Decorative sheet, decorative member, and method for producing decorative sheet

Abstract

To provide a decorative sheet capable of imparting a design feeling such as a grain pattern or the like not only visually but also tactually and a method for manufacturing the decorative sheet.SOLUTION: The surface-protecting layer 5, which is the outermost layer, has an embossed portion 5a as the uneven shape, and the gloss-matte expression is expressed by using a region of the outermost layer where the uneven shape is formed (a region of the embossed portion 5a) and a region where the uneven shape is not formed (a region excluding the embossed portion 5a). At this time, a difference in glossiness with respect to incident light at an incident angle of 85 ° between a region where the uneven shape is formed and a region where the uneven shape is not formed is 3 or more, and a difference in arithmetic average roughness Ra between the regions is 6 μm or more. As a result, a sufficient difference in glossiness is developed between the region of the embossed portion 5a and the region excluding the embossed portion 5a, and a sufficient difference in arithmetic average roughness Ra is developed, so that a gloss-matte design can be visually and tactilely developed.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet, a decorative member, and a method for manufacturing a decorative sheet. [Background technology]

[0002] Conventionally, decorative sheets have been proposed that enhance design by producing a gloss / matte finish. For example, a method has been proposed for producing a gloss / matte finish by providing a gloss adjustment layer having a pattern based on the gloss state on a surface protective layer (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6613719 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the decorative sheet described in Patent Document 1, because a gloss-adjusting layer is provided on the surface of the decorative sheet, the gloss-adjusting layer may peel off due to wear of the surface of the decorative sheet, potentially leading to a loss of the gloss-matt design. Also, by aligning the pattern of the picture-printed layer with the uneven pattern provided in the transparent thermoplastic resin layer and the gloss-adjusting layer, it is possible to achieve a gloss-matt appearance that can be seen with the naked eye, such as a wood grain pattern, but it is insufficient to impart a gloss-matt design feel to the touch of the decorative sheet, i.e., to the touch.

[0005] The present invention has been made in consideration of the above points, and aims to provide a decorative sheet, a decorative member, and a method for manufacturing a decorative sheet that can express a design feel such as a wood grain pattern not only visually but also tactilely. [Means for solving the problem]

[0006] According to one aspect of the present invention, there is provided a decorative sheet having an uneven surface on the outermost layer, which exhibits a glossy matte appearance by utilizing areas of the outermost layer where the uneven surface is formed and areas where the uneven surface is not formed, wherein the difference in gloss level between the areas where the uneven surface is formed and the areas where the uneven surface is not formed for light incident at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between the areas where the uneven surface is formed and the areas where the uneven surface is not formed is 6 μm or more. According to another aspect of the present invention, there is provided a decorative member comprising a substrate and a decorative sheet of the above-described aspect provided on at least one side of the substrate, wherein the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

[0007] According to another aspect of the present invention, there is provided a method for producing a decorative sheet having a textured top layer, which exhibits a glossy matte appearance by utilizing areas of the top layer where the textured shape is formed and areas where the textured shape is not formed, by laminating a pattern layer, a transparent resin layer, and a surface protective layer as the top layer, in that order, on one side of a colored resin layer, and on the other side of the colored resin layer, a light absorbing section that is in tune with the pattern of the pattern layer is formed by using a predetermined material that is more light absorbing for light of a predetermined wavelength than the colored resin layer, and after irradiating the surface protective layer with light having a power of the predetermined wavelength that is stronger than the power of light of other wavelengths, the surface protective layer is pressed with an embossing plate to form the textured shape, and the difference in gloss between the areas where the textured shape is formed and the areas where the textured shape is not formed is 3 or more for light incident at an incident angle of 85°, and the difference in arithmetic mean roughness Ra between the areas where the textured shape is formed and the areas where the textured shape is not formed is 6 μm or more. [Effects of the Invention]

[0008] According to one embodiment of the present invention, it is possible to obtain a decorative sheet, a decorative member, and a method for manufacturing a decorative sheet that can provide a gloss / matt appearance visually and tactilely. [Brief explanation of the drawings]

[0009] [Figure 1]1 is a cross-sectional view schematically illustrating an example of a decorative sheet according to one embodiment of the present invention. [Figure 2] 1A to 1C are process diagrams schematically illustrating an example of a procedure for producing a decorative sheet according to one embodiment of the present invention. [Figure 3] FIG. 3 is a cross-sectional view schematically illustrating an example of a decorative member according to a modified example of the first embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present technology will be described with reference to the drawings.

[0011] The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., differ from the actual ones. Furthermore, the embodiments shown below are merely examples of configurations for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims.

[0012] [Configuration of decorative sheet] 1, a decorative sheet 1 according to one embodiment of the present invention is formed by laminating, in this order, a colored thermoplastic resin layer (colored resin layer) 2, a pattern layer 3, a transparent thermoplastic resin layer (transparent resin layer) 4, and a surface protective layer 5, with an embossed portion 5a formed in the surface protective layer 5. Furthermore, on the surface of the colored thermoplastic resin layer 2 opposite the pattern layer 3, a light absorbing portion 6 is formed in a position that matches the pattern of the pattern layer 3, and a primer layer 7 is formed so as to cover the colored thermoplastic resin layer 2 including the light absorbing portion 6.

[0013] [Colored thermoplastic resin layer] Examples of materials for the colored thermoplastic resin layer 2 include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc. Among these, polyolefin-based resins are preferred in terms of environmental compatibility, processability, and price. The grade and composition of the resin can also be selected taking into consideration ease of sheeting, printability, and suitability for bending.

[0014] The hue of the colored thermoplastic resin layer 2 can be appropriately selected as the base color of the design layer 3. The colored thermoplastic resin layer 2 can be colored, for example, by mixing or kneading a colorant such as a pigment into the thermoplastic resin during sheeting. Alternatively, a colored layer can be provided as a solid ink layer using a coating or printing technique before providing the light-absorbing portion 6. The thickness of the colored thermoplastic resin layer 2 is not particularly limited.

[0015] [Picture layer] The design layer 3 is a printed layer on which a design pattern is printed to impart design to the decorative sheet 1. Known printing methods can be used to form the design layer 3. The printing method is not particularly limited, but gravure printing is preferred considering productivity and design quality. For example, if the colored thermoplastic resin layer 2 is available in a rolled state, printing to form the design layer 3 can be performed using a roll-to-roll printing device. Other printing methods include offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, and transfer printing from a transfer sheet. When using such printing methods, the design pattern of the design layer 3 can be formed by multicolor printing using the usual process colors of yellow, red, blue, and black, or by multicolor printing using special colors, in which plates of the individual colors that make up the design pattern are prepared.

[0016] Furthermore, the pattern of the pattern layer 3 may be any pattern, taking into consideration the design of the flooring or fittings. For example, a marble grain pattern can be used to evoke the image of a stone floor such as marble. For example, various wood grains or cork can be used as the pattern for a wood-based design. In addition to patterns of natural materials, artificial patterns based on these motifs or geometric patterns can also be used. Other examples of patterns include wood grain patterns composed of spring wood and autumn wood regions and vessels in the cross section of tree rings, leather (grain) patterns, stone grain patterns on the surface of stone such as marble, granite, and sandstone, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, geometric shapes, letters, symbols, abstract patterns, floral patterns, landscapes, characters, and the like.

[0017] Printing ink is a mixture of a solvent and solid components such as a colorant and a binder resin. Examples of solvents include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. The solvents may be used alone or in combination of two or more.

[0018] Examples of binder resins include chlorine-based resins, urethane resins, acrylic urethane resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. Examples of chlorine-based resins include polyvinyl chloride resins such as polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, and vinyl chloride-vinyl acetate-(meth)acrylic copolymers, as well as polypropylene chloride and chlorinated polypropylene. Here, (meth)acrylic means acrylic or methacrylic. The binder resin may be a single type or a combination of two or more types.

[0019] Examples of colorants include inorganic pigments such as carbon black, iron black, titanium white (titanium oxide), antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; and organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue. The colorants may be used alone or in combination of two or more. Here, the solvent contained in the printing ink will eventually volatilize, so the design layer 3 is formed mainly from solid components such as colorants and binder resins.

[0020] The printing ink may also contain other components such as stabilizers, plasticizers, catalysts, and curing agents. The printing ink may be selected based on the printing method. It is preferable to select the printing ink taking into consideration adhesion to the colored thermoplastic resin layer 2, printability, and weather resistance as a flooring material or fitting. The thickness of the design layer 3 can be adjusted appropriately, taking into consideration the decorative properties required of the design layer 3, the three-dimensional formability of the decorative sheet 1, and the like. The thickness of the design layer 3 is typically 1 μm or more and 1 mm or less, preferably 2 μm or more and 0.1 mm or less, and more preferably 2 μm or more and 50 μm or less.

[0021] To improve the adhesion between the design layer 3 and the transparent thermoplastic resin layer 4, an adhesive layer (not shown) may be provided on the surface of the design layer 3 that comes into contact with the transparent thermoplastic resin layer 4. By strengthening this adhesion, the decorative sheet 1 can be given the ability to be bent to conform to curved surfaces and right-angled surfaces. The resin used in the adhesive layer (not shown) is not particularly limited. For example, a two-component curing urethane resin can be used as the resin used in the adhesive layer. The adhesive resin may also be bonded to the design layer 3 with a urethane adhesive. For example, a coating device or a gravure printing device can be used to apply the resin used in the adhesive layer (not shown).

[0022] Furthermore, a glittering layer (not shown) may be provided between the picture layer 3 and the transparent thermoplastic resin layer 4 in order to suitably impart design effects such as a sense of depth and brightness to the decorative sheet 1. The glittering layer (not shown) preferably contains a glittering pigment and a binder resin. Examples of glittering pigments include pearlescent pigments and metallic pigments. Pearlescent pigments are particularly preferred because they can prevent a decrease in the light transmittance of the glittering layer and therefore do not impair the visibility of the picture layer 3.

[0023] Pearl pigments are pigments that can impart pearlescent luster. Examples include base particles whose surfaces are coated with a metal oxide. The base particles are preferably scaly particles such as mica. Examples of metal oxides include oxides of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium. The metal oxides may be used alone or in combination. Specific examples include oxide-coated mica such as titanium mica, iron oxide-coated mica, iron oxide-coated mica titanium, Prussian blue-coated mica titanium, Prussian blue-iron oxide-coated mica titanium, chromium oxide-coated mica titanium, carmine-coated mica titanium, organic pigment-coated mica titanium, titanium oxide-coated mica, and titanium oxide-coated synthetic mica; oxide-coated glass powder such as titanium oxide-coated glass powder and iron oxide-coated glass powder; oxide-coated metal particles such as titanium oxide-coated aluminum powder; scaly flakes such as basic lead carbonate, lead hydrogen arsenate, and bismuth oxide chloride; fish scale powder, shell fragments, and pearl fragments.

[0024] Examples of metallic pigments include pigments made of metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold powder, and silver, and alloys of these metals. The metallic pigments may be used alone or in combination of two or more.

[0025] From the viewpoint of providing excellent design effects, for example, when forming the glittering layer using gravure printing, the average particle diameter of the glittering pigment is preferably 40 μm or less, and more preferably 30 μm or less. From the same viewpoint, the ratio of [average particle diameter of glittering pigment / thickness of glittering layer] is preferably 0.01 or more and 15 or less, and more preferably 0.5 or more and 10 or less. In this specification, "average particle diameter" refers to the value that can be determined as the mass average value D50 in particle size distribution measurement using laser light diffraction method.

[0026] Examples of binder resins include thermoplastic resins and cured products of curable resin compositions, with the cured products of curable resin compositions being preferred from the viewpoint of durability. Examples of cured products of curable resin compositions include cured products of thermosetting resin compositions and cured products of ionizing radiation curable resin compositions. From the viewpoint of interlayer adhesion, the cured products of thermosetting resin compositions are preferred.

[0027] Examples of thermosetting resin compositions used in the glossy layer include polyester resin compositions, epoxy resin compositions, polyurethane resin compositions, aminoalkyd resin compositions, melamine resin compositions, guanamine resin compositions, urea resin compositions, and thermosetting acrylic resin compositions. These thermosetting resin compositions include monomers and / or prepolymers constituting each resin, and a curing agent added as needed. The ionizing radiation-curable resin composition used in the glossy layer can be the same as the ionizing radiation-curable resin composition of the surface protective layer 5 described below.

[0028] The content of the glittering pigment in the glittering layer is preferably 10 to 90 parts by mass, and more preferably 50 to 80 parts by mass, relative to 100 parts by mass of the binder resin. By setting the content of the glittering pigment to 10 parts by mass or more, it is possible to impart a sufficient glossy appearance, and by setting it to 90 parts by mass or less, it is possible to prevent impairment of the visibility of the design layer described below. From the same viewpoint, the thickness of the glittering layer is preferably 1 μm to 30 μm, and more preferably 5 μm to 20 μm.

[0029] The glittering layer can be formed into any pattern depending on the design desired. Examples include wood grain, leather, stone, sand, tile, brickwork, fabric, geometric shapes, letters, symbols, abstract patterns, floral patterns, landscapes, and characters. It is preferable that the arbitrary pattern have shading to further enhance the design effect. Shading may be formed by varying the size or thickness of the halftone dots, but it is preferable to form it by varying the density of the halftone dots (i.e., the size of the halftone dots is uniform and the shading is formed by the density of the halftone dots).

[0030] The glittering layer can be formed, for example, by applying a coating liquid containing a glittering pigment and a binder resin using a general-purpose printing method such as gravure printing. When the shade of the glittering layer is formed by the density of halftone dots, the halftone dots on the printing plate can be formed using an FM (frequency modulation) screen.

[0031] [Transparent thermoplastic resin layer] The transparent thermoplastic resin layer 4 is a resin layer that provides thickness and depth for design purposes, as well as protecting the design layer 3 and imparting good surface properties to improve the weather resistance and abrasion resistance of the decorative sheet 1. Materials that can be used for the transparent thermoplastic resin layer 4 include, for example, vinyl chloride resin, acrylic resin, and polyolefin-based resin (polypropylene resin, polyethylene resin). In particular, polyolefin-based resins are preferred in terms of environmental compatibility, processability, and cost. The grade and composition of the resin can be selected taking into consideration not only environmental compatibility, processability, and cost, but also ease of sheeting, printability, and suitability for bending. When selecting a material for bending, it is important to consider the prevention of whitening or cracking at the bent portion.

[0032] A lamination method can be used as a method for forming the transparent thermoplastic resin layer 4. Furthermore, for example, when the transparent thermoplastic resin layer 4 and an adhesive layer (not shown) are formed simultaneously, a method can be used in which they are formed by co-extrusion.

[0033] [Surface protective layer] The surface protective layer 5 is a layer that imparts surface properties such as abrasion resistance to the decorative sheet 1. The surface protective layer 5 also adjusts the surface gloss of the decorative sheet 1. The surface protective layer 5 may be a single layer or multiple layers. For example, the surface protective layer 5 may be formed by providing two layers, a first surface protective layer (not shown) and a second surface protective layer (not shown), in this order on the transparent thermoplastic resin layer 4. When providing a surface protective layer 5 consisting of a first surface protective layer (not shown) and a second surface protective layer (not shown), each layer may be applied and the coating cured using a known coating device, heat drying device, or ionizing radiation irradiation device depending on the type of curable resin.

[0034] The surface protective layer 5 is primarily composed of a curable resin. That is, it is preferable that the resin component of the surface protective layer 5 is substantially composed of a curable resin. "Substantially" refers to, for example, 80 parts by mass or more when the total resin is 100 parts by mass. The surface protective layer 5 may contain weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, etc., as needed.

[0035] Examples of materials that can be used for the surface protective layer 5 include ionizing radiation-curable resins and two-component curable urethane-based resins. The ionizing radiation-curable resins are not particularly limited. For example, transparent resins primarily composed of prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds in the molecule that can undergo polymerization and crosslinking reactions upon exposure to ionizing radiation such as infrared rays, ultraviolet rays, or electron beams can be used. These prepolymers or monomers can be used alone or in combination. Specific examples of prepolymers or monomers include compounds containing radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, and cationically polymerizable functional groups such as epoxy groups in the molecule. Polyene / thiol-based prepolymers, which are combinations of polyene and polythiol, are also preferred. Here, the term "(meth)acryloyl group" refers to an acryloyl group or a methacryloyl group.

[0036] Examples of prepolymers having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, silicone (meth)acrylate, etc. The molecular weight of these is preferably about 250 to 100,000.

[0037] Furthermore, examples of the monomer having a radically polymerizable unsaturated group include monofunctional monomers such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and phenoxyethyl(meth)acrylate. Examples of the polyfunctional monomer include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0038] Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers.

[0039] Examples of polyene-based prepolymers include those obtained by adding allyl alcohol to both ends of polyurethanes made from diols and diisocyanates, and examples of thiol-based prepolymers include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

[0040] The ionizing radiation may be, for example, electromagnetic waves or charged particles having energy sufficient to cause a curing reaction of molecules in an ionizing radiation-curable resin (composition). Examples of the curing reaction include crosslinking and curing reactions. The ultraviolet light source may be, 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, or a metal halide lamp. The wavelength of the ultraviolet light is preferably, for example, 190 nm or more and 380 nm or less. The electron beam source may be, for example, an electron beam accelerator such as a Cockcroft-Walton type, a Van de Graaf type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, or a high-frequency type. In particular, those capable of irradiating electrons having an energy of 100 keV or more and 1000 keV or less (more preferably, an electron having an energy of 100 keV or more and 300 keV or less) are preferred.

[0041] The two-component curing urethane resin is not particularly limited. For example, a resin containing a polyol component having OH groups as a base component and an isocyanate component as a curing agent component can be used. Examples of the polyol component having OH groups include acrylic polyol, polyester polyol, polyether polyol, and epoxy polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate.

[0042] [Antiviral agents] An antiviral agent may be added to the surface protective layer 5. Examples of the antiviral agent that can be used include inorganic antibacterial agents such as antibacterial zeolite, antibacterial apatite, and antibacterial zirconia, which are formed by incorporating metal ions such as silver ions, copper ions, and zinc ions into inorganic compounds such as zeolite, apatite, and zirconia. Other antiviral agents that can be used include zinc pyridinone, 2-(4-thiazolyl)-benzimidazole, 10,10-oxybisphenoxanodine, organic nitrogen-sulfur halogen compounds, and pyridine-2-thiol oxide, but silver-based antiviral agents are superior in terms of antiviral effect.

[0043] The antiviral agent may also be configured such that a silver-based material is supported on an inorganic material. This allows for the production of a decorative sheet 1 with excellent durability of the antiviral effect. The amount of the antiviral agent added to the surface protective layer 5 is preferably within a range of 0.2 parts by mass or more and 10 parts by mass or less relative to the solid content of the surface protective layer 5. When the amount of the antiviral agent added is 0.2 parts by mass or more, the antiviral agent acts effectively, improving antiviral properties. When the amount of the antiviral agent added is 10 parts by mass or less, scratch resistance is improved.

[0044] The average particle diameter (D50) of the antiviral agent is desirably 0.5 to 2 times the thickness of the surface protective layer 5. In other words, when the average particle diameter of the antiviral agent is Φ and the thickness of the surface protective layer 5 is D, it is desirably the relationship "0.5D≦Φ≦2D" holds. When the average particle diameter Φ of the antiviral agent is 0.5 to 2 times the thickness D of the surface protective layer 5, the contact area with the antiviral agent is increased and the surface area of ​​the antiviral agent itself is increased, resulting in improved antiviral properties. Furthermore, the average particle size (D50) of the antiviral agent is preferably 1 μm or more and 10 μm or less. When the average particle size (D50) of the antiviral agent is 1 μm or more, the contact area between the surface protective layer 5 and the antiviral agent is increased, resulting in good antiviral properties. When the average particle size (D50) of the antiviral agent is 10 μm or less, scratch resistance is improved.

[0045] [Embossed part] An embossed portion 5a consisting of a concave-convex pattern is formed on the surface of the surface protection layer 5 to impart a given design. Examples of concave-convex patterns include the vascular grooves of a wood grain board, the uneven surface of a stone slab (such as the cleavage plane of granite), the texture of a cloth surface, a matte finish, a sand grain, a hairline, and linear grooves. The embossed portion 5a is provided so that the concave-convex pattern is in harmony with the pattern of the pattern layer 3. This allows the decorative sheet 1 to be given a good texture close to that of actual wood or stone. The concave-convex pattern can be formed, for example, by embossing. The embossing method is not particularly limited. For example, a known sheet-fed embossing machine or rotary embossing machine can be used.

[0046] The embossed portion 5a is formed so that the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for light incident at an incident angle of 85° is 3 or more and the difference in arithmetic mean roughness Ra is 6 μm or more. More preferably, the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for light incident at an incident angle of 85° is 5 or more and the difference in arithmetic mean roughness Ra is 10 μm or more. By forming the embossed portion 5a so that the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for light incident at an incident angle of 85° is 3 or more, a visual gloss matte effect is more reliably achieved. Furthermore, by forming the embossed portion 5a so that the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a is 6 μm or more, an embossed design is also imparted to the tactile feel.

[0047] [Light absorbing part] The light-absorbing portions 6 are formed of a material that has light-absorbing properties for light of a predetermined wavelength, for example, a material that has infrared absorbing properties. As will be described in detail later, the light-absorbing portions 6 are provided to facilitate the formation of the embossed portions 5a in desired positions (positions that are in sync with the pattern on the pattern layer 3), that is, to easily impart to the decorative sheet 1 a texture similar to that of actual wood or stone. In this embodiment, the light absorbing portion 6 is formed using, for example, ink containing a material having an infrared absorbing effect. As the ink used for the light absorbing portion 6, for example, urethane-based printing ink can be used.

[0048] The color of the ink used for the light-absorbing portions 6 is not particularly limited, and a dark black ink or a colorless, transparent, or light-colored (light-colored) ink that is relatively nearly transparent can be used. The color (shade) of the ink may be selected appropriately depending on the design to be expressed, etc. Because the light-absorbing portions 6 are provided on the surface of the colored thermoplastic resin layer 2 opposite the pattern layer 3, even when the light-absorbing portions 6 are printed using dark black ink, the visual impact of the light-absorbing portions 6 on the decorative sheet 1 can be reduced, and there is no need to make the decorative sheet 1 a dark color in consideration of the visual impact of the light-absorbing portions 6, and a gloss matte design can be expressed even with a light-colored decorative sheet.

[0049] The material having infrared absorption properties in the gloss matte developing pattern portion 8 can be at least one or more of inorganic materials such as carbon black, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), lanthanum hexaboride (LaB6), cesium-doped tungsten oxide, etc. Furthermore, organic materials such as near-infrared absorbing materials, infrared absorbing materials, and phthalocyanine-based materials, as well as existing materials having infrared absorption properties, can also be used.

[0050] The light absorbing portions 6 are arranged at positions that are synchronized with the pattern of the pattern layer 3. For example, in the case of a wood grain patterned pattern layer 3, the gloss matte developing pattern portions 8 are formed at positions that overlap with the wood grain board conduit grooves of the pattern layer 3 in a planar view. Note that synchronization here means that the light absorbing portions 6 are formed at positions that overlap with the pattern of the pattern layer 3 in a planar view.

[0051] The thickness of the light absorbing parts 6 may be any thickness that can soften the transparent thermoplastic resin layer 4 and the surface protective layer 5 to an extent that allows sufficient formation of unevenness in the surface protective layer 5 during embossing, which will be described later. In order to obtain a sufficient gloss matte effect, the difference in gloss between the areas where the light absorbing parts 6 are formed and the areas where they are not formed is preferably 5 or more, i.e., the image density level is preferably 60% or more.

[0052] [Light of a specified wavelength] As described above, the light absorbing portion 6 is made of a material that has a light absorbing property for light of a predetermined wavelength. Examples of light of a predetermined wavelength include infrared light, ultraviolet light, visible light, electron beams, X-rays, and ion beams.

[0053] [Primer layer] The primer layer 7 is a base layer that improves adhesion and corrosion resistance with a substrate (not shown) to which the decorative sheet 1 is attached. The primer layer 7 is provided on the surface of the colored thermoplastic resin layer 2 opposite the pattern layer 3. The primer layer 7 is formed using, for example, polyester resin, organic additives, pigments, etc. The primer layer 7 may contain an anti-rust pigment to improve corrosion resistance. The thickness of the primer layer 7 is, for example, in the range of 1 μm to 10 μm. The primer layer is not necessarily provided.

[0054] [Method for manufacturing decorative sheet] The method for manufacturing a decorative sheet in this embodiment is a method for manufacturing a decorative sheet that has a textured top layer and that uses the areas of the top layer where the textured top layer is formed and the areas where the textured top layer is not formed to create a glossy matte appearance, by laminating a pattern layer, a transparent resin layer, and a surface protective layer as the top layer in this order on one side of a colored resin layer, and forming a light absorbing section that is in tune with the pattern of the pattern layer on the other side of the colored resin layer using a predetermined material that is more light absorbing for light of a predetermined wavelength than the colored resin layer, and irradiating the surface protective layer with light having a power of the predetermined wavelength that is stronger than the power of light of other wavelengths, and then forming the textured top layer by pressing an embossing plate into the surface protective layer, and forming the textured top layer so that the difference in gloss between the areas where the textured top layer is formed and the areas where the textured top layer is not formed is 3 or more for light incident at an incident angle of 85°, and the difference in arithmetic mean roughness Ra between the areas where the textured top layer is not formed is 6 μm or more.

[0055] An example of a method for producing a decorative sheet according to this embodiment will be described below with reference to FIG. First, a colored thermoplastic resin layer 2 is formed (FIG. 2(a)). For example, it is formed by laminating a 55 μm thick layer made of PE (polyethylene resin) or a 50 μm thick layer made of PBT (polybutylene terephthalate resin). The thickness of the colored thermoplastic resin layer 2 may be within a range of 45 μm to 130 μm.

[0056] Next, one surface of the colored thermoplastic resin layer 2 is printed using, for example, a urethane-based printing ink to form a design layer 3. Next, the light-absorbing portions 6 are printed on the surface of the colored thermoplastic resin layer 2 opposite the pattern layer 3 (FIG. 2(b)). For example, the light-absorbing portions 6 are printed using a black ink containing carbon black, which is a urethane-based printing ink, at predetermined positions that match the pattern of the pattern layer 3. Then, a primer layer 7 is formed on the colored thermoplastic resin layer 2 including the light-absorbing portions 6 by laminating, for example, a medium so as to cover the light-absorbing portions 6 (FIG. 2(c)).

[0057] Next, a transparent thermoplastic resin layer 4 is formed by laminating, for example, 80 μm of PP (polypropylene) resin using an extrusion lamination method on the surface of the design layer 3 opposite the colored thermoplastic resin layer 2 (FIG. 2(d)). Furthermore, a surface protection layer 5 containing, for example, a UV-curable acrylic resin composition as its main component is laminated on the transparent thermoplastic resin layer 4. As a result, the design layer 3, transparent thermoplastic resin layer 4, and surface protection layer 5 are laminated in this order on one surface of the colored thermoplastic resin layer 2. The thickness of the transparent thermoplastic resin layer 4 may be within a range of 35 μm to 130 μm. An adhesive layer made of an adhesive resin containing a urethane adhesive may be provided between the design layer 3 and the transparent thermoplastic resin layer 4.

[0058] Next, an after-embossing step is performed, in which the laminate in which these layers are stacked as shown in Fig. 2(d) is irradiated with infrared light (irradiation light) from the side of the surface protective layer 5 (Fig. 2(e)), and immediately after the infrared irradiation, an embossing plate 20 such as an embossing roll is pressed onto the surface of the surface protective layer 5 (Fig. 2(f)). This forms embossed portions 5a, and the decorative sheet 1 is formed (Fig. 2(g)).

[0059] The embossing plate 20 has a textured pattern in which the intervals between the projections and recesses are relatively short, such as a matte finish, and in plan view as shown in Fig. 2(g), multiple projections and recesses are included within the area of ​​the light-absorbing portion 6. Infrared irradiation is performed so that the transparent thermoplastic resin layer 4 and the surface protective layer 5 are softened by the infrared irradiation, and a textured shape that can satisfactorily express a gloss matte design can be formed when the embossing plate 20 is pressed.

[0060] The embossed portion 5a is formed so that the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for light incident at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a is 6 μm or more. Preferably, the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for light incident at an incident angle of 85° is 5 or more, and the difference in arithmetic mean roughness Ra is 10 μm or more.

[0061] Here, the light absorbing portions 6 are formed of black ink having infrared absorbing properties. Therefore, when the laminate is irradiated with infrared rays, the transparent thermoplastic resin layer 4 and the surface protective layer 5 are more likely to soften in the portions of the surface protective layer 5 that overlap with the light absorbing portions 6 in a plan view, compared to the portions that do not overlap with the light absorbing portions 6. In other words, after infrared irradiation, the transparent thermoplastic resin layer 4 and the surface protective layer 5 have portions that are more likely to soften and portions that are less likely to soften.

[0062] When the embossing plate 20 is pressed against the transparent thermoplastic resin layer 4 and the surface protective layer 5 in this state, unevenness is likely to be formed in the softened portions and is less likely to be formed in the portions that do not soften, and therefore unevenness is likely to be formed in the softened portions of the transparent thermoplastic resin layer 4 and the surface protective layer 5, i.e., in the portions that overlap with the light absorbing portions 6 in plan view. As a result, shapes with larger unevenness are likely to be formed in the positions of the transparent thermoplastic resin layer 4 and the surface protective layer 5 that overlap with the light absorbing portions 6 in plan view compared to positions that do not overlap with the light absorbing portions 6, and embossed portions 5a consisting of large uneven shapes are formed on the surface of the surface protective layer 5.

[0063] This allows the embossed portions 5a to be formed in positions that are in sync with the pattern of the pattern layer 3, meaning that, without the need for highly accurate positioning, the embossed portions 5a can be easily formed in sync with the pattern of the pattern layer 3. Therefore, it is possible to provide a decorative sheet 1 that has a texture close to the real thing, expresses good colors that are close to the real thing, and has excellent design properties.

[0064] The timing for pressing the embossing plate onto the transparent thermoplastic resin layer 4 and the surface protective layer 5 after infrared irradiation is not limited to immediately after infrared irradiation, but may be any timing that allows the plate to be pressed onto the surfaces of the transparent thermoplastic resin layer 4 and the surface protective layer 5 to selectively form an uneven shape in the parts softened by infrared irradiation.

[0065] The embossed portion 5a is formed so that the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for light incident at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a is 6 μm or more. This allows a sufficient visual gloss matte effect to be achieved, and the difference in tactile sensation between the embossed portion 5a and the portion excluding the embossed portion 5a is significant, allowing a gloss matte design to be achieved in terms of tactile sensation as well.

[0066] In addition, other processes may be included between the process of creating the surface protection layer 5 and the process of performing infrared irradiation, and the key point is that the infrared irradiation should be performed in a state where the transparent thermoplastic resin layer 4 and the surface protection layer 5 have been formed.

[0067] [Effects of this embodiment] (1) By pressing the embossing plate 20 after infrared irradiation, it is possible to impart a large uneven shape to the portion that overlaps with the light-absorbing portion 6 in a plan view. In other words, the embossed portion 5a can be easily formed in the desired position without having to perform high-precision positioning of the region where the uneven shape is to be formed. As a result, a decorative sheet with excellent design properties can be easily obtained. Furthermore, since the light absorbing portion 6 is provided in harmony with the pattern of the pattern layer 3, an embossed portion 5a can be formed in harmony with the pattern of the pattern layer 3, that is, a gloss matte effect in harmony with the pattern can be easily achieved.

[0068] (2) The embossed portion 5a is formed so that the difference in gloss between the embossed portion 5a and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a is 6 μm or more, thereby fully expressing the gloss matte design both visually and tactilely.

[0069] (3) By providing the embossed portion 5a, which is composed of a large uneven shape, a glossy matte appearance is achieved, which prevents the occurrence of pattern peeling of the glossy matte design. Therefore, for example, a glossy matte appearance can be achieved even in flooring materials. Furthermore, by using the embossed portion 5a to create a glossy matte design, the scratch resistance of the decorative sheet 1 can be improved, which means that the decorative sheet can have a longer life. Furthermore, because pattern peeling does not occur, as occurs when a gloss adjustment layer is used, good bending suitability can be obtained when the decorative member is made.

[0070] (4) In the decorative sheet 1 according to this embodiment, at least one inorganic material selected from the group consisting of carbon black, tin-doped indium oxide, antimony-doped tin oxide, lanthanum hexaboride, and cesium-doped tungsten oxide can be used as the material in the light-absorbing portion 6 that has light-absorbing properties for infrared rays. This allows the transparent thermoplastic resin layer 4 and the surface protective layer 5 to be softened more reliably by infrared irradiation in the areas overlapping with the light absorbing parts 6, and more reliably allows the areas overlapping with the light absorbing parts 6 to be strongly embossed. As a result, a decorative sheet with excellent design properties can be obtained more easily. As shown in Figure 3, the decorative sheet 1 according to the above embodiment may be attached to a base material 9, which is a base material for a decorative material, to form a decorative member 10. In the decorative member 10, the decorative sheet 1 may be provided on at least one side of the base material 9, or may be provided on both sides.

[0071] [Base material] The substrate 9 can be a wood substrate or a metal substrate. Examples of wood substrates that can be used include wood veneers, wood plywood, laminated lumber, particle board, medium-density fiberboard, and hard fiberboard. Examples of metal substrates that can be used include steel plates and aluminum plates. The substrate 9 can also be made of resins such as plastics, or composite materials thereof. That is, the substrate 9 can be a resin substrate. The substrate 9 can also be a non-combustible substrate made of, for example, non-combustible steel plates or non-combustible materials as specified in Ministry of Construction Notification No. 1400.

[0072] Thus, decorative member 10 comprises substrate 9 and decorative sheet 1 provided on at least one side of substrate 9. Substrate 9 can be any of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate. This makes it possible to provide a decorative material that has a texture closer to the real thing, has excellent design properties, and is able to prevent the pattern from coming off. [Example]

[0073] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. [Example 1] (Example 1-1) A wood grain pattern is printed using urethane printing ink on one surface of a colored thermoplastic resin layer 2 made of a 50 μm thick PBT base fabric to form a pattern layer 3. Next, light absorbing portions 6 are printed on the surface of the colored thermoplastic resin layer 2 opposite the pattern layer 3 at predetermined positions that are in harmony with the pattern of the pattern layer 3. Specifically, the light absorbing portions 6 are formed at positions that overlap with the wood grain board conduit grooves of the wood grain pattern pattern layer 3 in a plan view.

[0074] Next, a medium is laminated on the colored thermoplastic resin layer 2 containing the light-absorbing portions 6 to form a primer layer 7. Subsequently, PP (polypropylene) resin is laminated on the surface of the design layer 3 opposite the colored thermoplastic resin layer 2 using an extrusion lamination method, via an adhesive layer made of an adhesive resin containing a urethane adhesive, to form a transparent thermoplastic resin layer 4 with a thickness of 80 μm. Furthermore, a surface protective layer 5 containing a UV-curable acrylic resin composition as its main component is laminated on the transparent thermoplastic resin layer 4. As a result, the design layer 3, adhesive layer, transparent thermoplastic resin layer 4, and surface protective layer 5 are laminated in this order on one surface of the colored thermoplastic resin layer 2.

[0075] Next, an after-embossing step is carried out, in which infrared rays (irradiation light) are irradiated from the surface protective layer 5 side by heating using an IR heater, and immediately after the infrared irradiation, an embossing plate 20 with a matte pattern is pressed onto the surface of the surface protective layer 5. The embossing process was carried out so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a were 9.8 and 3.8, respectively, for incident light at an incident angle of 85°, and so that the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm. This resulted in a decorative sheet in which embossed portions 5a consisting of larger irregularities were formed in the areas of the surface protective layer 5 and the transparent thermoplastic resin layer 4 that overlap the light absorbing portions 6 in a planar view compared to the non-overlapping areas.

[0076] (Example 1-2) The decorative sheet of Example 1-2 was obtained in the same manner as in Example 1-1, except that in the manufacturing process of the decorative sheet of Example 1-1, the embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 10.5 and 7.5, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 7 μm.

[0077] (Examples 1-3) The decorative sheet of Example 1-3 was obtained in the same manner as in Example 1-1, except that in the manufacturing process of the decorative sheet of Example 1-1, the embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 11 and 6, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 7 μm.

[0078] (Examples 1-4) The decorative sheet of Example 1-4 was obtained in the same manner as in Example 1-1, except that in the manufacturing process of the decorative sheet of Example 1-1, the embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 12 and 8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 6 μm.

[0079] (Examples 1-5) The decorative sheet of Example 1-5 was obtained in the same manner as Example 1-1, except that in the manufacturing process of the decorative sheet of Example 1-1, the embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 12 and 8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 10 μm.

[0080] (Comparative Example 1-1) A decorative sheet was obtained in the same manner as in Example 1-1, except that the post-embossing step was not performed. That is, a picture layer 3 was formed on one side of a colored thermoplastic resin layer 2, and then a light-absorbing portion 6 and a primer layer 7 were formed on the other side. After that, a transparent thermoplastic resin layer 4 and a surface protective layer 5 were laminated in this order via an adhesive layer on the side of the picture layer 3 opposite the light-absorbing portion 6, and this laminate was obtained as the decorative sheet of Comparative Example 1-1 (a decorative sheet without an embossed portion).

[0081] (Comparative Example 1-2) A decorative sheet was obtained in the same manner as in Example 1-1, except that no after-embossing step was performed and a gloss-adjusting layer was provided on the surface of the surface protective layer opposite the transparent thermoplastic resin layer. That is, a picture layer 3 was formed on one surface of a colored thermoplastic resin layer 2, and then a light-absorbing portion 6 and a primer layer 7 were formed on the other surface. After that, a transparent thermoplastic resin layer 4 and a surface protective layer 5 were laminated in this order via an adhesive layer on the surface of the picture layer 3 opposite the light-absorbing portion 6. Furthermore, a gloss-adjusting layer made of, for example, an acrylic resin was provided on the surface of this surface protective layer 5 opposite the transparent thermoplastic resin layer 4 in a position that overlaps with the light-absorbing portion 6 in a planar view.

[0082] (Comparative Examples 1-3) In the manufacturing process of the decorative sheet of Example 1-1, the embossing was performed so that the gloss of the embossed portion 5a and the portion excluding the embossed portion 5a at an incident light angle of 85° was 11.5 and 9.5, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 7 μm. The decorative sheet of Comparative Example 1-3 was obtained in the same manner as in Example 1-1, except that the embossing was performed so that the gloss of the embossed portion 5a and the portion excluding the embossed portion 5a at an incident light angle of 85° was 11.5 and 9.5, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 7 μm.

[0083] (Comparative Examples 1-4) In the manufacturing process of the decorative sheet of Example 1-1, the embossing was performed so that the gloss of the embossed portion 5a and the portion excluding the embossed portion 5a at an incident light angle of 85° was 10.5 and 7.5, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 5 μm. The decorative sheet of Comparative Example 1-4 was obtained in the same manner as in Example 1-1, except that the embossing was performed so that the gloss of the embossed portion 5a and the portion excluding the embossed portion 5a at an incident light angle of 85° was 10.5 and 7.5, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 5 μm.

[0084] 〔evaluation〕 For each of the decorative sheets of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4, the gloss and arithmetic mean roughness Ra at an incident angle of 85° were measured for the embossed portion and the portion excluding the embossed portion, and the difference in gloss and arithmetic mean roughness between the embossed portion and the portion excluding the embossed portion was determined to evaluate the gloss matte design (sensory evaluation) and the texture of the duct portion.

[0085] In Examples 1-1 to 1-5, the portions of the resulting decorative sheet that overlap with the light-absorbing portions in a planar view were evaluated as gloss portions and vessel portions, and the portions that do not overlap with the light-absorbing portions were evaluated as matte portions and non-vessel portions. In Comparative Example 1-1, the portions of the resulting decorative sheet with a wood grain vessel pattern were evaluated as vessel portions, and the other portions were evaluated as non-vessel portions. In Comparative Example 1-2, the portions of the resulting decorative sheet with the gloss adjustment layer were evaluated as gloss portions and vessel portions, and the portions excluding the gloss adjustment layer were evaluated as matte portions and non-vessel portions. In Comparative Examples 1-3 and 1-4, the portions of the resulting decorative sheet that overlap with the light-absorbing portions in a planar view were evaluated as gloss portions and vessel portions, and the portions that do not overlap with the light-absorbing portions were evaluated as matte portions and non-vessel portions.

[0086] [Measurement of Glossiness] For the decorative sheets of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4, gloss measurements were performed at an incident angle of 85° for the portions of the surface protective layer that overlap with the light absorbing portions in plan view (gloss portions) and the portions that do not overlap (matte portions) using a micro-TRI-gloss manufactured by BYK Co. The difference between the glossiness of the portions that overlap with the light absorbing portions in plan view and the glossiness of the portions that do not overlap was then determined.

[0087] [Gloss Matte Design (Sensory Evaluation)] The decorative sheets of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 were evaluated for gloss / matt feeling by visual inspection, gloss difference, and tactile sensation. The evaluation criteria were as follows. ◎◎: The difference in glossiness between the portion of the surface protective layer that overlaps with the light absorbing portion in plan view (gloss portion) and the portion that does not overlap with the light absorbing portion (matte portion) is greater than "5", and the gloss matte design is manifested to the extent that the difference between the portion that overlaps with the light absorbing portion in plan view and the portion that does not overlap with the light absorbing portion can be recognized when touched, and the difference between the gloss portion and the matte portion can be recognized. ⊚: The gloss difference is greater than "3", and even if misalignment occurs between the light-absorbing portion and the embossed portion during the manufacturing process, a stable gloss matte is achieved. ◯: The gloss difference is greater than "3", and gloss matte is exhibited. ×: It is not possible to visually confirm whether gloss matt has appeared or not.

[0088] [Tactile sensation of the conduit] ⊚: The difference in feel between the ductal and non-ductal parts is noticeable. ○: The difference in texture between the ductal and non-ductal parts can be felt to some extent. ×: No difference in feel between the ductal part and the non-ductal part can be felt.

[0089] [Measurement of arithmetic mean roughness Ra] The arithmetic mean roughness Ra, as defined in JIS B 0601, was measured for the portions of the surface protective layer that overlap with the light-absorbing portion in a planar view (conduit portions) and the portions that do not overlap with the light-absorbing portion (non-conduit portions) using a small surface roughness measuring instrument, Surftest SJ-410, manufactured by Mitutoyo Corporation. The arithmetic mean roughness Ra was calculated by subtracting the arithmetic mean roughness Ra of the non-conduit portions from the arithmetic mean roughness Ra of the conduit portions. The measurement results and evaluation results are shown in Table 1.

[0090] [Table 1]

[0091] 〔result〕 In the decorative sheets of Examples 1-1 to 1-5, the difference in gloss between the glossy portion and the matte portion for incident light at an incident angle of 85° was "3" or more, and the difference in arithmetic mean roughness Ra was 6 μm or more, and both the difference in gloss and the difference in arithmetic mean roughness Ra were sufficient. In this case, the glossy matte design and the tactile feel of the duct portion were both good, and the glossy matte design could be expressed both visually and tactilely.

[0092] In contrast, in the decorative sheet of Example 1-1, the decorative sheet of Comparative Example 1-1, which is a decorative sheet consisting of a laminate obtained by performing a process of forming a laminate in which the primer layer 7, light absorbing portion 6, colored thermoplastic resin layer 2, design layer 3, transparent thermoplastic resin layer 4, and surface protective layer 5 are laminated, has a difference in gloss between the gloss portion and the matte portion for incident light at an incident angle of 85° of 2.2, and because no embossing plate was used, the difference in arithmetic mean roughness Ra was zero. Furthermore, the gloss / matt design could not be confirmed visually or tactilely, and the duct portions could not be felt tactilely.

[0093] In addition, the decorative sheet of Comparative Example 1-2, which had a gloss adjustment layer on the side opposite the transparent thermoplastic resin layer of the surface protection layer in the decorative sheet of Comparative Example 1-1, had a difference in gloss between the gloss and matte parts for incident light at an angle of 85° of 6.6, which is a sufficient difference in gloss to produce a visually good gloss matte design, but the difference in arithmetic mean roughness Ra was zero, and the duct parts could not be felt by touch.

[0094] Furthermore, the decorative sheet of Comparative Example 1-3 had a difference in glossiness between the glossy and matte portions for light incident at an angle of 85° of "2", meaning that it was not possible to produce a visually favorable gloss matte design, but the difference in arithmetic mean roughness Ra was 7 μm, meaning that the duct parts could be felt to the touch.The decorative sheet of Comparative Example 1-4 had a difference in glossiness between the glossy and matte portions for light incident at an angle of 85° of "3", meaning that it was possible to produce a visually favorable gloss matte design, but the difference in arithmetic mean roughness Ra was 5 μm, meaning that the duct parts could not be felt to the touch.

[0095] [Example 2] The effect of adding an antiviral agent will be explained by showing examples, but the present invention is not limited to the following examples. Example 2-1 In the decorative sheet shown in Example 1-1, 0.2 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=1D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0096] (Example 2-2) In the decorative sheet shown in Example 1-1, 0.2 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 10 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=0.5D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0097] (Example 2-3) In the decorative sheet shown in Example 1-1, 0.2 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 2.5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=2D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0098] (Examples 2-4) In the decorative sheet shown in Example 1-1, 10 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=1D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0099] (Examples 2-5) In the decorative sheet shown in Example 1-1, 0.1 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=1D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0100] (Examples 2-6) In the decorative sheet shown in Example 1-1, 11 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=1D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0101] (Examples 2-7) In the decorative sheet shown in Example 1-1, 0.2 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 1 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ was Φ=0.2D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0102] (Examples 2-8) In the decorative sheet shown in Example 1-1, 0.2 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 13 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, was Φ=2.6D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0103] (Examples 2-9) In the decorative sheet shown in Example 1-1, 0.2 parts by mass of silver-based zeolite was added as a silver-based inorganic antibacterial agent to the surface protective layer 5. The thickness of the surface protective layer 5 was 5 μm, the average particle diameter (D50) of the antiviral agent (silver-based zeolite) was 1.5 μm, and the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, i.e., the relationship between the thickness D of the surface protective layer 5 and the average particle diameter Φ, was Φ=0.3D. Then, as in Example 1-1, embossing was performed so that the gloss of the embossed portion 5a of the decorative sheet and the portion excluding the embossed portion 5a for incident light at an incident angle of 85° were 9.8 and 3.8, respectively, and the difference in arithmetic mean roughness Ra between the embossed portion 5a and the portion excluding the embossed portion 5a was 12.3 μm.

[0104] 〔evaluation〕 The decorative sheets of Examples 2-1 to 2-9 were each evaluated for antiviral performance and scratch resistance. (Antiviral performance) Antiviral tests were conducted in accordance with ISO 21702. A 50mm square test sample was placed in a sterile dish, and 0.4mL of virus solution was inoculated onto the sample. The virus solution used contained an enveloped virus (influenza virus). The sample was then covered with a 40mm square piece of polyethylene film. After the dish was covered, the sample and virus were inoculated under conditions of 25°C and 90% humidity or higher. After the specified time (24 hours), 10mL of SCDLP medium was poured into the dish to wash out the virus. The virus infectivity of the washed-out solution was measured using the plaque method.

[0105] [Measurement of virus infectivity (plaque method)] Host cells were cultured in monolayer on a 6-well plate, and 0.1 mL of serially diluted washout solution was inoculated into each well. After incubation for 1 hour at 37°C in 5% CO2, the virus was allowed to adsorb to the cells. After that, agar medium was poured into the 6-well plate and incubated for an additional 2-3 days. After incubation, the cells were fixed and stained, and the number of plaques formed was counted.

[0106] [Calculation of virus infectivity] According to the following formula, 1cm of sample 2 The virus infectivity per 1000 cells was calculated. V = (10 × C × D × N) / A V: 1cm sample 2 Viral infectivity per (PFU / cm 2 ) C: Number of plaques measured D: Dilution ratio of the well in which the plaques were counted N: SCDLP amount A: Contact area between sample and virus (area of ​​polyethylene film)

[0107] [Calculation of antiviral activity value] The antiviral activity value was calculated according to the following formula: Here, when the antiviral activity value was 2 log10 or more, it was determined that there was an antiviral effect. Antiviral activity value = log(Vb) - log(Vc) Log(Vb): 1cm of unprocessed sample after 24 hours 2 Common logarithm of viral infectivity per Log(Vc): 1cm of antiviral treated sample after 24 hours 2 Common logarithm of viral infectivity per The calculated antiviral activity values ​​were evaluated using the following three levels: "◎", "〇", and "×".

[0108] [Evaluation criteria] ◎: Antiviral activity value is 3 log10 or higher ○: Antiviral activity value is 2 log10 or higher ×: Antiviral activity value is less than 2 log10 (Scratch resistance) A pencil hardness test was conducted on the decorative sheets 1 of Examples 2-1 to 2-9 that were produced. Specifically, the decorative sheets of Examples 2-1 to 2-9 were placed in a pencil hardness tester specified in JIS K 5600, the state of scratches was checked, and the pencil hardness was measured. The pencil hardness was evaluated using the following three levels: "◎", "◯", and "×". The pencil hardness was measured and evaluated using a decorative floor material in which the decorative sheets of Examples 2-1 to 2-9 that were produced were bonded to a 3 mm thick MDF (Medium Density Fiberboard) (hardwood type) as a substrate 9.

[0109] [Evaluation criteria] ◎: Pencil hardness is 3H or higher ○: Pencil hardness is 2H to H ×: Pencil hardness is less than H The evaluation results are shown in Table 2.

[0110] [Table 2]

[0111] 〔result〕 Examples 2-1 to 2-4, in which the amount of antiviral agent added was within the range of 0.2 parts by mass or more and 10 parts by mass or less, the average particle diameter (D50) of the antiviral agent was 1 μm or more and 10 μm or less, and the average particle diameter (D50) of the antiviral agent was 0.5 to 2 times the thickness of surface protective layer 5, were evaluated as "◎" or "◯" in both the pencil hardness test and the antiviral property test, confirming that good antiviral property and scratch resistance were obtained. On the other hand, when the amount of antiviral agent added was less than 0.2 parts by mass or more than 10 parts by mass, or the average particle diameter (D50) of the antiviral agent was less than 1 μm or more than 10 μm, or the average particle diameter (D50) of the antiviral agent was less than 0.5 times or more than 2 times the thickness of surface protective layer 5, the evaluation result was "×" in either the pencil hardness test or the antiviral property test. It should be noted that, as can be seen from Table 2, it was confirmed that an antiviral effect was obtained against influenza virus, and similar evaluation confirmed that an antiviral effect was also obtained against feline calicivirus.

[0112] The present invention can have the following configurations, for example. (1) A decorative sheet having an uneven surface on the outermost layer, which exhibits a glossy matte appearance by utilizing an area of ​​the outermost layer where the uneven surface is formed and an area where the uneven surface is not formed, A decorative sheet characterized in that the difference in gloss between the area where the uneven shape is formed and the area where the uneven shape is not formed for incident light at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between the area where the uneven shape is formed and the area where the uneven shape is not formed is 6 μm or more.

[0113] (2) The decorative sheet according to (1) above, wherein the difference in glossiness for incident light at an incident angle of 85° is 5 or more.

[0114] (3) The decorative sheet according to (1) or (2) above, wherein the difference in the arithmetic mean roughness Ra is 10 μm or more.

[0115] (4) a pattern layer, a transparent resin layer, a surface protection layer as the outermost layer, and a light absorbing portion laminated on the other surface of the colored resin layer, the light absorbing portion being made of a predetermined material that is more light absorbing than the colored resin layer for light of a predetermined wavelength, and being positioned in sync with the pattern of the pattern layer; The decorative sheet according to any one of (1) to (3) above, wherein the uneven shape is formed in a position of the surface protective layer that overlaps with the light absorbing portion in a plan view.

[0116] (5) The decorative sheet according to (4) above, wherein the predetermined material is a material that is light-absorbent to infrared rays.

[0117] (6) The decorative sheet according to (4) above, wherein the predetermined material is at least one inorganic material selected from the group consisting of carbon black, tin-doped indium oxide, antimony-doped tin oxide, lanthanum hexaboride, and cesium-doped tungsten oxide.

[0118] (7) A substrate; The decorative sheet according to any one of (1) to (6) above is provided on at least one surface of the substrate, The decorative member is characterized in that the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

[0119] (8) A method for producing a decorative sheet having an uneven surface on the outermost layer, which exhibits a glossy matte appearance by utilizing an area of ​​the outermost layer where the uneven surface is formed and an area where the uneven surface is not formed, a pattern layer, a transparent resin layer, and a surface protective layer as the outermost layer are laminated in this order on one surface of a colored resin layer; a light absorbing portion that is synchronized with the pattern of the pattern layer is formed on the other surface of the colored resin layer using a predetermined material that is more light absorbing than the colored resin layer for light of a predetermined wavelength; and after irradiating the surface protective layer with light having a power of the predetermined wavelength that is stronger than the power of light of other wavelengths, an embossing plate is pressed onto the surface protective layer to form the uneven shape; A method for manufacturing a decorative sheet, characterized in that the area where the uneven shape is formed and the area where the uneven shape is not formed are formed so that the difference in glossiness for incident light at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between them is 6 μm or more. [Explanation of symbols]

[0120] 1 decorative sheet 2 Colored thermoplastic resin layer 3. Picture layer 4 Transparent thermoplastic resin layer 5 Surface protective layer 5a Embossed part 6 Light absorbing part 7 Primer layer

Claims

1. A decorative sheet having an uneven surface on the outermost layer, which exhibits a glossy matte appearance by utilizing an area where the uneven surface is formed and an area where the uneven surface is not formed, A decorative sheet characterized in that the difference in gloss between the area where the uneven shape is formed and the area where the uneven shape is not formed for incident light at an incident angle of 85° is 3 or more, and the difference in arithmetic mean roughness Ra between the area where the uneven shape is formed and the area where the uneven shape is not formed is 6 μm or more.

2. 2. The decorative sheet according to claim 1, wherein the difference in gloss level for incident light at an incident angle of 85° is 5 or more.

3. 3. The decorative sheet according to claim 1, wherein the difference in arithmetic mean roughness Ra is 10 μm or more.

4. a pattern layer, a transparent resin layer, a surface protection layer as the outermost layer, and a light absorbing portion laminated on the other surface of the colored resin layer, the light absorbing portion being made of a predetermined material that is more light absorbing than the colored resin layer for light of a predetermined wavelength, and being positioned in sync with the pattern of the pattern layer; 3. The decorative sheet according to claim 1, wherein the unevenness is formed in a position of the surface protective layer that overlaps with the light absorbing portion in a plan view.

5. 5. The decorative sheet according to claim 4, wherein the predetermined material is a material that is light-absorbent with respect to infrared rays.

6. 5. The decorative sheet according to claim 4, wherein the predetermined material is at least one inorganic material selected from the group consisting of carbon black, tin-doped indium oxide, antimony-doped tin oxide, lanthanum hexaboride, and cesium-doped tungsten oxide.

7. A substrate; The decorative sheet according to claim 1 or 2 is provided on at least one surface of the substrate, The decorative member is characterized in that the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

8. A method for producing a decorative sheet having an uneven surface on the outermost layer, which exhibits a glossy matte appearance by utilizing an area of ​​the outermost layer where the uneven surface is formed and an area where the uneven surface is not formed, a pattern layer, a transparent resin layer, and a surface protective layer as the outermost layer are laminated in this order on one surface of a colored resin layer; a light absorbing portion that is synchronized with the pattern of the pattern layer is formed on the other surface of the colored resin layer using a predetermined material that is more light absorbing than the colored resin layer for light of a predetermined wavelength; and after irradiating the surface protective layer with light having a power of the predetermined wavelength that is stronger than the power of light of other wavelengths, an embossing plate is pressed onto the surface protective layer to form the uneven shape; A method for manufacturing a decorative sheet, characterized in that the area where the uneven shape is formed and the area where the uneven shape is not formed have a difference in gloss level for incident light at an incident angle of 85° of 3 or more, and are formed so that the difference in arithmetic mean roughness Ra between them is 6 μm or more.

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