Decorative board, transparent resin film, and method for manufacturing decorative board

Abstract

To provide a decorative sheet capable of having an excellent weather resistance in a recess part of a rugged shape of a transparent resin film even if the rugged shape is formed on an outermost surface of the transparent resin film, and in addition having a flame resistance, and also to provide a transparent resin film and a manufacturing method of a decorative sheet.SOLUTION: A decorative sheet includes a substrate, a pattern layer and a transparent resin film laminated in this order in a thickness direction. The transparent resin film at least includes a thermoplastic resin layer, and a rugged shape on a side opposite to a side to be laminated on the pattern layer. The thermoplastic resin contains a flame retardant. The decorative sheet further includes at least one layer containing an ultraviolet light absorber between the pattern layer and the thermoplastic resin layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative board, a transparent resin film, and a method for producing a decorative board. [Background technology]

[0002] In recent years, the widespread use of inkjet printing methods using inkjet printers has made it possible to produce a wide variety of products in small lots, even for decorative sheets used in building materials and decorative molded products, and to print complex patterns (letters, numbers, figures, etc.) as picture layers. Furthermore, inkjet printing has the advantage that the substrate to be printed on is not limited to film, but can also be used to print on flat plates and substrates with uneven or curved surfaces. However, since the image layer printed by inkjet printing is located on the outermost surface of the substrate, its surface performance such as scratch resistance, contamination resistance, and weather resistance is insufficient, and a transparent resin film is required to protect the image layer.

[0003] As an example of such a transparent resin film, Patent Document 1 discloses an overlaminate film in which a protective layer is provided on one side of a transparent polypropylene containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer and an adhesive layer is provided on the other side.

[0004] However, in conventional decorative panels equipped with a transparent resin film, although the design was improved by the uneven shape of the transparent resin film, the uneven shape caused variations in the thickness of the transparent resin film, resulting in variations in weather resistance, and the weather resistance was particularly poor in thin film portions, leaving room for improvement. This tendency was particularly noticeable in the case of picture layers printed by inkjet printing, which use a wide variety of inks.

[0005] Furthermore, because such transparent resin films are laminated onto the surface of buildings and used as decorative panels, they are sometimes required to meet the requirements for obtaining non-combustible certification, which demonstrates their resistance to fire. The non-combustible certification requirements are the specified requirements for total heat release, maximum heat release rate, and occurrence of cracks and holes in heat release tests in accordance with ISO 5660-1, as stipulated in Article 2, Paragraph 9 of the Building Standards Act of Japan.

[0006] As a decorative sheet to be used for a decorative panel that satisfies the above-mentioned requirements, a decorative sheet has been proposed in which a base sheet, a transparent resin layer, and a surface protective layer are laminated in that order, with each layer having a thickness within a specific range, and which contains a flame retardant (see, for example, Patent Document 2).

[0007] Although the decorative sheets described above are also excellent in non-combustibility, there has been no study into the resistance of fire to spreading in the decorative sheet on the substrate in the event of a fire. For components that are installed on horizontal surfaces, such as decorative floor materials, flame retardancy is an important feature in ensuring evacuation time, as it limits the area of ​​the burning decorative sheet from expanding in the event of a fire, making it difficult for the fire to spread.

[0008] Therefore, there is a demand for the development of a transparent resin film that has excellent weather resistance, particularly in the thin film portion, and excellent flame retardancy, making it difficult for fire to spread. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-120255 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-182379 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention aims to provide a decorative board, a transparent resin film, and a method for manufacturing a decorative board that have excellent weather resistance in the recesses of the uneven shape of the transparent resin film, even if an uneven shape is formed on the outermost surface of the transparent resin film, and that also have flame retardancy. [Means for solving the problem]

[0011] As a result of intensive research into solving the above-mentioned problems, the inventors have discovered that a decorative panel having excellent weather resistance and flame retardancy can be obtained by laminating a substrate, a pattern layer, and a transparent resin film in this order in the thickness direction, the transparent resin film having at least a thermoplastic resin layer and having an uneven shape on the side opposite to the side laminated to the pattern layer, the transparent resin film containing a flame retardant, and having at least one layer containing an ultraviolet absorber between the pattern layer and the thermoplastic resin layer, even if an uneven shape is formed on the surface, and have thus completed the present invention.

[0012] The present invention is a decorative board having a substrate, a pattern layer, and a transparent resin film laminated in this order in the thickness direction, wherein the transparent resin film has at least a thermoplastic resin layer and has an uneven shape on the side opposite to the side laminated to the pattern layer, the transparent resin film contains a flame retardant, and has at least one layer containing an ultraviolet absorber between the pattern layer and the thermoplastic resin layer.

[0013] In the decorative board of the present invention, the thickness of the recesses of the uneven shape of the transparent resin film is preferably 80 μm or more. The transparent resin film preferably has an uneven shape on the side that is laminated to the design layer. Furthermore, it is preferable that the uneven shape of the transparent resin film on the side laminated to the design layer has an Rzmax defined by JIS B 0601 (2001) of 80 μm or less. The transparent resin film preferably contains a flame retardant. Furthermore, it is preferable that the transparent resin film has a surface protective layer laminated on the side of the thermoplastic resin layer opposite to the side laminated to the pattern layer, and it is more preferable that the surface protective layer contains a flame retardant. The surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergenic agent. The flame retardant is preferably at least one selected from the group consisting of metal phosphinate flame retardants, phosphazene flame retardants, and NOR-type hindered amine flame retardants. The thermoplastic resin layer preferably contains a filler. It is also preferable that an adhesive layer be provided between the design layer and the transparent resin film. Furthermore, it is preferable that the thickness of the adhesive layer is 10 μm or more and is greater than the Rzmax defined in JIS B 0601 (2001) of the uneven shape on the side of the transparent resin film that is laminated to the pattern layer. The adhesive layer is preferably a layer containing the ultraviolet absorber. The adhesive layer preferably contains an ultraviolet absorber in an amount of 0.5% by mass to 2% by mass. The ultraviolet absorber contained in the adhesive layer is preferably a triazine-based ultraviolet absorber. The transparent resin film preferably has an adhesive primer layer on the side of the thermoplastic resin layer that is to be laminated to the design layer. The adhesive primer layer is preferably a layer containing the ultraviolet absorber. The ultraviolet absorber contained in the adhesive primer layer is preferably a triazine-based ultraviolet absorber. The present invention also provides a transparent resin film used to protect a design layer laminated on one side of a substrate. In addition, the manufacturing method for decorative panels of the present invention is characterized by having a step of forming an adhesive layer on the surface of the transparent resin film that will be laminated to the pattern layer, and a step of bonding the transparent resin film and the pattern layer together via the adhesive layer. [Effects of the Invention]

[0014] The decorative board of the present invention is excellent in weather resistance and flame retardancy even when an uneven shape is formed on the outermost surface of the transparent resin film. Furthermore, the transparent resin film of the present invention can impart excellent weather resistance and flame retardancy to decorative sheets. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a cross-sectional view schematically showing a preferred example of the decorative board of the present invention. [Figure 2] 1 is a cross-sectional view schematically showing a preferred example of a transparent resin film constituting the decorative board of the present invention. [Figure 3] 1 is a cross-sectional view schematically showing a preferred example of a transparent resin film constituting the decorative board of the present invention. [Figure 4] 4(a) and 4(b) are schematic diagrams for explaining the method for evaluating flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0016] First, the decorative board of the present invention will be described. The decorative board of the present invention is a decorative board in which a substrate, a pattern layer, and a transparent resin film are laminated in this order in the thickness direction, and the transparent resin film has at least a thermoplastic resin layer and has an uneven shape on the side opposite to the side laminated to the pattern layer, the thermoplastic resin layer contains a flame retardant, and has at least one layer containing an ultraviolet absorber between the pattern layer and the thermoplastic resin layer.

[0017] A preferred example of the decorative board of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view schematically showing a preferred example of the decorative board of the present invention. As shown in Figure 1, the decorative board 10 of the present invention has a substrate 11, a pattern layer 12, and a transparent resin film 20 laminated in this order in the thickness direction, and the transparent resin film 20 has an uneven shape on the side opposite to the side on which the pattern layer 12 is laminated. As shown in FIG. 1, it is preferable to have an adhesive layer 13 between the design layer 12 and the transparent resin film 20 . Each component of the decorative board of the present invention will be described below. In the following description, the lower and upper limits of numerical ranges expressed with "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).

[0018] [Base material] The decorative board of the present invention has a substrate, a pattern layer, and a transparent resin film laminated in this order in the thickness direction. The substrate is not particularly limited and may be appropriately determined depending on the intended use of the decorative board of the present invention, for example. The material constituting the substrate is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, metal materials, and inorganic materials. Among these, resin materials and wood materials that are rigid and lightweight are preferred as the material constituting the substrate. A composite material of these may also be used. The resin material preferably contains, for example, a thermoplastic resin. Preferred examples of the thermoplastic resin include polyvinyl resins such as polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol resin; polyolefin resins such as polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer (EVA), and ethylene-(meth)acrylic acid resin; polyester resins such as polyethylene terephthalate (PET); acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer, and polyvinyl chloride resin sheets; thermoplastic resins and copolymers; 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; thermoplastic elastomers; and mixtures thereof. Among these, polyolefin resins, acrylonitrile-butadiene-styrene copolymer resins, polyvinyl chloride resins, and ionomers are preferred. Furthermore, the resin materials may be foamed.

[0019] The substrate may be colored. In this case, a colorant (pigment or dye) can be added to the thermoplastic resin. Examples of colorants that can be used include inorganic pigments such as titanium dioxide, carbon black, and iron oxide, and organic pigments such as phthalocyanine blue, as well as various dyes. One or more of these can be selected from known or commercially available colorants. The amount of colorant added can also be appropriately determined depending on the desired color tone, etc. The base material may also contain various additives such as fillers such as wood flour and calcium carbonate, matting agents such as silica, foaming agents, flame retardants, lubricants such as talc, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers.

[0020] Examples of the wood materials include various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melapy, and the core material may be any of veneer, wood single board, wood plywood (including LVL), particle board, medium density fiberboard (MDF), high density fiberboard (HDF), and laminated wood made from these materials, or a laminated material made by appropriately stacking these. Examples of the metal material include iron and aluminum.

[0021] The substrate may also contain an inorganic compound, which can reduce the linear expansion coefficient of the substrate and, as a result, improve the water resistance of the decorative board.

[0022] The substrate may also contain a flame retardant, which will be described later. By containing a flame retardant, the flame retardancy of the substrate is further improved. As the flame retardant, any of those described later in connection with the transparent resin film can be appropriately selected and used.

[0023] Furthermore, when the substrate has a base material made of a plurality of resins, the types of resins forming the base material made of a plurality of resins may be the same or different, and the thicknesses of the base material made of a plurality of resins may be the same or different.

[0024] In the present invention, the substrate may have a hollow structure, or may have a slit groove or a through hole formed in a part of the substrate.

[0025] The thickness of the substrate is not particularly limited, and is preferably 0.01 mm or more, and more preferably 0.1 mm or more and 50 mm or less. The substrate may be substantially plate-shaped other than a flat plate, and may have an uneven or curved surface.

[0026] [Picture layer] The decorative board of the present invention has a pattern layer laminated on one side of the substrate. The pattern layer is a layer that imparts decorativeness to the decorative panel of the present invention, and may be, for example, a uniformly colored concealing layer (solid print layer), a pattern layer formed by printing various patterns using ink and a printing press, or a layer that combines a concealing layer and a pattern layer (hereinafter referred to as a pattern layer).

[0027] By providing the above-mentioned hiding layer, when the above-mentioned substrate is colored or has color unevenness, it is possible to give it an intended color and adjust the color of the surface. Furthermore, by providing a pattern layer, it is possible to impart to the decorative panel patterns such as wood grain patterns, stone patterns that imitate the surface of rock, such as marble patterns (e.g., travertine marble patterns), fabric patterns that imitate fabric or cloth-like patterns, tile patterns, brickwork patterns, or combinations of these, such as marquetry and patchwork, as well as patterns of letters, symbols, abstract patterns, floral patterns, landscapes, characters, etc. These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, as well as by multi-color printing using spot colors, in which plates of the individual colors that make up the pattern are prepared.

[0028] The ink composition used for the design layer is a mixture of a binder resin with an appropriate amount of a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. There are no particular limitations on the binder resin, and preferred examples include urethane resin, acrylic resin, urethane-acrylic resin, urethane-acrylic copolymer resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin, polyester resin, nitrocellulose resin, etc. Any of these binder resins can be used alone or in combination of two or more. Preferred examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments consisting of scaly flakes of dyes, aluminum, brass, and the like; and pearlescent pigments consisting of scaly flakes of titanium dioxide-coated mica and basic lead carbonate, and the like.

[0029] The thickness of the design layer is not particularly limited, but is preferably 0.1 μm or more, and more preferably 0.5 μm or more and 600 μm or less. If the thickness of the design layer is within the above range, the decorative board of the present invention can be provided with an excellent design and hiding properties. In addition, when the substrate itself has a design in advance, such as a veneer, it is not necessary to provide a pattern layer.

[0030] The method for forming the design layer is not particularly limited, and for example, the design layer may be formed on any desired location, such as on the front side of the substrate, 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). The substrate may also be partially or entirely colored, or multiple types of resins may be mixed.

[0031] [Layer containing ultraviolet absorber] The decorative board of the present invention has at least one layer containing an ultraviolet absorber between the design layer and the thermoplastic resin layer of the transparent resin film described below. The layer containing the ultraviolet absorber may be an adhesive primer layer provided in the transparent resin film described later, or an adhesive layer described later, or both of these may be layers containing the ultraviolet absorber.

[0032] [Transparent resin film] The decorative board of the present invention has a transparent resin film laminated on the side of the design layer opposite to the side having the substrate. The transparent resin film has at least a thermoplastic resin layer, and has an uneven shape on the side opposite to the side laminated with the design layer. The transparent resin film further contains a flame retardant. The layer containing the flame retardant may be a thermoplastic resin layer or a surface protective layer.

[0033] [Thermoplastic resin layer] The thermoplastic resin layer serves to protect the design layer laminated on one surface of the substrate, and may be translucent or colored as long as it is transparent and the design layer can be seen. Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, and olefin-based thermoplastic elastomers, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer resin, terephthalic acid-ethylene glycol-1,4-cyclohexanedimethanol copolymer resin, and polyester-based thermoplastic elastomers, acrylic resins such as polymethyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer resin, and methyl (meth)acrylate-styrene copolymer resin, polycarbonate resin, polyvinyl chloride, polystyrene, and ionomers. Among these, polypropylene is preferably used because of its high tensile strength, excellent chemical resistance, and excellent production process. In this specification, (meth)acrylate means acrylate or methacrylate.

[0034] The thermoplastic resin layer may be unstretched, but may also be uniaxially or biaxially stretched as required. The thickness of the thermoplastic resin layer is not particularly limited, but a preferred lower limit is 20 μm, a preferred upper limit is less than 500 μm, and a more preferred lower limit is 60 μm, and a more preferred upper limit is 420 μm. If the thickness of the thermoplastic resin layer is less than 20 μm, the tensile strength may be insufficient and the surface of the design layer may not be protected, while if it is 500 μm or more, the transmittance of the transparent resin film may decrease, reducing the visibility of the design in the design layer.

[0035] The thermoplastic resin layer may be composed of one layer, or may be a laminate composed of two or more layers.

[0036] Furthermore, when the thermoplastic resin layer is composed of multiple layers, the types of resins that form the layers may be the same or different, and the thicknesses of the substrates made of multiple resins may be the same or different. The method for laminating two or more thermoplastic resin layers is not limited as long as it is a common method, and examples thereof include dry lamination and extrusion thermal lamination.

[0037] The thermoplastic resin layer preferably contains a flame retardant. When the thermoplastic resin layer is composed of two or more layers, it is effective to add a flame retardant to the outermost layer side in order to improve the flame retardancy.

[0038] Examples of the flame retardant include metal phosphinate flame retardants, phosphazene flame retardants, NOR-type hindered amine flame retardants, halogen-based flame retardants, antimony-based flame retardants, metal hydroxide-based flame retardants, and phosphate ester-based flame retardants. Among these, metal phosphinate flame retardants or phosphazene flame retardants are preferred from an environmental perspective or because the amount added can be reduced and the transparency of the layer containing the flame retardant can be maintained, and NOR-type hindered amine flame retardants are preferred because they have the effect of reducing the amount of heat generated in the heat generation test of ISO 5660-1.

[0039] Examples of the metal phosphinate flame retardant include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, and titanium tetrakisdiphenylphosphinate. Commercially available examples of the metal phosphinate flame retardant include those manufactured by Clariant Japan under the trade names "EXOLITE OP-930," "EXOLITE OP-935," "EXOLITE OP-1230," "EXOLITE OP-1240," and "EXOLITE OP-1312."

[0040] Examples of the phosphazene-based flame retardant include cyclic and / or chain C phosphazenes such as phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,m-tolyloxyphosphazene, o,p-tolyloxyphosphazene, m,p-tolyloxyphosphazene, o,m,p-tolyloxyphosphazene, etc.), and (poly)xylyloxyphosphazene. 1-6 Alkyl C 6-20 Cyclic and / or chain C phosphazenes such as aryloxyphosphazenes, (poly)phenoxytolyloxyphosphazenes (e.g., phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o,m-tolyloxyphosphazene, phenoxy o,p-tolyloxyphosphazene, phenoxy m,p-tolyloxyphosphazene, phenoxy o,m,p-tolyloxyphosphazene, etc.), (poly)phenoxyxylyloxyphosphazene, and (poly)phenoxytolyloxyxylyloxyphosphazene. 6-20 Aryl C 1-10 Alkyl C 6-20Examples include aryloxyphosphazenes, and preferred are cyclic and / or chain phenoxyphosphazenes, cyclic and / or chain C 1-3 Alkyl C 6-20 Aryloxyphosphazene, C 6-20 Aryloxy C 1-3 Alkyl C 6-20 Examples of the aryloxyphosphazenes include cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc. Other examples include compounds having a crosslinked structure of a 4,4'-diphenylene group, such as a compound having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4'-diphenylene)isopropylidene group, a compound having a crosslinked structure of a 4,4'-oxydiphenylene group, and a compound having a crosslinked structure of a 4,4'-thiodiphenylene group.

[0041] Examples of the NOR type hindered amine flame retardant include 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino)-s-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate; oligomeric compounds which are condensation products of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2, Oligomeric compounds which are condensation products of 4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine with 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)-6-chloro-s-triazine]; and reaction products of peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, and N,N'-ethane-1,2-diylbis(1,3-propanediamine). Examples of the compound (N,N',N'''-tris{2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)n-butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine); bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate; 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one; bis(1-stearyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and the like.Commercially available NOR-type hindered amine flame retardants include Flamestat NOR116FF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, and TINUVIN PA123 manufactured by BASF, and LA-81 manufactured by ADEKA Corporation.

[0042] The flame retardants may be used alone or in combination of two or more.

[0043] The content of the flame retardant is preferably 3% by mass or more, and more preferably 4.4% by mass or more, based on 100% by mass of the total mass of the thermoplastic resin layers. The content of the flame retardant is preferably 20% by mass or less, and more preferably 15% by mass or less, based on 100% by mass of the total mass of the thermoplastic resin layers. By setting the lower limit of the content of the flame retardant within the above range, the flame retardancy of the transparent resin film is further improved. By setting the upper limit of the content of the flame retardant within the above range, the transparency of the transparent resin film is further maintained.

[0044] At least one of the thermoplastic resin layers may contain a filler. The filler is not particularly limited as long as it does not impair the transparency of the thermoplastic resin layer. In order to further improve the sharpness (meaning the visibility of the pattern layer) of the decorative sheet of the present invention, a filler having an average particle size equal to or smaller than the wavelength of visible light is preferred. Examples of fillers include inorganic fillers such as silica, calcium carbonate, talc, and clay.

[0045] The filler is preferably contained in the same layer as the layer containing the flame retardant. That is, when the thermoplastic resin layer is composed of one layer, the thermoplastic resin layer preferably contains the flame retardant and the filler, and when the thermoplastic resin layer is composed of two or more layers, the filler is preferably contained in the same thermoplastic resin layer as the layer containing the flame retardant.

[0046] The thermoplastic resin layer (when the thermoplastic resin layer is composed of two or more layers, the layer containing the flame retardant) preferably further contains an inorganic filler having a polar group on its surface. When the thermoplastic resin layer containing the flame retardant contains an inorganic filler having a polar group on its surface, the sharpness and flame retardancy of the decorative sheet of the present invention are further improved. This is thought to be because the polar portion of the flame retardant is attracted to the polar group on the surface of the inorganic filler having a polar group, and the presence of the flame retardant on the surface improves dispersibility. As the inorganic filler having a polar group on its surface, a hydrophilic inorganic filler can be used, for example, an inorganic filler having a hydroxyl group such as a silanol group on its surface, and more specifically, hydrophilic silica can be used.

[0047] The silica used as the filler may be either a natural product or a synthetic product, and may be either crystalline or amorphous. Furthermore, the synthetic amorphous silica may be prepared by either a wet method or a dry method. The method for preparing the synthetic wet-process silica prepared by the wet method is not particularly limited, and examples thereof include a precipitation method and a gel method. The method for preparing the synthetic dry-process silica prepared by the dry method is not particularly limited, and examples thereof include a combustion method and an arc method. In order to further improve the sharpness of the decorative sheet of the present invention, silica with a small average particle size is preferred, and fumed silica obtained by a combustion method and hydrophilic fumed silica are more preferred.

[0048] The BET specific surface area of ​​the above hydrophilic fumed silica filler is 50m 2 / g or more is preferable, and 130m 2 / g or more is more preferable, and 200m 2 / g or more is even more preferable. When the lower limit of the BET specific surface area of ​​the filler is in the above range, the average particle size is small, and in the case of hydrophilic fumed silica, the silanol content increases, so that the decrease in transparency of the thermoplastic resin layer due to the addition of the filler is further suppressed, and the dispersibility of the flame retardant is further improved, thereby further improving the sharpness of the decorative sheet of the present invention and the flame retardancy of the transparent resin film. In addition, when the lower limit of the BET specific surface area of ​​the filler is in the above range, the flame retardancy of the transparent resin film is improved and it is possible to reduce the content of the flame retardant.

[0049] In this specification, the BET specific surface area is a BET specific surface area measured by a nitrogen adsorption method in accordance with DIN66131.

[0050] The hydrophilic fumed silica used as the filler may be commercially available, such as AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, and AEROSIL 380 manufactured by Nippon Aerosil Co., Ltd.

[0051] When the thermoplastic resin layer contains a flame retardant and a filler, the content of the filler in the thermoplastic resin layer is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and even more preferably 200 parts by mass or more, based on 100 parts by mass of the flame retardant in the thermoplastic resin layer. By setting the lower limit of the filler content in the thermoplastic resin layer within the above range, the sharpness of the decorative sheet of the present invention is further improved. Furthermore, the content of the filler in the thermoplastic resin layer is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0052] The thermoplastic resin layer may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma discharge treatment, ultraviolet (UV) treatment, and flame treatment, within the scope of the present invention. Furthermore, the thermoplastic resin layer may contain various additives such as a matting agent, a foaming agent, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component (e.g., rubber) to further improve performance such as heat resistance and shrinkage rate.

[0053] [Adhesive primer layer] The transparent resin film preferably has an adhesive primer layer on the side of the thermoplastic resin layer that is laminated to the design layer. By providing the adhesive primer layer, the adhesion between the transparent resin film and the design layer can be further strengthened.

[0054] The adhesive primer layer preferably contains a binder resin. Examples of the binder resin include urethane resin, acrylic resin, acrylic-urethane resin, acrylic-urethane copolymer resin, cellulose resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, etc. In view of adhesion to the design layer and production efficiency, those containing urethane resin are preferred.

[0055] The thickness of the adhesive primer layer is preferably 0.5 μm or more and 10 μm or less. If it is 0.5 μm or more, adhesion to the pattern layer can be suitably ensured, and if it is 10 μm or less, the transparent resin film does not become too thick, sufficient transparency can be obtained, and the design of the decorative sheet can be suitably ensured. Blocking during film formation can also be suppressed. Note that blocking is a phenomenon in which films are difficult to separate when forming a transparent resin film, applying an adhesive primer, etc., and then rolling it up into a roll and then unrolling it. Furthermore, the adhesive primer layer may contain inorganic fine particles such as silica.

[0056] The adhesive primer layer is preferably a layer containing the ultraviolet absorber. When the adhesive primer layer contains the ultraviolet absorber, weather resistance can be suitably imparted to the decorative board of the present invention.

[0057] As the ultraviolet absorber, for example, organic or inorganic ultraviolet absorbers can be used, and among them, organic ultraviolet absorbers that are excellent in transparency are preferably used. Examples of the organic ultraviolet absorber include 2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole; benzotriazole-based ultraviolet absorbers such as 2'-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as benzotriazole and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole; 2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2'-dihydroxy-4,4'-tetrahydroxybenzophenone; benzophenone-based ultraviolet absorbers such as 2-hydroxybenzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; and salicylate-based ultraviolet absorbers such as phenyl salicylate and 4-t-butyl-phenyl-salicylate. Among these, triazine-based ultraviolet absorbers are preferred from the viewpoint of providing weather resistance, designability, bleeding suppression, and the like.

[0058] Examples of the triazine-based ultraviolet absorber include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoate tris(2-ethylhexyl), 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, Examples include N,N',N''-tri(m-tolyl)-1,3,5-triazine-2,4,6-triamine, 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol. In addition, reactive UV absorbers in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton can also be used. Alternatively, if high transparency is not required, inorganic UV absorbers can also be added. Examples of inorganic UV absorbers that can be used include titanium oxide, cerium oxide, iron oxide, and zinc oxide, each having a particle size of 0.2 μm or less.

[0059] The content of the ultraviolet absorber is appropriately determined depending on the ultraviolet absorbing ability of the ultraviolet absorber used. When a triazine-based ultraviolet absorber is used as the ultraviolet absorber, it is preferable that the content of the triazine-based ultraviolet absorber in the adhesive primer layer be 1% by mass or more and 10% by mass or less. If the content in the adhesive primer layer is less than 1% by mass, sufficient weather resistance may not be imparted, and if the content in the adhesive primer layer exceeds 10% by mass, the transparency of the film may be impaired, reducing the design of the decorative panel, or sufficient adhesion to the pattern layer, etc. may not be obtained, reducing the processability of the transparent resin film. The content of the ultraviolet absorber is more preferably 2% by mass or more and 7% by mass or less.

[0060] [Surface protection layer] The transparent resin film preferably has a surface protective layer on the side of the thermoplastic resin layer opposite to the side laminated to the pattern layer. By having the above-mentioned surface protective layer, the durability (scratch resistance, contamination resistance, weather resistance, etc.) of the above-mentioned transparent resin film can be improved, the surface of the pattern layer can be more suitably protected, and deterioration of the design due to scratches on the above-mentioned transparent resin film itself can be suitably prevented. The surface protective layer may be a single layer, or may be a multi-layer structure made of the same or different materials, or may be a suitable mixture of the materials shown below.

[0061] The surface protection layer is not particularly limited, but examples thereof include a crosslinked and cured product of a two-component curable resin or an ionizing radiation curable resin composition. The crosslinked and cured product is preferably transparent, and may be translucent or colored as long as it is transparent and allows the pattern layer described below to be visible. The binder resin of the adhesive primer layer may be used as the two-component curing resin. As the ionizing radiation-curable resin, for example, an oligomer (hereinafter, so-called prepolymer, macromonomer, etc.) having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule and / or a monomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule is preferably used. Here, ionizing radiation refers to electromagnetic waves or charged particles having energy capable of polymerizing or crosslinking molecules, and typically includes electron beams (EB) or ultraviolet rays (UV).

[0062] Examples of the oligomer or monomer include compounds having a radically polymerizable unsaturated group such as a (meth)acryloyl group or a (meth)acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group in the molecule. These oligomers and monomers can be used alone or in combination. In this specification, the (meth)acryloyl group refers to an acryloyl group or a methacryloyl group.

[0063] As the oligomer having a radically polymerizable unsaturated group in the molecule, for example, oligomers such as urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, etc. can be preferably used, and urethane (meth)acrylate oligomers are more preferred. As the molecular weight, those having a molecular weight of about 250 to 100,000 are usually used.

[0064] Furthermore, as the monomer having a radically polymerizable unsaturated group in the molecule, for example, a polyfunctional monomer is preferred, and a polyfunctional (meth)acrylate is more preferred. Examples of the polyfunctional (meth)acrylate include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, bisphenol A ethylene oxide-modified di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate {pentafunctional (meth)acrylate}, dipentaerythritol hexa(meth)acrylate {hexafunctional (meth)acrylate}, etc. Here, the polyfunctional monomer refers to a monomer having multiple radically polymerizable unsaturated groups.

[0065] In the present invention, it is more preferable that the ionizing radiation curable resin composition contains an ionizing radiation curable resin component consisting of a urethane acrylate oligomer and a polyfunctional monomer, and it is particularly preferable that the ionizing radiation curable resin component has a urethane acrylate oligomer / polyfunctional monomer (mass ratio) of 6 / 4 to 9 / 1. This mass ratio range allows for more excellent scratch resistance. If necessary, in addition to the ionizing radiation curable resin component, a monofunctional monomer may be used as appropriate within the scope of the present invention. Examples of the monofunctional monomer include methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0066] When the ionizing radiation curable resin composition is crosslinked by ultraviolet light, it is preferable to add a photopolymerization initiator to the ionizing radiation curable resin composition. When the ionizing radiation curable resin composition is a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ethers can be used alone or in combination as the photopolymerization initiator. When the ionizing radiation-curable resin composition is a resin system having a cationically polymerizable unsaturated group, the photopolymerization initiator may be an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a methacerone compound, a benzoin sulfonate ester, or the like, either alone or in combination. The amount of these photopolymerization initiators added is about 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation-curable resin component.

[0067] The surface protective layer preferably contains a flame retardant. By adding a flame retardant to the surface protective layer, char formation and radical scavenging ability in combustion gases are expressed in response to heat applied from the surface during combustion, thereby reducing flammability. The content of the flame retardant in the surface protective layer is preferably such that the lower limit of the content of the flame retardant is 3% by mass or more, more preferably 4.4% by mass or more, and the upper limit of the content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less, where the total mass of the surface protective layer is 100%.

[0068] The surface protective layer preferably contains the flame retardant and the inorganic filler, from the viewpoint of improving the flame retardancy of the transparent resin film while maintaining the sharpness of the decorative board of the present invention. As the inorganic filler, those described in the thermoplastic resin layer above can be appropriately selected and used, and silica is preferred, and in consideration of the dispersibility of the flame retardant, fumed silica is more preferred, and among the fumed silica, hydrophilic fumed silica is even more preferred.

[0069] The surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent. By including an antibacterial agent or an antiviral agent in the surface protective layer, antibacterial properties and antiviral properties can be imparted to the decorative sheet. Furthermore, by including an antiallergenic agent in the surface protective layer, the decorative sheet can be provided with antiallergenic properties.

[0070] The above antibacterial agents and antiviral agents can generally be broadly classified into organic and inorganic types. Organic antibacterial and antiviral agents include quaternary ammonium salts, quaternary phosphonium salts, pyridines, pyrithiones, benzimidazoles, organic iodines, isothiazolinones, anions, and ethers. Inorganic antibacterial and antiviral agents include those in which metal ions such as silver, copper, and zinc are supported on zeolite, apatite, zirconia, glass, molybdenum oxide, and the like. The above antibacterial agents and antiviral agents may be used alone or in combination of two or more.

[0071] Among the above organic antibacterial and antiviral agents, benzimidazole compounds or anionic compounds that maintain a particle shape are particularly suitable. The term "maintaining a particle shape" means that the particles are present in a particle state without dissolving in the ionizing radiation-curable resin composition that forms the curable resin of the surface protective layer. Therefore, in the process of forming the surface protective layer, the particles of the benzimidazole compound or the particles of the anionic compound tend to float up, making it possible to easily distribute the particles of the benzimidazole compound or the particles of the anionic compound on the outermost surface side of the surface protective layer. Furthermore, by distributing the benzimidazole compound particles or the anionic compound particles unevenly on the outermost surface side of the surface protective layer, the amount of antibacterial agent or antiviral agent added that is necessary to obtain predetermined antibacterial and antiviral properties can be reduced, making it easier to prevent a decrease in the scratch resistance of the surface protective layer.

[0072] The anionic antibacterial and antiviral agents are preferably those containing, for example, styrene resins, styrene polymer derivative compounds, and unsaturated carboxylic acid derivative compounds. Furthermore, the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably contain at least one structure selected from the group consisting of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all of these structures. This is because there are two types of viruses: enveloped and non-enveloped, and it is believed that the structures of antibacterial agents and antiviral agents that can effectively inhibit the activity of each type of virus are different. Therefore, for example, if an effect on only influenza viruses, which are non-enveloped viruses, is expected, it is sufficient to contain only a styrene polymer derivative compound, and in particular, in some cases, a sufficient effect can be obtained by containing only a styrene resin alone.

[0073] As the inorganic antibacterial agent or antiviral agent, a silver-based antibacterial agent or antiviral agent is preferred from the viewpoint of being non-toxic to living organisms and excellent in safety. Among these, phosphate glass-supported silver compounds, silver zeolite compounds, and molybdenum oxide-silver double salt compounds are more preferred because they exhibit antibacterial and antiviral properties even in small amounts, allowing the amount added to be reduced. The average particle size of the inorganic antibacterial agent or antiviral agent is preferably, for example, 0.1 to 10 μm. If the average particle size is within the above range, the antibacterial agent and antiviral agent can be suitably dispersed, and antibacterial and antiviral properties can be suitably imparted without unevenness.

[0074] When the silver-based antibacterial agent or antiviral agent is added to the surface protective layer, discoloration may occur depending on the surface protective layer (the discoloration may occur due to heat or light in the paint state to which the agent is added, or may occur due to heat or light after the surface protective layer is formed). In such cases, however, it is possible to improve the situation by adding an ultraviolet inhibitor, a light stabilizer, or the like at the appropriate time. For example, when a benzotriazole compound is used for the molybdenum oxide silver double salt compound, it is expected that discoloration can be prevented.

[0075] The content of the antibacterial agent or antiviral agent is, for example, about 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation curable resin.

[0076] The antiallergen agent contains at least either an inorganic compound or an organic compound, and may be used alone or in combination of two or more. The antiallergen agent may also have the above-mentioned antibacterial or antiviral properties.

[0077] The inorganic compound is preferably a material that supports a metal. As the material supporting the above metal, for example, at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate, and magnesium phosphate is preferred, and among these, titanium oxide, zirconium phosphate, etc. are preferred. The metal supported on the metal-supporting material is preferably at least one selected from the group consisting of gold, silver, platinum, zinc and copper, and among these, silver, zinc and the like are preferred. Suitable commercially available products include "Parafine ANV-100: inorganic compound with silver support" manufactured by Ohara Palladium Co., Ltd. and "Atomy Ball TZ-R: titanium oxide with zinc support" manufactured by JGC Catalysts Co., Ltd. These anti-allergen agents are effective against various allergens such as dust mites and pollen.

[0078] The organic compound is preferably a water-insoluble polymer containing a phenolic hydroxyl group, a polyphenol compound supported on an inorganic solid acid, or a polymer containing at least one monomer component selected from the group consisting of styrenesulfonic acid and salts thereof.

[0079] As the water-insoluble polymer containing a phenolic hydroxyl group, commercially available products such as "Allerbuster (trade name)" manufactured by Sekisui Chemical Co., Ltd. and "Marukalinker M (trade name)" manufactured by Maruzen Oil Co., Ltd. can be used.

[0080] Examples of the polyphenol compound supported on an inorganic solid acid include a combination of a polyphenol compound and a zirconium compound, and examples of commercially available products include "Allerremove (trade name)" manufactured by Toa Gosei Co., Ltd. These antiallergen agents are effective against various allergens such as dust mites and pollen.

[0081] As the styrene sulfonic acid and salts thereof, materials such as those disclosed in Japanese Patent No. 6136433 can be used, and preferred examples include a homopolymer of styrene sulfonate, a styrene sulfonate-styrene sulfonic acid copolymer, a styrene sulfonate-styrene copolymer, a styrene sulfonic acid-styrene copolymer, and a styrene sulfonate-styrene sulfonic acid-styrene terpolymer.

[0082] The antiallergenic agent may be a mixture of an organic compound and an inorganic compound, for example, a mixture of an anionic phenolic material and a zinc-based material having antiallergenic properties.

[0083] Examples of the anionic phenolic materials include tannin, tannic acid, tartar emetic, phenolsulfonic acid formaldehyde resin, sulfone compounds of novolak resins, methanesulfonic acid of novolak resins, methanesulfonic acid of resol resins, benzylated phenolsulfonic acid, thiophenol compounds, dihydroxy, diphenylsulfone compounds, ligand compounds, and metal chelate compounds thereof.

[0084] The zinc-based material is suitably selected from a water-soluble zinc compound, a water-insoluble zinc compound, a zinc / metal oxide composite material, etc., and is preferably a water-dispersed composite particle of a water-insoluble zinc compound and / or a water-insoluble zinc / metal oxide, with an average particle size of 50 μm or less, and the metal oxide containing at least one of titania, silica, and alumina.

[0085] The content of the antiallergen agent is, for example, about 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation curable resin.

[0086] The ionizing radiation-curable resin composition may further contain various additives as needed, such as thermoplastic resins such as urethane resins, polyvinyl acetal resins, polyester resins, polyolefin resins, styrene-based resins, polyamide resins, polycarbonate resins, acetal resins, vinyl chloride-vinyl acetate copolymer resins, vinyl acetate resins, acrylic resins, and cellulose-based resins, lubricants such as silicone resins, waxes, and fluorine resins, ultraviolet absorbers such as benzotriazole, benzophenone, and triazine, light stabilizers such as hindered amine-based radical scavengers, gloss and texture adjusters such as silica, acrylic beads, and mica, and colorants such as dyes and pigments.

[0087] As the electron beam source of ionizing radiation, for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graaf type, resonant transformer type, insulating core transformer type, or linear type, dynamitron type, high frequency type, etc. can be used, which irradiate electrons having an energy of 70 to 1000 keV. The irradiation dose of the electron beam is preferably, for example, about 1 to 10 Mrad. As the ultraviolet light source of the ionizing radiation, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp, etc. can be used, and the wavelength of the ultraviolet light is usually in the wavelength range of 190 to 380 nm.

[0088] The thickness of the surface protective layer is not particularly limited, but a preferred lower limit is 0.1 μm, a preferred upper limit is 50 μm, and a more preferred lower limit is 1 μm, and a more preferred upper limit is 30 μm. If the thickness of the surface protective layer is less than 0.1 μm, sufficient durability (scratch resistance, contamination resistance, weather resistance, etc.) may not be imparted, and if it exceeds 50 μm, the transmittance of the transparent resin film of the present invention may decrease, resulting in reduced visibility of the pattern on the pattern layer.

[0089] It is preferable that a primer layer for the surface protective layer be provided between the surface protective layer and the thermoplastic resin layer. By providing the primer layer for the surface protective layer, the adhesion between the surface protective layer and the thermoplastic resin layer can be further strengthened. The primer layer for a surface protective layer preferably contains the ultraviolet absorber. When the primer layer for a surface protective layer contains the ultraviolet absorber, weather resistance can be more suitably imparted to the decorative board of the present invention. As the primer layer for the surface protective layer, the same as the above-mentioned primer layer for adhesion can be suitably used.

[0090] [Uneven shape] The transparent resin film has an uneven shape on the side opposite to the side laminated to the design layer. The depth of the unevenness on the side opposite to the side laminated to the pattern layer is not particularly limited, but it is preferable to appropriately adjust it so that the center line average roughness Ra as specified in JIS B 0601 (1982) is within the range of 1 μm or more and 30 μm or less.

[0091] The transparent resin film may have an uneven shape on the side that is laminated to the design layer. When the transparent resin film has an uneven shape to be laminated to the design layer on the side to be laminated to the design layer, it is preferable that the Rzmax of the uneven shape as defined in JIS B 0601 (2001) is 80 μm or less. If the Rzmax defined by JIS B 0601 (2001) of the uneven shape on the side laminated to the pattern layer exceeds 80 μm, air bubbles may easily get trapped between the pattern layer and the transparent resin film, which may reduce the design properties of the decorative panel of the present invention. It is more preferable that the roughness on the side laminated to the design layer has an Rzmax defined by JIS B 0601 (2001) of 60 μm or less. In this specification, the Rzmax can be obtained by measuring under the following conditions using a surface roughness measuring device (SURFCOM-FLEX-50A, manufactured by Tokyo Seimitsu Co., Ltd.). (Measurement conditions) 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 λs value: 8.0 μm If the uneven shape has a directional property, measurements are taken in the flow direction and in the direction perpendicular to it, and the larger value of the two is taken as Rzmax.

[0092] The method for forming the uneven shape is not particularly limited, and examples thereof include a method of embossing with heat and a method of transferring the uneven shape using a shaping sheet. Examples of heat embossing include a method of embossing using a well-known sheet-type or rotary embossing machine. Examples of embossed patterns include sand grain, hairline, matte finish, wood grain vessel grooves, uneven stone surface, cloth surface texture, and linear grooves. The temperature at which the embossing process is carried out is not particularly limited, but a temperature at which the loss of the uneven pattern during thermocompression molding, that is, the so-called embossing return, is reduced, is preferred. Furthermore, when the side laminated to the pattern layer has an uneven shape, the uneven shape may be formed on both sides of the transparent resin film by the above method, or the uneven shape may be formed on one side of the transparent resin film by the above method, and the uneven shape on the other side may be formed to follow the uneven shape formed on the one side.

[0093] The thickness of the transparent resin film is not particularly limited, but the thickness of the concave portion of the uneven shape is preferably 80 μm or more. If the thickness of the concave portion of the uneven shape of the transparent resin film is less than 80 μm, the decorative board of the present invention may not be able to be provided with sufficient durability (wear resistance, scratch resistance). Here, the "concave portion having a concave-convex shape" will be described. FIG. 2 is a cross-sectional view schematically showing a preferred example of the transparent resin film that constitutes the decorative board of the present invention. In the transparent resin film 20 shown in FIG. 2, an adhesive primer layer 21, a thermoplastic resin layer 22, a surface protection layer primer layer 23, and a surface protection layer 24 are laminated in this order in the thickness direction. The "depression of the uneven shape" refers to the thinnest part of the thickness of the transparent resin film, and is the part that includes the deepest depression of the uneven shape of the surface protection layer 24, and can be confirmed by observing the cross section of the transparent resin film 20 with a microscope. In Figure 2, the length from the surface having the surface protective layer 24 to the opposite surface is the total thickness of the transparent resin film 20, and the length from the bottom of the deepest recess on the surface protective layer 24 side to the surface of the adhesive primer layer 21 is the "thickness of the recess of the uneven shape." In addition, when an uneven shape is formed on the surface on the surface protective layer 24 side, and an uneven shape is generated on the opposite surface, as shown in Figure 3, a protrusion will be generated on the opposite surface corresponding to the deepest recess of the uneven shape on the surface protective layer 24 side of the transparent resin film 20, and the length from the bottom of the deepest recess of the uneven shape on the surface protective layer 24 side of the transparent resin film 20 to the opposite surface where such a protrusion exists will be the "thickness of the recess of the uneven shape." The lower limit of the total thickness of the transparent resin film is preferably 100 μm, the upper limit thereof is preferably 500 μm, the lower limit thereof is more preferably 140 μm, and the upper limit thereof is more preferably 460 μm. There is no particular upper limit to the thickness of the recesses of the uneven shape of the transparent resin film, but it is preferably 500 μm, for example.

[0094] The transparent resin film is preferably used to protect a design layer laminated on one side of the substrate. A transparent resin film used to protect a design layer laminated on one side of such a substrate is also an embodiment of the present invention.

[0095] [Adhesive layer] The decorative board of the present invention preferably has an adhesive layer between the design layer and the transparent resin film.

[0096] By providing the adhesive layer, the adhesion between the design layer and the transparent resin film can be further strengthened.

[0097] The adhesive layer preferably contains a binder resin. Examples of the binder resin include urethane resin, acrylic resin, acrylic-urethane resin, acrylic-urethane copolymer resin, cellulose resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, etc. Urethane resin is preferred in view of adhesion between the design layer and the transparent resin film and production efficiency.

[0098] The thickness of the adhesive layer is not particularly limited, but if the thickness is 10 μm or more and the transparent resin film has an uneven shape on the side laminated to the pattern layer, it is preferable that the thickness is greater than the Rzmax of the uneven shape defined in JIS B 0601 (2001). If the thickness of the adhesive layer is 10 μm or more and is greater than the Rzmax defined in JIS B 0601 (2001) of the uneven shape on the side of the transparent resin film to be laminated to the pattern layer, as described below, adhesion between the pattern layer and the transparent resin film can be suitably ensured. On the other hand, if the thickness of the adhesive layer is 10 μm or less, sufficient adhesion between the pattern layer and the transparent resin film may not be achieved, and if the thickness is smaller than the Rzmax defined in JIS B 0601 (2001) of the uneven shape on the side of the transparent resin film to be laminated to the pattern layer, air bubbles may get trapped between the pattern layer and the transparent resin film, reducing the design. The adhesive layer may contain inorganic fine particles such as silica.

[0099] The method for attaching the adhesive layer is not particularly limited, but it can be obtained, for example, by a heat melting method, a thermal lamination method, or by laminating using a water-based adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, or a hot melt adhesive.

[0100] The adhesive layer is preferably a layer containing the ultraviolet absorber. When the adhesive layer is a layer containing the ultraviolet absorber, excellent weather resistance can be suitably imparted to the decorative board of the present invention.

[0101] As the ultraviolet absorber, for example, organic or inorganic ultraviolet absorbers can be used, and among them, organic ultraviolet absorbers that are excellent in transparency are preferably used. Examples of the organic ultraviolet absorber include 2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole; benzotriazole-based ultraviolet absorbers such as 2'-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as benzotriazole and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole; 2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2'-dihydroxy-4,4'-tetrahydroxybenzophenone; benzophenone-based ultraviolet absorbers such as 2-hydroxybenzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; and salicylate-based ultraviolet absorbers such as phenyl salicylate and 4-t-butyl-phenyl-salicylate. Among these, triazine-based ultraviolet absorbers are preferred from the viewpoint of providing weather resistance, designability, bleeding suppression, and the like. As the triazine-based ultraviolet absorber, any of the triazine-based ultraviolet absorbers described above for the adhesive primer layer can be appropriately selected and used. In addition, reactive UV absorbers in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton can also be used. Alternatively, if high transparency is not required, inorganic UV absorbers can also be added. Examples of inorganic UV absorbers that can be used include titanium oxide, cerium oxide, iron oxide, and zinc oxide, each having a particle size of 0.2 μm or less.

[0102] The content of the ultraviolet absorber is determined appropriately depending on the ultraviolet absorbing ability of the ultraviolet absorber used. When a triazine-based ultraviolet absorber is used as the ultraviolet absorber, it is preferable that the content of the triazine-based ultraviolet absorber in the adhesive layer be 0.5% by mass or more and 2% by mass or less. If the content in the adhesive layer is less than 0.5% by mass, sufficient weather resistance may not be imparted, and if the content in the adhesive layer exceeds 2% by mass, the transparency of the adhesive layer may be impaired, reducing the design of the decorative panel, or sufficient adhesion may not be obtained between the pattern layer and the transparent resin film described below, reducing the processability of the decorative panel of the present invention. The content of the ultraviolet absorber is more preferably 1% by mass or more and 1.5% by mass or less.

[0103] The various additives added to each layer of the transparent resin film (such as inorganic fillers added to the primer layer or surface protective layer) are preferably vesiculated. The method for vesiculating the various additives is not particularly limited, and they can be vesiculated by known methods, among which supercritical reverse phase evaporation is preferred.

[0104] Other examples of the vesicle-forming method include the Bangham method, extrusion method, hydration method, reverse phase evaporation method, and freeze-thaw method. To briefly explain this vesicle formation method, the Bangham method involves placing chloroform or a chloroform / methanol mixed solvent in a flask or other container, then adding and dissolving phospholipids. The solvent is then removed using an evaporator to form a thin film of lipids, and a dispersion of additives is added. The mixture is then hydrated and dispersed in a vortex mixer to obtain vesicles. The extrusion method is a method in which a thin film of phospholipid solution is prepared and passed through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain vesicles. The hydration method is a preparation method that is almost the same as the Bangham method, but in this method, vesicles are obtained by dispersing the particles by gentle stirring without using a mixer. The reverse phase evaporation method involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method uses cooling and heating as external perturbations, and vesicles are obtained by repeating this cycle.

[0105] The supercritical reverse phase evaporation method will be described in detail below. The supercritical reverse phase evaporation method is a method in which a substance that forms the outer membrane of a vesicle is uniformly dissolved in carbon dioxide in a supercritical state or under temperature or pressure conditions above the supercritical point, and an aqueous phase containing various additives as water-soluble or hydrophilic encapsulation substances is added to the mixture to form capsule-like vesicles that encapsulate various additives as encapsulation substances in a single layer of membrane. Carbon dioxide in a supercritical state refers to carbon dioxide in a supercritical state at or above its critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa), and carbon dioxide under temperature or pressure conditions above its critical point refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. This method can produce unilamellar vesicles with a diameter of 50 to 800 nm. Generally, a vesicle is a general term for a small vesicle having a spherical, closed membrane structure and containing a liquid phase inside, and in particular, a liposome is one whose outer membrane is composed of biological lipids such as phospholipids.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] [Manufacturing method of decorative panels] Examples of methods for manufacturing the decorative board of the present invention include a heat melting method, a heat lamination method, and a method of laminating the substrate, the pattern layer, and the transparent resin film using a water-based adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot melt adhesive, an adhesive that forms the adhesive layer described above, or the like. In particular, it is preferable to have a step of forming the adhesive layer on the surface of the transparent resin film that will be laminated to the pattern layer, and a step of bonding the transparent resin film and the pattern layer together via the adhesive layer. Such a method for producing the decorative board of the present invention is also an aspect of the present invention. The manufacturing method for decorative panels of the present invention prevents the occurrence of so-called air bubbles, in which air gets into the uneven shape on the side of the transparent resin film that is laminated to the pattern layer, and suppresses a decrease in the design of the pattern layer. The thickness of the decorative board of the present invention is not particularly limited, and is preferably 0.05 mm or more, and more preferably 1 mm or more and 50 mm or less, for example. [Example]

[0112] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0113] Example 1 A transparent polypropylene film (60 μm thick) was prepared, and one side of the transparent polypropylene film was coated with a two-component curing urethane resin containing 5% by mass of a triazine-based UV absorber (product name: Adekastab LA-46, manufactured by ADEKA Corporation) and an isocyanate curing agent to form a 2 μm-thick adhesive primer layer. Next, a transparent polypropylene resin (80 μm thick) containing a flame retardant (phosphinic acid metal salt-based flame retardant, product name: Pekoflam STC, manufactured by Archroma) was melt-extruded onto the other side of the transparent polypropylene film (the side opposite the adhesive primer), and the two layers were laminated by thermal lamination to form a two-layer thermoplastic resin layer. The content of the flame retardant was 6 parts by mass of the metal phosphinate flame retardant, based on 100 parts by mass of the flame retardant-containing transparent polypropylene resin. The thermoplastic resin layer had a thickness of 140 μm, and the content of the metal phosphinate flame retardant was 3.3% by mass, with the total mass of the thermoplastic resin layer being 100% by mass. After corona treatment was performed on the surface of the above flame retardant-containing transparent polypropylene resin (80 μm) (the side opposite the adhesive primer), a two-component curing urethane resin using isocyanate as a curing agent was applied to form a 2 μm thick primer layer for surface protection. Next, a urethane acrylate oligomer, an ionizing radiation curable resin, was applied as a surface protective layer to the surface coated with the primer layer using the gravure coating method, and then irradiated with an electron beam at an acceleration voltage of 165 keV and 5 Mrad to form a surface protective layer with a thickness of 15 μm. The surface protective layer side was heated with an infrared non-contact heater, and then immediately embossed with heat and pressure to form a concave-convex shape, producing a transparent resin film. The resulting transparent resin film had a thickness of 159 μm, and the thickness of the concave portions of the concave-convex shape was 80 μm. On the other hand, a high density fiberboard (HDF) (thickness: 3 mm) was prepared, and a pattern layer having a thickness of 2 μm was provided on one surface of the HDF using an inkjet printer to prepare a substrate. A two-component curing polyester resin using isocyanate as a curing agent was applied to the surface of the obtained transparent resin film having the adhesive primer layer to form an adhesive layer with a thickness of 30 μm, and the adhesive primer layer of the obtained transparent resin film and the above-mentioned pattern layer were laminated so as to face each other. 2 The laminate was then cured at room temperature for 3 days under a pressure of 1000 kJ / min, to obtain a decorative panel.

[0114] Example 2 A transparent resin film and a decorative board were produced in the same manner as in Example 1, except that the flame retardant contained in the flame retardant-containing polypropylene resin was changed to a phosphazene flame retardant (Lavitol FP-10, manufactured by Fushimi Pharmaceutical Co., Ltd.). The thickness of the obtained transparent resin film and the thickness of the recesses of the uneven shape were as shown in Table 1.

[0115] Example 3 A transparent polypropylene film (thickness 60 μm) was prepared, and a two-component curing urethane resin using isocyanate as a curing agent was coated on one side of the transparent polypropylene film, and a 2 μm thick adhesive primer layer was formed. A transparent resin film was produced in the same manner as in Example 1, except that embossing was performed using a deeper embossing plate different from that in Example 1. The thickness of the obtained transparent resin film and the thickness of the recesses in the uneven shape were as shown in Table 1. A two-component curing polyester resin using an isocyanate curing agent was applied to the adhesive primer layer side of the obtained transparent resin film to form an adhesive layer with a thickness of 90 μm, and the obtained transparent resin film was laminated so that the adhesive primer layer of the obtained transparent resin film faced the above-mentioned pattern layer. At this time, a triazine-based ultraviolet absorber (product name Adeka STAB LA-46, manufactured by ADEKA Corporation) was added to the above-mentioned two-component curing polyester resin so as to be 1% by mass. Then, 10 kg / m 2 The laminate was then cured at room temperature for 3 days under a pressure of 1000 kJ / min, to obtain a decorative panel.

[0116] Example 4 A transparent polypropylene film (50 μm thick) was prepared, and a two-component curing urethane resin containing 5% by mass of a triazine-based UV absorber (product name: Adeka STAB LA-46, manufactured by ADEKA Corporation) and using an isocyanate as a curing agent was coated on one side of the transparent polypropylene film (50 μm thick) to obtain a 2 μm thick adhesive primer layer. Next, a flame-retardant-containing transparent polypropylene resin (50 μm thick) was melt-extruded onto the other side of the transparent polypropylene film (50 μm thick) (the side opposite the adhesive primer layer), and these were laminated by thermal lamination to obtain a two-layer thermoplastic resin layer. The content of the flame retardant was 7.5 parts by mass of the metal phosphinate flame retardant, based on 100 parts by mass of the flame retardant-containing transparent polypropylene resin. The thermoplastic resin layer had a thickness of 100 μm, and the content of the metal phosphinate flame retardant was 3.5% by mass, with the total mass of the thermoplastic resin layer being 100% by mass. Thereafter, a primer layer for a surface protective layer and a surface protective layer were formed in the same manner as in Example 1, and then embossing was carried out with a deep embossing plate different from that in Example 3 to obtain a transparent resin film. A two-component curing polyester resin using isocyanate as a curing agent was applied to the surface of the obtained transparent resin film having the adhesive primer layer to form an adhesive layer with a thickness of 90 μm, and the obtained transparent resin film was laminated so that the adhesive primer layer and the pattern layer of the film faced each other. Other than the above, a decorative board was produced in the same manner as in Example 1. The thickness of the obtained transparent resin film and the thickness of the recesses of the uneven shape were as shown in Table 1.

[0117] Example 5 A transparent resin film and a decorative plate were produced in the same manner as in Example 1, except that embossing was performed using the embossing plate used in Example 4. The thickness of the obtained transparent resin film and the thickness of the recesses of the uneven shape were as shown in Table 1.

[0118] Example 6 A transparent resin film was produced in the same manner as in Example 2, except that a transparent polypropylene-based resin (thickness 30 μm, thermoplastic resin layer) containing a flame retardant (phosphazene-based flame retardant, Rabitol FP-10, manufactured by Fushimi Pharmaceutical Co., Ltd.) and hydrophilic fumed silica (AEROSIL 50, manufactured by Nippon Aerosil Co., Ltd.) was used as the transparent polypropylene-based resin to be melt-extruded. A decorative material was also produced in the same manner as in Example 2. The contents of the flame retardant and hydrophilic fumed silica were each 6 parts by mass, based on 100 parts by mass of the flame retardant-containing transparent polypropylene resin. The thickness of the thermoplastic resin layer with a two-layer structure was 140 μm, and the contents of the flame retardant and hydrophilic fumed silica were 3.1% by mass, respectively, based on the total mass of the thermoplastic resin layer with a two-layer structure being 100% by mass.

[0119] (Example 7) A transparent resin film and a decorative board were produced in the same manner as in Example 1, except that 3 parts by mass of a phosphoric acid-based silver-loaded glass compound (manufactured by Koa Glass Co., Ltd. / PG-711) was added as an antiviral agent to 100 parts by weight of the radiation-curable resin.

[0120] (Example 8) A transparent resin film and a decorative board were produced in the same manner as in Example 1, except that an anionic phenolic material having anti-allergenic properties (DIC Corporation's "EXP20530A") was blended at a solid content ratio of 23% by mass and a zinc-based material having anti-allergenic properties (DIC Corporation's "EXP20530B") was blended at a solid content ratio of 23% by mass with respect to the radiation-curable resin.

[0121] (Comparative Example 1) A transparent resin film and a decorative board were produced in the same manner as in Example 1, except that a transparent polypropylene-based resin that does not contain a flame retardant was used for melt extrusion. The thickness of the obtained transparent resin film and the thickness of the concave portion of the concavo-convex shape were as shown in Table 1.

[0122] (Comparative Example 2) A transparent polypropylene film (thickness: 60 μm) was prepared, and a two-component curable urethane resin using isocyanate as a curing agent was coated on one surface of the transparent polypropylene film to provide an adhesive primer layer with a thickness of 2 μm. A transparent resin film and a decorative board were produced in the same manner as in Example 1. The thickness of the obtained transparent resin film and the thickness of the concave portion of the concavo-convex shape were as shown in Table 1.

[0123] (Measurement of Rzmax) The Rzmax defined by JIS B 0601 (2001) of the uneven shape of the transparent resin film on the side laminated to the picture layer in the decorative panels obtained in the examples and comparative examples was measured using a surface roughness measuring device ("SURFCOM-FLEX-50A", manufactured by Tokyo Seimitsu Co., Ltd.) under the following conditions. (Measurement conditions) 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 λs value: 8.0 μm When the uneven shape had a directional property, measurements were taken in the flow direction and in the direction perpendicular to the flow direction, and the larger value in both directions was taken as Rzmax.

[0124] (Evaluation method) <Abrasion resistance (Taber abrasion test)> The decorative panels obtained in the examples and comparative examples were subjected to a test in accordance with the Abrasion Test A of the Japanese Agricultural Standards for flooring using a Taber type abrasion tester (manufactured by Rigaku Kogyo Co., Ltd.) and an abrasion wheel (S-42) at a load of 1 kg, and the pattern remaining on the design layer after 1000 revolutions was evaluated. The results are shown in Table 1. ++: More than 80% of the pattern remains +: More than half but less than 80% of the pattern layer remains -: Less than half of the pattern layer remains

[0125] <Color difference after weather resistance test> The decorative panels obtained in the examples and comparative examples were placed in an ultra-accelerated weathering tester (Iwasaki Electric Co., Ltd., Eye Super UV Tester) set under the following conditions, and after 17 cycles of 20 hours of irradiation and 4 hours of condensation, the panels were removed. (Accelerated test conditions) Black panel temperature: 63℃ ·Humidity: 50%RH ·Irradiation intensity: 60W / m2 (365nm) Thereafter, the change in color difference of the decorative board before and after the accelerated test was measured using a colorimeter (CR-300 manufactured by Minolta Co., Ltd.). That is, the L value, a value, and b value of the decorative board before and after the accelerated test were measured, and the color difference change ΔE was calculated using the following formula 1. The results are shown in Table 1. ΔE=[(ΔL) 2 +(Δa) 2 +(Δb) 2 ] 1 / 2 formula 1 ++:ΔE<1.0 +:1.0≦ΔE<1.5 -:ΔE≧1.5 ΔL = |L value (after weather resistance test) - L value (before weather resistance test)| Δa = |a value (after weather resistance test) - a value (before weather resistance test)| Δb = |a value (after weather resistance test) - a value (before weather resistance test)|

[0126] <Design> The printed patterns of the decorative boards obtained in the examples and comparative examples were visually evaluated. The results are shown in Tables 1 and 2. ++: The printed pattern is clearly visible +: The print appears slightly cloudy -: The print pattern is not clearly visible

[0127] <Film forming properties> For the Examples and Comparative Examples, the presence or absence of defects (blocking) during the production of the obtained transparent resin films was confirmed, and the film formability was evaluated. The results are shown in Table 1. ++: Did not block +: Slight blocking -: Blocked

[0128] <Processability (adhesion strength)> For the Examples and Comparative Examples, the transparent resin film obtained was laminated so that the side opposite to the side having the concave-convex shape was in contact with the side of the substrate having the pattern layer, and the adhesion strength was evaluated. The results are shown in Table 1. ++: Adhesion was satisfactory (adhesion strength exceeding 20N / 25mm) +: Adhesion strength was slightly weak (adhesion strength 15N / 25mm or more, 20N / 25mm or less) -: The adhesive strength was very weak (adhesion strength less than 15N / 25mm) The adhesive strength was measured using a Tensilon universal testing machine "RTC-1250A" (manufactured by Orientec) for the decorative panels obtained in the examples and comparative examples, measuring the maximum peel strength [N / 25mm width] when peeling between the transparent resin film and the substrate laminated to the picture layer at a tensile speed of 200mm / min and a peel angle of 180°.

[0129] <Flame retardancy evaluation> [Horizontal burning (flame retardancy: difficulty in spreading fire)] The decorative panel was cut into a size of 9 cm x 30 cm to serve as a test specimen. As shown in Figures 4(a) and (b), a rectangular metal stand 103 was placed on the stand 102 of a commercially available household heater 101 (voltage: AC 100 V, power consumption: 1200 W). A test specimen 105 was placed in a metal frame 104 set on the stand. The heater angle was adjusted to 45° and the heater output was set to 4 / 5. A fire spread test was conducted. Specifically, the test specimen was preheated for 2 minutes using the household heater. Next, as shown in Figure 4(a), the end 106 of the test specimen on the heater side in the longitudinal direction was ignited by heating with a lighter 107 for 1 minute. The fire spread along the length of the test specimen 105 was then observed visually, and the fire spread distance (L1) (and burning duration) were evaluated as follows. The results are shown in Table 1. [Fire Distance (L1)] The test piece was ignited, and the flame from the lighter was removed. The distance the fire spread from the initial ignition was measured and taken as the fire spread distance (L1), which was then evaluated according to the following criteria. Note that a rating of + or higher is considered to be satisfactory for practical use. +: L1 is less than 10 cm -: L1 is 10cm or more

[0130] <Antiviral> The transparent resin films produced in Examples 1 and 7 were subjected to an antiviral performance test in accordance with the antiviral testing method (ISO 21702) to evaluate their antiviral activity against influenza viruses. The results are shown in Table 3. +: Antiviral activity value of 2.0 or higher -: Antiviral activity value less than 2.0

[0131] <Anti-allergenic> The transparent resin films prepared in Examples 1 and 8 were cut into small pieces and immersed in an aqueous solution of mite allergen for 1 day, after which the amount of allergen was visually confirmed by horizontal development chromatography (Mighty Checker). The results are shown in Table 4. +: A reduction in the amount of allergens was confirmed. -: No reduction in allergen levels was confirmed

[0132] [Table 1]

[0133] [Table 2]

[0134] [Table 3]

[0135] [Table 4]

[0136] From Table 1, it was confirmed that the decorative boards obtained in the examples had excellent weather resistance and also excellent flame retardancy. Furthermore, in Examples 1 to 3, in which the thickness of the concave portions of the uneven shape of the transparent resin film, Rzmax, and the thickness of the adhesive layer were within the predetermined ranges and a triazine-based ultraviolet absorber was used, the abrasion resistance, designability, and processability were also excellent. Furthermore, from Example 6, it was confirmed that the designability was improved by including a flame retardant and a filler in the thermoplastic resin layer. On the other hand, Comparative Example 1, which did not contain a flame retardant, was inferior in flame retardancy, and Comparative Example 2, which did not contain an ultraviolet absorber, was inferior in weather resistance. From Table 3, it was confirmed that the transparent resin film produced in Example 7 has antiviral properties. From Table 4, it was confirmed that the transparent resin film produced in Example 8 had antiallergenic properties. [Industrial Applicability]

[0137] According to the present invention, a decorative board having excellent weather resistance can be provided. Because the decorative board of the present invention has excellent weather resistance, it is suitable for use in building materials such as fittings, doors such as sliding doors, flooring materials, walls, ceilings, and various decorative molded articles. [Explanation of symbols]

[0138] 10 Decorative panels 11 Base material 12 Picture layer 13 Adhesive layer 20 Transparent resin film 21 Adhesive primer layer 22 Thermoplastic resin layer 23 Surface protection primer layer 24 Surface protective layer 101 Household heater 102 Household heater stand 103 Rectangular stand 104 Metal Frame 105 test specimens 106 End 107 writer

Claims

1. A decorative board in which a substrate, a pattern layer, and a transparent resin film are laminated in this order in the thickness direction, the transparent resin film has at least a thermoplastic resin layer and has an uneven shape on the side opposite to the side laminated with the pattern layer, the transparent resin film contains a flame retardant, At least one layer containing an ultraviolet absorber is provided between the design layer and the thermoplastic resin layer, the flame retardant is at least one selected from the group consisting of a metal phosphinate flame retardant, a phosphazene flame retardant, and a NOR-type hindered amine flame retardant, The thermoplastic resin layer is composed of two or more layers, and the outermost thermoplastic resin layer contains a flame retardant, and the flame retardant is contained in an amount of 3% by mass or more and 20% by mass or less, with the total mass of the outermost thermoplastic resin layers being 100% by mass. A decorative panel characterized by:

2. 2. The decorative board according to claim 1, wherein the thickness of the concave portions of the concave-convex shape of the transparent resin film is 80 [mu]m or more.

3. 3. The decorative board according to claim 1, wherein the transparent resin film has an uneven surface on the side where the pattern layer is laminated.

4. The decorative board according to claim 3, wherein the Rzmax defined in JIS B 0601 (2001) of the uneven shape of the transparent resin film on the side laminated to the picture layer is 80 μm or less.

5. The decorative board according to any one of claims 1 to 4, wherein the transparent resin film has a surface protective layer on the side of the thermoplastic resin layer opposite to the side laminated to the pattern layer.

6. The decorative board according to claim 5 , wherein the surface protective layer contains a flame retardant.

7. The decorative board according to claim 5 or 6, wherein the surface protective layer contains at least one of an antibacterial agent, an antiviral agent, and an antiallergenic agent.

8. The decorative board according to any one of claims 1 to 7, wherein the thermoplastic resin layer contains a filler.

9. The decorative board according to any one of claims 1 to 8, further comprising an adhesive layer between the design layer and the transparent resin film.

10. The thickness of the adhesive layer is 10 μm or more and is greater than the Rzmax defined in JIS B 0601 (2001) of the uneven shape on the side of the transparent resin film that is laminated to the picture layer. A decorative board as described in claim 9.

11. The decorative board according to claim 9 or 10, wherein the adhesive layer is a layer containing the ultraviolet absorber.

12. The decorative board according to claim 11, wherein the adhesive layer contains the ultraviolet absorber in an amount of 0.5% by mass or more and 2% by mass or less.

13. 13. The decorative board according to claim 11, wherein the ultraviolet absorber contained in the adhesive layer is a triazine-based ultraviolet absorber.

14. The decorative board according to any one of claims 1 to 13, wherein the transparent resin film has an adhesive primer layer on the side of the thermoplastic resin layer that is laminated to the pattern layer.

15. The decorative board according to claim 14, wherein the adhesive primer layer is a layer containing the ultraviolet absorber.

16. 16. The decorative board according to claim 15, wherein the ultraviolet absorber contained in the adhesive primer layer is a triazine-based ultraviolet absorber.

17. A transparent resin film used to protect a pattern layer laminated on one side of a substrate, the transparent resin film has at least a thermoplastic resin layer and has an uneven shape on the side opposite to the side laminated with the pattern layer, the transparent resin film contains a flame retardant, At least one layer containing an ultraviolet absorber is provided between the design layer and the thermoplastic resin layer, the flame retardant is at least one selected from the group consisting of a metal phosphinate flame retardant, a phosphazene flame retardant, and a NOR-type hindered amine flame retardant, The thermoplastic resin layer is composed of two or more layers, the outermost thermoplastic resin layer contains a flame retardant, and the total mass of the outermost thermoplastic resin layers is 100 mass%, and the transparent resin film contains the flame retardant in an amount of 3 mass% to 20 mass%.

18. A method for producing a decorative board according to any one of claims 1 to 16, forming an adhesive layer on the surface of the transparent resin film that will be laminated to the pattern layer; a step of bonding the transparent resin film and the pattern layer via the adhesive layer. A method for manufacturing a decorative panel.

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