inorganic particles in addition to said fine particles.

8. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the cross-linked curable resin layer further contains a triazine-based ultraviolet absorber and / or a light stabilizer.

9. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the allergen-reducing agent contains the carboxylic acid derivative and the styrene polymer derivative in a mass ratio of 1:1 to 10:

1.

10. A decorative sheet having allergen-reducing properties as described in claim 1 or 2, wherein when the thickness of the smooth portion of the cross-linked cured resin layer is divided into three equal parts into a lower layer, a middle layer, and an upper layer, the center points of 50% or more of the allergen-reducing agents are present in the middle layer or the upper layer.

11. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the allergen-reducing agent is contained in an amount of 1 part by mass to 10 parts by mass relative to 100 parts by mass of the cross-linked curable resin.

12. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the average thickness of the smooth portion of said cross-linked curable resin layer is 2 μm or more and 35 μm or less.

13. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the average particle size of the allergen-reducing agent is from 2 μm to 15 μm.

14. 3. The decorative sheet having allergen-reducing properties according to claim 1, wherein the cross-linking curable resin contains an ionizing radiation curable resin.

15. The Martens hardness of the cross-linked cured resin layer is 30 N / mm ２ More than 180N / mm ２ 3. The decorative sheet having allergen-reducing properties according to claim 1 or 2, wherein:

16. 3. A decorative sheet having allergen-reducing properties as described in claim 1 or 2, which is composed of a laminate having at least a base sheet, a picture pattern layer, a transparent thermoplastic resin layer, and the cross-linked cured resin layer in that order in the thickness direction.

17. The Martens hardness of the substrate sheet and / or the transparent thermoplastic resin layer is 30 N / mm ２ 80N / mm or more ２ 17. The decorative sheet having allergen-reducing properties according to claim 16, wherein:

18. 3. An adhesive-processed sheet having allergen-reducing properties, comprising a laminate comprising, in order in the thickness direction, an adhesive sheet and the decorative sheet having allergen-reducing properties according to claim 1 or 2.

19. 3. A decorative board having allergen-reducing properties, comprising a laminate comprising, in order in the thickness direction, a decorative board substrate and the decorative sheet having allergen-reducing properties according to claim 1 or 2.

20. A decorative board having allergen-reducing properties, comprising a laminate having at least, in order in the thickness direction, a decorative board substrate and the adhesive-processed sheet having allergen-reducing properties according to claim 18.

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