Decorative sheet and decorative material

Abstract

To provide a decorative sheet having a touch close to wood not only in appearance but also in touch.SOLUTION: The decorative sheet 51 includes a primary film layer 10, a pattern layer 20 formed on the primary film layer, an adhesive layer 41 formed on the pattern layer, a transparent resin layer 42 formed on the adhesive layer, and a surface protective layer 30 formed on the transparent resin layer. The surface-protecting layer has a ridge-like raised side 30a on the front side, a load length ratio Rmr (10%) at a cut level of 10% of the front side of 0.05 or more and 0.35 or less, a root mean square slope Rdq of the front side of 0.15 or more and 0.4 or less, and a root mean square height Rq of the front side of 0.4 μm or more and 4.0 μm or less.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet and also to a decorative material to which the decorative sheet is attached. [Background technology]

[0002] Decorative sheets used to decorate residential interior materials and the like are widely known (see, for example, Patent Document 1). A major role of decorative sheets is to impart a wood grain appearance, but printing techniques for wood grain patterns are improving day by day, and the appearance has reached a level where it is difficult for users to distinguish the wood grain pattern from real wood. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2024-32536 Summary of the Invention [Problem to be solved by the invention]

[0004] In wood grain pattern decorative sheets, including the one described in Patent Document 1, the texture is made to resemble wood by providing the surface with irregularities that match the surface shape of wood using embossing or the like. However, because the substrate to which the decorative sheet is attached is not wood, simply making the surface irregularities the same does not result in the same texture, and this can cause an unnatural feeling. The inventors have conducted extensive research into this point and have completed the present invention.

[0005] An object of the present invention is to provide a decorative sheet that has a texture similar to that of wood, not only in appearance but also in feel. [Means for solving the problem]

[0006] A first aspect of the present invention is a decorative sheet comprising a base fabric layer, a pattern layer formed on the base fabric layer, an adhesive layer formed on the pattern layer, a transparent resin layer formed on the adhesive layer, and a surface protection layer formed on the transparent resin layer. The surface protective layer has ridge-like protrusions on its surface, and the load length ratio Rmr(10%) at a cutting level of 10% on the surface is 0.05 or more and 0.35 or less, the root mean square slope Rdq of the surface is 0.15 or more and 0.4 or less, and the root mean square height Rq of the surface is 0.4 μm or more and 4.0 μm or less.

[0007] Another decorative sheet according to the first embodiment comprises a base layer, a design layer formed on the base layer, and a surface protective layer formed on the design layer. The surface protective layer has ridge-like protrusions on its surface, and the load length ratio Rmr(10%) at a cutting level of 10% on the surface is 0.05 or more and 0.35 or less, the root mean square slope Rdq of the surface is 0.15 or more and 0.4 or less, and the root mean square height Rq of the surface is 0.4 μm or more and 4.0 μm or less.

[0008] A second aspect of the present invention is a decorative material comprising the decorative sheet according to the first aspect and a substrate to which the decorative sheet is bonded. This decorative material has a primer layer between the decorative sheet and the substrate. [Effects of the Invention]

[0009] According to the present invention, a decorative sheet can be provided that has a texture similar to that of wood, as well as an appearance similar to that of wood. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing a decorative sheet according to a first embodiment of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view showing a decorative material using the decorative sheet. [Figure 3] FIG. 2 is a schematic cross-sectional view showing a decorative sheet according to a second embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] A first embodiment of the present invention will be described with reference to Fig. 1. The decorative sheet according to this embodiment is attached to the surface of a substrate such as a wood board, an inorganic board, or a metal plate, and imparts a desired appearance to the surface of the substrate.

[0012] As shown in Fig. 1, the decorative sheet 1 comprises a raw fabric layer 10, a design layer 20, and a surface protective layer 30. The raw fabric layer 10 may be colored or may be transparent.

[0013] The raw fabric layer 10 can be made of any material selected from the group consisting of paper, synthetic resin, synthetic resin foam, rubber, nonwoven fabric, synthetic paper, and metal foil. Examples of paper include tissue paper, titanium dioxide paper, and resin-impregnated paper. Examples of synthetic resin include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic. Examples of rubber include ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane. Examples of nonwoven fabric include organic and inorganic nonwoven fabrics. Examples of metals for the metal foil include aluminum, iron, gold, and silver. The thickness of the raw fabric layer 10 is preferably within the range of 20 μm to 250 μm, taking into consideration the ease of printing and costs.

[0014] The raw fabric layer 10 according to this embodiment has a configuration in which skin layers 12 are provided on both sides of a core layer 11 in the thickness direction. The materials described above can be used for the core layer 11. The skin layer 12 contains a resin material and a nucleating agent or an inorganic material. The above is merely one embodiment, and it goes without saying that the raw fabric layer 10 may have a single layer structure without a skin layer.

[0015] The skin layer 12 will be described in detail below. The resin material is, for example, a thermoplastic resin. There are no particular limitations on the thermoplastic resin, and the same resin material as that of the base layer 12A can be used.

[0016] The nucleating agent can be nano-sized, and is preferably added to the polypropylene resin in the form of a nucleating agent vesicle encapsulated in a vesicle having a single-layer outer membrane. The nucleating agent may be encapsulated in the vesicle with a portion exposed. By including a nucleating agent in the skin layer 12, the crystallinity of the skin layer is improved, thereby improving the scratch resistance (scratch resistance) of the decorative sheet 1. The average particle size of the nucleating agent is preferably 1 / 2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is 400 nm or more and 750 nm or less, the average particle size is preferably 375 nm or less.

[0017] Because nano-sized nucleating agents have extremely small particle sizes, the number of nucleating agents present per unit volume and their surface area increase inversely proportional to the cube of the particle diameter. As a result, the distance between nucleating agent particles becomes shorter. When crystal growth occurs from the surface of one nucleating agent particle added to a resin, the end of the growing crystal immediately comes into contact with the end of a crystal growing from the surface of another nucleating agent particle adjacent to the first nucleating agent particle. The ends of the crystals inhibit each other's growth, halting the growth of each crystal. This allows the average particle size of spherulites in the crystalline portion of a crystalline resin to be reduced, for example, to 1 μm or less. This results in a resin film with high crystallinity and high hardness. Furthermore, the stress concentration between spherulites that occurs during bending is efficiently dispersed, resulting in a resin film that is less susceptible to cracking and whitening during bending.

[0018] When a nucleating agent is simply added, the particle size increases due to secondary aggregation of the nucleating agent in the resin. On the other hand, when nucleating agent vesicles are added, the dispersion in the resin improves, resulting in a significant increase in the number of crystal nuclei per amount of nucleating agent added compared to when a nucleating agent is simply added. This reduces the average particle size of spherulites in the crystalline portion of the resin, suppressing cracking and whitening during bending. Therefore, adding nucleating agent vesicles can further increase the degree of crystallinity, achieving both improved modulus and higher levels of processability.

[0019] When a nucleating agent is used, the skin layer can be configured, for example, by adding the nucleating agent in an amount preferably ranging from 0.05 to 0.5 parts by mass, more preferably from 0.1 to 0.3 parts by mass, per 100 parts by mass of polypropylene resin as the main component. When nucleating agent vesicles are used, the amount of nucleating agent added to the resin material is the amount converted to the nucleating agent in the nucleating agent vesicles. If the amount of nucleating agent added is less than 0.05 parts by mass, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the skin layer may not be sufficiently improved. Furthermore, if the amount of nucleating agent added is more than 0.5 parts by mass, the crystalline nuclei of the polypropylene may be excessive, inhibiting the growth of spherulites of the polypropylene. As a result, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the skin layer may not be sufficiently improved.

[0020] Techniques for nano-sizing nucleating agents include, for example, solid-phase methods, which involve mechanically grinding the nucleating agent to obtain nano-sized particles; liquid-phase methods, which involve synthesizing or crystallizing nano-sized particles in a solution containing the nucleating agent; and gas-phase methods, which involve synthesizing or crystallizing nano-sized particles from a gas or vapor containing the nucleating agent. Examples of solid-phase methods include ball mills, bead mills, rod mills, colloid mills, conical mills, disk mills, hammer mills, and jet mills. Examples of liquid-phase methods include crystallization, coprecipitation, sol-gel processes, liquid-phase reduction, and hydrothermal synthesis. Examples of gas-phase methods include electric furnace processes, chemical flame processes, laser processes, and thermal plasma processes.

[0021] Among nano-sizing techniques, supercritical reverse-phase evaporation is preferred. Supercritical reverse-phase evaporation is a method for producing capsules (nano-sized vesicles) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Supercritical carbon dioxide refers to carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa). Carbon dioxide under temperature or pressure conditions above the critical point refers to carbon dioxide under conditions where only the temperature or pressure exceeds the critical conditions.

[0022] In a specific nano-process using supercritical reverse-phase evaporation, an aqueous phase is first injected into a mixture of supercritical carbon dioxide, phospholipids as an outer membrane-forming substance, and a nucleating agent as an encapsulating substance, and the mixture is stirred to generate an emulsion of supercritical carbon dioxide and aqueous phase. Next, the pressure is reduced, causing the carbon dioxide to expand and evaporate, resulting in a phase inversion, producing nanocapsules (nanovesicles) in which the phospholipids cover the surface of the nucleating agent particles with a single-layer membrane. Unlike conventional encapsulation methods, in which the outer membrane on the surface of the nucleating agent particles becomes multi-layered, this supercritical reverse-phase evaporation method makes it easy to produce capsules with a single membrane, allowing for the preparation of smaller capsules. Nucleating agent vesicles can be prepared by, for example, the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, etc. Among these, it is particularly preferable to prepare nucleating agent vesicles using supercritical reverse phase evaporation method.

[0023] The outer membrane constituting the nucleating agent vesicle is composed of, for example, a monolayer membrane, and the outer membrane is composed of a substance containing, for example, a biological lipid such as a phospholipid. Nucleating vesicles whose outer membrane is composed of materials containing biological lipids such as phospholipids are referred to herein as nucleating liposomes. Examples of phospholipids constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0024] Other substances that form the outer membrane of the vesicles include dispersants such as nonionic surfactants and mixtures of these with cholesterols or triacylglycerols. Among these, nonionic surfactants can be used alone or in combination with one or more of the following: polyglycerol 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-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. Cholesterols that can be used include, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, and cholecalciferol.

[0025] The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In this embodiment, the nucleating agent vesicle is preferably a radical scavenger liposome having an outer membrane made of a phospholipid. The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes. Examples of nucleating agents include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts, which are non-melting and expected to have good transparency. However, if the material itself can be made transparent by the nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. Furthermore, a non-melting nucleating agent may be appropriately mixed with melting benzylidene sorbitol.

[0026] When an inorganic material is used instead of a nucleating agent, various inorganic fine particles made of inorganic materials such as nano-sized silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate can be used as the inorganic particles. The amount of the inorganic material can be, for example, in the range of 0.05 parts by mass to 0.5 parts by mass relative to 100 parts by mass of the resin material.

[0027] When the skin layer 12 is provided, it is not necessarily required to provide it on both sides of the core layer 11, and it may be provided only on the pattern layer 20 side.

[0028] The design layer 20 has a background color and a pattern that constitute the design of the decorative sheet 1. The design layer 20 is formed using printing ink. Examples of binders for the ink include soluble nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyesters, and modified products thereof, which can be used alone or in combination. The binder may be water-based, solvent-based, or emulsion-based, and may be a one-component type or a two-component type that uses a curing agent. The design layer 20 may be formed by curing a layer formed with a curable ink by irradiation with ultraviolet light, electron beams, or the like. The most common method is to use a urethane-based ink that is cured with an isocyanate. The ink used to form the design layer 20 may further contain, in addition to the binder, pigments, colorants such as dyes, extender pigments, solvents, and various additives that are commonly found in inks. Examples of versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

[0029] Since the decorative sheet 1 creates a tactile sensation similar to the warmth of wood, the pattern of the pattern layer 20 is appropriately selected from various wood grain patterns. Using this as a base, it is also possible to apply a design to the pattern layer 20 by vapor deposition or sputtering of various metals. It is preferable that a light stabilizer be added to the ink, which can suppress deterioration of the decorative sheet 1 itself caused by light degradation of the ink, and extend the life of the decorative sheet 1.

[0030] The surface protection layer 30 has an uneven surface consisting of multiple ridge-like ridges 30a, where "ridge-like" means a linear convex shape in a planar view. The shape of the ridges cannot be controlled, as will become clear during the manufacturing process described below, but they may be curved or linear, and are usually curved. Curved ridges are also preferred from the standpoint of fingerprint resistance. The ridges may or may not be branched in a planar view of the decorative sheet.

[0031] The inventors created and prototyped various embossed plates with surface shapes that would create a tactile sensation similar to the warmth of wood, but found it difficult to achieve this.However, by creating an uneven shape consisting of ridge-like protrusions of a specific pattern, they succeeded in consistently creating a tactile sensation similar to the warmth of wood.

[0032] Specifically, the surface of the surface protection layer 30 according to this embodiment has a load length ratio Rmr(10%) of 0.05 or more and 0.35 or less at a cut level of 10%. The load length ratio Rmr(10%) is preferably 0.1 or more and 0.3 or less, and more preferably 0.15 or more and 0.25 or less. The smaller the load length ratio Rmr(10%), the steeper the slope near the top of the convex portions, and therefore the amount of contact between the user's finger and the convex portions when touching the concave-convex structure with their finger is reduced, making it more difficult for the user's heat to be transferred to the decorative sheet, and increasing the sense of warmth felt by the user.

[0033] The load length ratio Rmr(10%) is the ratio of the load length of the roughness curve at a 10% cut level to the evaluation length. The 10% cut level is the level where the depth distance from the highest point on the roughness curve is 10% of the maximum cross-sectional height Rt. When a user lightly touches a textured structure with their finger, the finger touches a part of the textured structure that is approximately 10% of the height of the convex part from the highest point of the convex part. Therefore, the load length ratio Rmr(10%) correlates with the amount of contact between the finger and the convex part when the user lightly touches the textured structure with their finger. The load length ratio Rmr(10%) and the maximum cross-sectional height Rt are surface texture parameters specified in JIS B0601:2013.

[0034] The load length ratio Rmr (10%) is expressed by the following formula (1).

[0035]

number

[0036] In equation (1), ln is the evaluation length, and Ml(10%) is the load length of the roughness curve at the cutting level of 10%.

[0037] The uneven structure of the surface protection layer 30 has a root mean square slope Rdq of 0.15 or more and 0.4 or less, preferably 0.2 or more and 0.35 or less, and more preferably 0.25 or more and 0.3 or less.

[0038] The root mean square slope Rdq is the root mean square of the local slope of a roughness curve over a reference length. The root mean square slope Rdq is a parameter that can be used to evaluate the magnitude of the local slope angle. Specifically, the root mean square slope Rdq quantifies the steepness of the convex or concave portions contained in the uneven structure. The root mean square slope Rdq is a surface texture parameter specified in JIS B0601:2013.

[0039] The root mean square slope Rdq is expressed by the following equation (2).

[0040]

number

[0041] In equation (2), l is the sampling length and dZ(x) / dx is the local slope of the roughness curve.

[0042] The uneven structure on the surface of the surface protection layer 30 has a root mean square height Rq of 0.4 μm or more and 4.0 μm or less, preferably 1.0 μm or more and 3.5 μm or less, and more preferably 1.5 μm or more and 3.0 μm or less.

[0043] The root mean square height Rq is the root mean square of the ordinate value Z(x) of the roughness curve over the reference length l. The root mean square height Rq is a parameter that can be used to evaluate the height-direction size of the convex or concave portions contained in the uneven structure. The root mean square height Rq is a surface texture parameter specified in JIS B0601:2013.

[0044] The root mean square height Rq is expressed by the following formula (3).

[0045]

number

[0046] In equation (3), l is the reference length and Z(x) is the ordinate value of the roughness curve.

[0047] The surface protection layer 30 is preferably made of a cured product of an ionizing radiation curable resin. Here, "ionizing radiation" refers to a charged particle beam such as an electron beam. The ionizing radiation curable resin is cured by irradiation with ionizing radiation. The ionizing radiation curable resin can also be cured by ultraviolet light. The ionizing radiation curable resin used here is cured by irradiation with light having a wavelength of 200 nm or less, and has a high absorption coefficient for this light.

[0048] The ionizing radiation curable resin may be any known resin, such as various monomers or commercially available oligomers, including (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. The ionizing radiation curable resin may be either an aqueous resin or a non-aqueous (organic solvent-based) resin.

[0049] The main component of the ionizing radiation curable resin is preferably an acrylate. Here, the main component of the ionizing radiation curable resin means a component that accounts for 60 mass% or more of the ionizing radiation curable resin. The ionizing radiation curable resin preferably contains 70 mass parts or more of acrylate, more preferably 80 mass parts or more. The ionizing radiation curable resin is more preferably an acrylate.

[0050] The acrylate is preferably a difunctional or higher acrylate, more preferably a trifunctional or higher acrylate. In order to obtain a surface protective layer with excellent scratch resistance, the acrylate is preferably a trifunctional or higher acrylate. There is no upper limit to the number of functional groups of the acrylate, but according to one example, it is hexafunctional or less, preferably tetrafunctional or less.

[0051] The acrylate preferably contains a repeating unit. This repeating unit is, for example, any one of an ethylene oxide (EO) unit, a propylene oxide (PO) unit, and an ε-caprolactone (CL) unit. The repeating unit is preferably ethylene oxide or propylene oxide. In the acrylate, the repeating unit may be in an open ring state and interposed between the acryloyl group and the methylol group.

[0052] The number of repetitions of the repeating structure is preferably 3 or more, more preferably 15 or more. The number of repetitions of the repeating structure is, for example, 50 or less. If an acrylate with a high number of repetitions is used, the cured film is more likely to expand in the in-plane direction during the second irradiation step described below, and therefore wrinkles corresponding to the ridge portions 5B are more likely to appear on the coating film surface. Furthermore, if an acrylate with a high number of repetitions is used, the gloss value tends to decrease and the design tends to improve. However, if the number of repetitions is increased, the crosslinking density decreases, and the scratch resistance of the surface protective layer decreases. Furthermore, if an acrylate with a low number of repetitions is used, it may be difficult to achieve high processability.

[0053] In a preferred embodiment, the ionizing radiation curable resin is a trifunctional acrylate containing a repeating unit. The trifunctional acrylate containing a repeating unit is, for example, EO-modified, PO-modified, or CL-modified trimethylolpropane triacrylate, glycerin triacrylate, isocyanurate triacrylate, or pentaerythritol triacrylate. In the trifunctional acrylate containing a repeating unit, the number of repeating units is preferably 15 or more and 20 or less.

[0054] In another preferred embodiment, the ionizing radiation curable resin is a tetrafunctional acrylate containing a repeating unit. The tetrafunctional acrylate containing a repeating unit is, for example, EO-modified, PO-modified, or CL-modified pentaerythritol tetraacrylate. In the tetrafunctional acrylate containing a repeating unit, the number of repeating units is preferably 20 or more and 35 or less.

[0055] The repeat number of the repeating structure can be analyzed using MALDI-TOF-MS. Ionizing radiation curable resins may have a molecular weight distribution. If there is a molecular weight distribution, the repeat number is determined to be the repeat number corresponding to the molecular weight with the strongest peak in the MALDI-TOF-MS mass spectrum.

[0056] The inventors have discovered that by using an ionizing radiation curable resin and forming a surface protective layer through the following procedure, it is possible to consistently create a tactile sensation similar to the warmth of wood. First, a coating liquid for the surface protective layer is prepared. The coating liquid for the surface protective layer contains, for example, the resin described above. The coating liquid for the surface protective layer may further contain a solvent and additives for improving the functionality of the final product, such as antibacterial agents and antifungal agents. The coating liquid for the surface protective layer may further contain other additives such as ultraviolet absorbers and light stabilizers. Examples of ultraviolet absorbers that can be used include benzotriazoles, benzoates, benzophenones, and triazines. Examples of light stabilizers that can be used include hindered amines. Note that, according to the method described herein, a surface protective layer with low gloss can be formed without the use of a gloss adjuster (matt additive).

[0057] In the third irradiation step described below, when the entire coating film made of the coating liquid for surface protective layer is cured by ultraviolet irradiation, the coating liquid for surface protective layer preferably further contains a photoinitiator. The photoinitiator is not particularly limited, but examples thereof include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.

[0058] Next, the coating liquid for the surface protective layer is applied to one side of the raw fabric layer 10 (on the skin layer if the raw fabric layer 10 has a skin layer) to form a coating film made of the coating liquid for the surface protective layer. This coating film can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing, or various coating methods such as roll coating, knife coating, microgravure coating, and die coating.

[0059] After forming a coating film made from the coating liquid for the surface protective layer, a first irradiation step is carried out. In the first irradiation step, the coating film is irradiated with light having a wavelength of approximately 200 nm or more and 400 nm or less (hereinafter referred to as first radiation). This semi-cures the coating film. By semi-curing the coating film through the first irradiation step, it is possible to uniformly generate a wrinkled uneven structure (texture) that will be generated in the second irradiation step described below. Alternatively, by appropriately setting the irradiation conditions for the first irradiation step, it is possible to adjust the uneven structure, particularly the depth of the uneven structure.

[0060] The light source used in the first irradiation step can be selected from, for example, a high-pressure mercury lamp, a metal halide lamp, and a single-wavelength LED lamp emitting light with a wavelength of 200 nm or more and 400 nm or less.

[0061] The cumulative light intensity of the first irradiation step is 2 mJ / cm 2 More than 100mJ / cm 2 It is preferable that the dose is 10 mJ / cm or less. 2 More than 80mJ / cm 2 More preferably, it is 20 mJ / cm or less. 2 More than 60mJ / cm 2It is more preferable to set the integrated light amount to the following: If the integrated light amount is small, the effect of the first irradiation step described above will not be achieved; if the integrated light amount is large, the coating film will be completely cured, and wrinkles will not be formed in the subsequent second irradiation step.

[0062] After the first irradiation step is completed, the second irradiation step is carried out. In the second irradiation step, the coating film is irradiated with light having a wavelength of 200 nm or less (hereinafter referred to as the second radiation). The ionizing radiation curable resin contained in the coating liquid for the surface protective layer has a large absorption coefficient for the second radiation. Therefore, the second radiation incident on the coating film can only reach a position several tens to several hundreds of nm away from the outermost surface. Therefore, in the second irradiation step, the crosslinking reaction proceeds in the surface region of the coating film, forming an extremely thin cured film, while the crosslinking reaction does not proceed in other regions, leaving the coating film semi-cured.

[0063] The coating film after the second irradiation step has ridge-like wrinkles on its surface. The inventors believe that the reason why wrinkles are formed on the coating film surface by the second irradiation step is as follows. As described above, the second radiation can only reach a position tens to hundreds of nanometers from the outermost surface of the coating film. In other words, the crosslinking reaction of the ionizing radiation-curable resin caused by irradiation with the second radiation occurs only on the surface of the coating film, and regions more than tens to hundreds of nanometers from the outermost surface are partially uncured, resulting in the presence of highly fluid molecules. These highly fluid molecules swell the cured film, thereby increasing its volume. The increase in volume in the in-plane direction generates in-plane compressive stress, which causes the cured film to buckle, resulting in wrinkles on the surface of the coating film.

[0064] The second radiation can be extracted from excimer VUV (Vacuum Ultra Violet) light. Excimer VUV light can be produced from lamps that use rare gases or rare gas halide compounds. When high-energy electrons are externally applied to a lamp filled with rare gases or rare gas halide compounds, a large number of discharge plasmas (dielectric barrier discharges) are generated. This plasma discharge excites the atoms of the discharge gas (rare gas), momentarily transforming them into an excimer state. When returning from this excimer state to the ground state, light is emitted in a wavelength range specific to that excimer.

[0065] The gas used in the excimer lamp may be any conventional gas that emits light of 200 nm or less. Examples of gases that can be used include rare gases such as Xe, Ar, and Kr, and mixtures of rare gases such as ArBr and ArF with halogen gases. Excimer lamps have different wavelengths (center wavelengths) depending on the gas used, such as approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).

[0066] Considering the magnitude of photon energy and the difference between wavelength and bond energy of organic matter, it is preferable to use a xenon lamp that emits excimer light with a central wavelength of 172 nm as the light source. Also, considering the cost of maintaining the equipment and the availability of materials, it is preferable to use a xenon lamp as the light source.

[0067] The second irradiation step is carried out in an atmosphere with a low oxygen concentration. Oxygen has a high absorption coefficient for light of 200 nm or less. Therefore, the second irradiation step is preferably carried out in, for example, a nitrogen gas atmosphere. The oxygen concentration in the gas phase during the second irradiation step, i.e., the residual oxygen concentration in the reaction atmosphere, is preferably 2000 ppm or less, and more preferably 1000 ppm or less.

[0068] Furthermore, oxygen in the atmosphere inhibits radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere affects the formation of wrinkles on the coating surface. Therefore, changing the residual oxygen concentration in the reaction atmosphere can also change the surface properties of the surface protective layer 30.

[0069] The cumulative light intensity of the second radiation is 0.5 mJ / cm 2 More than 200mJ / cm 2 It is preferable that the dose is 1 mJ / cm or less. 2 More than 100mJ / cm 2 More preferably, it is 3 mJ / cm or less. 2 More than 50mJ / cm 2 It is more preferable that the dose is 5 mJ / cm or less, and 2 More than 30mJ / cm 2 It is most preferable to set the integrated light dose as follows: If the integrated light dose is small, the expansion of the cured film in the in-plane direction will be small; if the integrated light dose is large, the surface condition of the coating film will deteriorate.

[0070] After the second irradiation step is completed, a third irradiation step is carried out in which the coating film is irradiated with a third radiation to cure the entire coating film. The third radiation is ionizing radiation such as an electron beam, or ultraviolet radiation having a longer wavelength than the first radiation. The cumulative light intensity of the third radiation is 10 mJ / cm 2 More than 500mJ / cm 2 It is preferable that the dose is 50 mJ / cm or less. 2 More than 400mJ / cm 2 It is more preferable that the dose is 100 mJ / cm or less, and 2 More than 300mJ / cm 2 It is more preferable that:

[0071] The thickness of the surface protection layer 30 thus formed can be appropriately set, for example, to between 2 μm and 10 μm. On the surface of the surface protection layer 30, the ridge-like wrinkles that formed after the second irradiation step harden to form ridge-like ridges. It is difficult to control the specific shape of the ridges, and they usually do not match the grain of the design layer. However, regardless of the specific shape, the formed surface will consistently have the aforementioned load length ratio Rmr (10%), root-mean-square slope Rdq, and root-mean-square height Rq within the above-mentioned ranges. As a result, the surface protection layer 30 according to this embodiment reliably produces a tactile feel similar to the warmth of wood.

[0072] The inventors believe that the main reason why the above method can provide a surface protection layer 30 having surface properties characterized by the above parameters is as follows. As described above, by appropriately setting the irradiation conditions of the first radiation, it is possible to adjust the periodicity of the concave-convex structure and the depth of the concave-convex structure (i.e., the height-wise size of the convex and concave portions). For example, increasing the integrated light dose of the first radiation increases the degree of semi-curing of the semi-cured coating film obtained by irradiation with the first radiation. Subsequently, irradiation with the second radiation cures only the surface layer of the coating film, causing the cured film to buckle and form a concave-convex structure. The higher the degree of semi-curing of the coating film obtained by irradiation with the first radiation, the higher the bending rigidity of the surface layer (cured layer) of the coating film upon irradiation with the second radiation, and the higher the viscosity of the lower layer (semi-cured layer) located below the surface layer (cured layer). The higher the bending rigidity of the surface layer, the larger the periodicity of the concave-convex structure formed. The higher the viscosity of the lower layer, the more difficult it is to increase the volume of the surface layer, resulting in a shallower depth of the concave-convex structure. Thus, it is believed that the integrated light dose of the first radiation affects the periodicity of the concave-convex structure and the depth of the concave-convex structure.

[0073] The thickness of the coating film formed from the coating liquid for surface protective layer is also thought to affect the depth of the concave-convex structure. When the thickness of the coating film formed from the coating liquid for surface protective layer is large, the depth of the concave-convex structure is likely to be deep. Furthermore, the cumulative light amount of the second radiation also affects the degree of expansion of the cured film in the thickness direction and in-plane direction of the cured film, and is thought to affect the periodicity of the concave-convex structure and the depth of the concave-convex structure. Increasing the cumulative light amount of the second radiation tends to reduce the periodicity of the concave-convex structure and deepen the depth of the concave-convex structure. Furthermore, it is believed that the oxygen concentration in the gas phase during the second irradiation step affects the shape of the convex portions of the uneven structure. The low oxygen concentration in the gas phase during the second irradiation step has a greater effect on the crosslinking reaction closer to the surface of the coating film, so the crosslinking reaction is more likely to be accelerated at the tops of the convex portions during the second irradiation step. Therefore, curing is more likely to progress at the tops of the convex portions than in other parts of the convex portions. Furthermore, by combining the irradiation with the first radiation with the irradiation with the second radiation, the coating film is already semi-cured at the start of the second irradiation step. Therefore, curing progresses particularly quickly at the tops of the convex portions, and after curing has progressed, expansion of the cured film in the in-plane direction is less likely to occur. As a result, the slope near the tops of the convex portions is more likely to be steeper than in other parts of the convex portions.

[0074] The mechanism by which the surface protective layer 30 produces a tactile sensation similar to the warmth of wood is not fully understood, but the inventors believe it to be as follows. First, if the load length ratio Rmr (10%) is within the above-mentioned range, when a user lightly touches the uneven structure with their finger, the contact area between the finger and the protrusions is relatively small. Also, when the decorative sheet 1 is placed at room temperature, the surface temperature of the decorative sheet 1 is usually lower than the user's body temperature. Therefore, when a user touches the decorative sheet 1 with their finger, the user's heat is less likely to be transferred to the decorative sheet 1, and the user can feel the warmth as a tactile sensation.

[0075] Next, when the root-mean-square slope Rdq is within the above-mentioned range and the root-mean-square height Rq is within the above-mentioned range, the ridges are appropriately steep and have an appropriate size in the height direction. Therefore, when a user runs their finger over the surface of the surface protective layer 30, the decorative sheet 1 stimulates the user's finger and gives the user a feeling of appropriate roughness, i.e., a wood-like feel. It is believed that these factors combine to create the "warm feel of wood."

[0076] In addition, when the frequency of concave-convex structures is approximately the same, a concave-convex structure in which the shape of the apexes of the convex portions is steep will have a smaller load length ratio Rmr(10%) than a concave-convex structure in which the shape of the apexes of the convex portions is gentle. In this case, it is possible to distinguish between the two using only the parameter of the load length ratio Rmr(10%). On the other hand, a concave-convex structure in which the shape of the apexes of the convex portions is steep and the frequency of concave-convex portions is high may have the same load length ratio Rmr(10%) as a concave-convex structure in which the shape of the apexes of the convex portions is gentle and the frequency of concave-convex portions is low. In this case, it is not possible to distinguish between the two using only the parameter of the load length ratio Rmr(10%). In other words, it is not possible to express that the convex portions of the concave-convex structure are moderately steep and have a moderate size in the height direction (i.e., that they give the user a wood-like feel) using only the parameter of the load length ratio Rmr(10%). For this reason, it is appropriate to use the load length ratio Rmr (10%) in combination with the root mean square slope Rdq and root mean square height Rq as parameters to express the "warm feel of wood."

[0077] Because the surface protective layer 30 has the above-described surface properties, it can achieve a low gloss even without containing a gloss adjuster (matt additive). Gloss adjusters reduce the oil repellency of layers formed from resin materials, making surface protective layers containing gloss adjusters more susceptible to fingerprints. Surface protective layers without gloss adjusters are less likely to absorb oil and therefore less susceptible to fingerprints. Furthermore, surface protective layers with excellent oil repellency are less likely to develop oil stains or adsorb contaminants. Furthermore, surface protective layers without gloss adjusters do not lose gloss adjuster particles when scratched, and therefore decorative sheets 1 containing such surface protective layers 30 are less likely to develop gloss changes or scratches. The low gloss level described above can reduce the reflection of external light on the surface. Therefore, for example, if the pattern layer 20 has a wood grain pattern, the wood grain pattern can be clearly seen. Note that although the above parameters are related to low gloss, other parameters are also involved in achieving low gloss. For this reason, a low-gloss decorative sheet does not necessarily meet the requirements of the above parameters.

[0078] The oxygen in the gas phase during the second irradiation step not only absorbs short-wavelength ultraviolet light but also inhibits radical polymerization. The effect of oxygen in the gas phase on radical polymerization is greatest in the portion of the ionizing radiation-curable resin coating film adjacent to the gas phase, and decreases as the distance from the coating film surface increases. Therefore, by changing the oxygen concentration in the gas phase during the second irradiation step, the relationship between the distance from the coating film surface and the progress of the crosslinking reaction can be changed.

[0079] If this relationship changes, the thickness of the cured film formed on the surface of the coating film by the second irradiation step and the degree of expansion of the cured film in the in-plane direction as the crosslinking reaction progresses will change. As mentioned above, the degree of expansion of the cured film in the thickness direction and in the in-plane direction is also affected by the integrated light dose in the first and second irradiation steps. Furthermore, the degree of expansion of the cured film in the thickness direction and in the in-plane direction affects the surface properties of the surface protective layer. Furthermore, the thickness of the coating film also affects the formation of wrinkles.

[0080] Therefore, for example, by appropriately setting the composition of the ionizing radiation curable resin, the thickness of the coating film, the oxygen concentration in the gas phase in the second irradiation step, and the integrated light amount in the first and second irradiation steps, a surface protection layer having the desired surface properties can be obtained.

[0081] As shown in Figure 2, when the decorative sheet 1 according to this embodiment is attached to a desired base material 2, a decorative material 100 can be formed that has a wood-grain appearance and a feel similar to the warmth of wood. There are no particular restrictions on the material of the base material 2. Even if the base material 2 is made of wood, it does not necessarily have a good appearance, so the decorative sheet 1 may be attached to improve the appearance. A primer layer 110 and an adhesive layer 120 are provided between the decorative sheet 1 and the substrate 2. The primer layer 110 is provided between the decorative sheet 1 and the adhesive layer 120 to increase the adhesive strength with the adhesive layer 120. The material of the primer layer 110 can be the same as the binder of the design layer 20 .

[0082] A second embodiment of the present invention will be described with reference to Fig. 3. In the following description, components common to those already described will be assigned the same reference numerals and redundant description will be omitted.

[0083] 2 shows a schematic cross-sectional view of a decorative sheet 51 according to this embodiment. The decorative sheet 51 differs from the decorative sheet 1 according to the first embodiment in that it has an adhesive layer 41 and a transparent resin layer 42 between the design layer 20 and the surface protective layer 30.

[0084] The adhesive layer 41 is also called a heat-sensitive adhesive layer, an anchor coat layer, or a dry lamination adhesive layer, and bonds the design layer 20 and the transparent resin layer 42 together. The material of the adhesive layer 41 is not particularly limited, and can be appropriately selected from acrylic, polyester, polyurethane, epoxy, and other resin materials. Furthermore, an ethylene-vinyl acetate copolymer resin adhesive can also be used as the resin material for the adhesive layer 7. The coating method can be appropriately selected depending on the viscosity of the adhesive. Generally, gravure coating is used, and after the adhesive layer 41 is formed on the upper surface of the design layer 20 by gravure coating, a transparent resin layer 42 is laminated thereon.

[0085] An olefin-based resin is preferably used as the resin material of the transparent resin layer 42. Examples of the olefin-based resin include polypropylene, polyethylene, polybutene, and the like, as well as α-olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 Examples of the copolymer include homopolymers of α-olefins (e.g., 9-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene) or copolymers of two or more of these, and copolymers of ethylene or α-olefins with other monomers, such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.

[0086] From the viewpoint of improving the surface strength of the decorative sheet 51, it is preferable to use highly crystalline polypropylene for the transparent resin layer . If necessary, various additives such as heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters may be added to the transparent resin layer 42. Generally, phenol-based, sulfur-based, phosphorus-based, hydrazine-based, and other heat stabilizers are added, and hindered amine-based, and other light stabilizers are added in any combination.

[0087] The decorative sheet 51 according to this embodiment also achieves the same effects as the first embodiment due to the ridge-like protrusions of the design layer 20 and the surface protection layer.

[0088] The decorative sheet according to this embodiment will be described in more detail using examples. The technical scope of the present invention is not limited solely by the specific content of the examples.

[0089] (Example) A 55 μm thick olefin film (manufactured by Riken Technos Corporation) was used as the base layer. A woodgrain pattern layer was formed on one side of the base layer using a two-component urethane ink (V180 manufactured by Toyo Ink Co., Ltd.) containing a hindered amine light stabilizer (Chimasorb 944 manufactured by BASF). The amount of light stabilizer added was 0.5 parts by mass relative to the urethane ink binder. At the same time, a primer layer was formed on the opposite surface of the raw sheet layer using the ink.

[0090] Next, a mixture of 100 parts by mass of crystalline polypropylene resin (pentad fraction 97.8%, molecular weight distribution 2.3, MFR 18 g / 10 min), 0.5 parts by mass of a hindered amine-based light stabilizer (Chimasorb 944), and 0.5 parts by mass of a benzotriazole-based UV absorber (BASF Tinuvin 328) was extruded to form a transparent resin layer 70 μm thick.

[0091] Dry laminating adhesive (Mitsui Chemicals Takelac A540: application amount 2g / m) was applied to the pattern layer. 2 ) was applied to form an adhesive layer 41, which was then bonded to the transparent resin layer by extrusion lamination.

[0092] The following uncured liquid of ionizing radiation curable resin was prepared as a coating liquid for the surface protective layer: This resin is a trifunctional acrylate containing 15 repeating units. ·Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (EO 3 moles added) Product name: Miramer M3130 (Miwon)

[0093] The coating liquid for the surface protective layer was applied onto the transparent resin layer to form a coating film having a thickness of 4.3 μm. Subsequently, the coating film was subjected to a first irradiation step. Specifically, a high-pressure mercury lamp emitting ultraviolet rays with a main wavelength of 365 nm was used in the atmosphere, and the cumulative amount of ultraviolet rays was 60 mJ / cm. 2 The coating was semi-cured by irradiation so as to achieve the above condition. Furthermore, under atmospheric pressure, in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm, ultraviolet light with a wavelength of 172 nm was irradiated using a Xe excimer lamp with an integrated light intensity of 60 mJ / cm 2 The second irradiation step was carried out by irradiating the coating film so that ridge-like wrinkles were formed on the surface of the coating film. Finally, the coating film was irradiated with ionizing radiation in a third irradiation step to cure the entire film, thereby forming a surface protective layer having ridge-like protuberances. In this manner, a decorative sheet according to the example having a total thickness of 130 μm was produced.

[0094] (Comparative Example) The same procedures as in Example 1 were carried out up to the point where the design layer and the transparent resin layer were joined together. After the transparent resin layer was formed, it was embossed to form a pear-shaped surface. On the transparent resin layer, a coating solution for the surface protection layer having the following composition was applied at a rate of 5 g / m 2 This resin is a trifunctional acrylate, but does not contain a repeating structure. ·Ionizing radiation curable resin Type: Trimethylolpropane triacrylate Product name: NK Ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass ·Matte material Type: Silica (particle size 5 μm) Product name: Silysia (registered trademark) 250N (manufactured by Fuji Silysia Chemical Ltd.) 5 parts by mass Thereafter, the coating film was cured by carrying out only the third irradiation step without carrying out the first and second irradiation steps. Thus, a decorative sheet according to a comparative example was produced. Therefore, the surface protective layer of the comparative example did not have ridge-like protrusions on the surface.

[0095] The decorative sheets of each example were evaluated for the following items. (surface shape parameters) The load length ratio Rmr (10%), root mean square slope Rdq, and root mean square height Rq were obtained using the above formulas (1) to (3) in accordance with JIS B0601:2013. (glossiness) The 60° gloss was measured using a Rhopoint IQ manufactured by Konica Minolta.

[0096] (skin feel) The skin feel was evaluated by the following method. First, preliminary preparations were made to ensure that the evaluation criteria for surface roughness were roughly consistent among the evaluators. Specifically, three standard test pieces with different surface properties were prepared (i.e., a test piece with an Rdq of less than 0.15, a test piece with an Rdq between 0.15 and 0.4, and a test piece with an Rdq of greater than 0.4). Next, five evaluators were blindfolded and asked to slide their fingers over the surface of the standard test piece while pressing it with their fingers, and then to classify the surface roughness-related tactile sensations into the following three groups. Group 1: There was little sense of roughness, so the feel was like a flat plastic plate. Group 2: It felt moderately rough, giving it a wood-like feel. Group 3: The roughness was felt strongly, giving it a feel similar to that of a file. The above procedure was repeated until the ratings by each rater were consistent for at least three consecutive times, and the ratings between raters were consistent for three consecutive times.

[0097] Next, we conducted preliminary preparations for the tactile sensation related to temperature sensation, using the same method as for the tactile sensation related to surface roughness, to ensure that the evaluation criteria were generally consistent among the evaluators. Specifically, three standard test pieces with different surface properties were prepared: one with an Rmr (10%) between 0.05 and 0.35, one with an Rmr (10%) greater than 0.35 and less than 0.4, and one with an Rmr (10%) between 0.4 and 0.7. Next, five evaluators, while blindfolded, pressed their fingers against the surface of the standard test pieces and then slid their fingers across the surface. They then classified the tactile sensation related to temperature sensation into the following three groups. Group A: A warm feeling was felt. Group B: A lukewarm feeling was observed. Group C: A cold sensation was felt. Again, the above procedure was repeated until the evaluations by each evaluator were consistent for three or more consecutive times, and the evaluation results between the evaluators were consistent for three consecutive times.

[0098] Next, for each of the decorative sheets produced in the above examples and comparative examples, each of the evaluators was blindfolded and asked to slide their fingers over the surface of the surface protective layer while pressing it with their fingers, and then to classify the tactile sensations related to surface roughness and temperature sensation into the three groups mentioned above. This procedure was repeated until the evaluations by each evaluator were consistent three or more times in a row, and the evaluation results between the evaluators were consistent three or more times in a row. From these results, the skin feel was evaluated based on the following two-point scale to determine whether it was close to the warmth of wood, with A being considered a pass. A (Warm wood feel): When the feel of surface roughness is classified as Group 2 and the feel of temperature is classified as Group a C (Textures other than the warmth of wood): Anything that does not fall under A above.

[0099] (Fingerprint resistance) As the fingerprint resistance, the ability to wipe off fingerprints was evaluated. First, the 60-degree gloss of the surface of each decorative sheet was measured, and this 60-degree gloss was taken as the initial gloss. Next, a liquid containing a higher fatty acid was applied to the surface protective layer as a fingerprint-resistant evaluation liquid, and the fingerprint-resistant evaluation liquid that had adhered to the surface of the decorative sheet was wiped off. Thereafter, the 60-degree gloss of the area from which the fingerprint-resistant evaluation liquid had been wiped off was measured again, and the gloss after wiping was obtained. Using the initial glossiness and the glossiness after wiping, the fingerprint wiping rate was calculated according to the following formula. Fingerprint removal rate (%) = (glossiness after wiping / initial glossiness) x 100 The fingerprint wiping rate of each example was evaluated on the following three-point scale, with only A being considered a pass. A: 70% or more but less than 250% B: 50% or more but less than 70%, or 250% or more but less than 300% C: Less than 50% or 300% or more

[0100] (Scratch resistance) The following three items were investigated. Pencil hardness: Tested in accordance with JIS K 5600-5-4:1999 using a 4B lead and a load of 750 g. Those that passed were marked with a circle. Steel wool test: 20 strokes with a 500g load were performed, and the appearance was evaluated on a 5-point scale from "5: No change in gloss" to "1: Complete peeling of the surface protection layer." Hoffman scratch test: Starting from 100g, the load was increased by 100g increments until a scratch was produced, and the maximum load value at which no scratch was produced was used.

[0101] (Stain resistance) The test solution was dropped onto the surface protective layer, covered with a watch glass, and after 24 hours, the surface was washed with water and visually inspected for appearance. Four types of test solution were used: 1% sodium hydroxide, 5% sulfuric acid, ethanol, and lacquer thinner. Each was evaluated using the following three levels: ○ (good): No change in appearance △(average): Gloss changes × (bad): bleaching is observed The results are shown in Table 1.

[0102] [Table 1]

[0103] As shown in Table 1, the Examples and Comparative Examples were similar in gloss and stain resistance. The decorative sheets of the Examples had three surface shape parameters all within the specified ranges, so they had a good feel to the touch that evoked the warmth of wood and also had good fingerprint resistance, but the decorative sheets of the Comparative Examples, which did not have ridged protuberances, did not have sufficient feel to the touch and fingerprint resistance. These results show that it is extremely difficult to create a feel similar to the warmth of wood with a simple uneven shape.

[0104] The present invention has been described above using various embodiments and examples, but the specific configurations are not limited to these embodiments, and modifications and combinations of configurations within the scope of the present invention are also included. [Explanation of symbols]

[0105] 1, 51 Decorative sheet 2 Base material 10 Original layer 11 Core layer 12 Skin Layer 20 Picture layer 30 Surface protective layer 30a ridges 41 Adhesive layer 42 Transparent resin layer 100 Cosmetic Materials 110 Primer layer 120 Bonding layer

Claims

1. The original opposition layer, A design layer formed on the base fabric layer; an adhesive layer formed on the pattern layer; a transparent resin layer formed on the adhesive layer; and a surface protection layer formed on the transparent resin layer; and Equipped with The surface protective layer is It has ridged ridges on its surface, a load length ratio Rmr(10%) at a cut level of 10% on the surface is 0.05 or more and 0.35 or less; the root mean square slope Rdq of the surface is 0.15 or more and 0.4 or less; The root mean square height Rq of the surface is 0.4 μm or more and 4.0 μm or less. Decorative sheet.

2. The original opposition layer, A design layer formed on the base fabric layer; a surface protection layer formed on the pattern layer; Equipped with The surface protective layer is It has ridged ridges on its surface, a load length ratio Rmr(10%) at a cut level of 10% on the surface is 0.05 or more and 0.35 or less; the root mean square slope Rdq of the surface is 0.15 or more and 0.4 or less; The root mean square height Rq of the surface is 0.4 μm or more and 4.0 μm or less. Decorative sheet.

3. The raw fabric layer is a core layer made of resin; a skin layer provided on the surface of the core layer facing the pattern layer and containing a nucleating agent or inorganic particles; The decorative sheet according to claim 2.

4. The thickness of the surface protection layer is 2 μm or more and 10 μm or less. The decorative sheet according to claim 1 or 2.

5. the 60° gloss of the surface protective layer is less than 10; The decorative sheet according to claim 1 or 2.

6. the surface protective layer contains a cured product of an ionizing radiation curable resin, The decorative sheet according to claim 1 or 2.

7. the ionizing radiation curable resin is a trifunctional acrylate containing a repeating structure, and the number of repeating units of the repeating structure is 15 or more and 20 or less; The decorative sheet according to claim 6.

8. the ionizing radiation curable resin is a tetrafunctional acrylate containing a repeating structure, and the number of repeating units of the repeating structure is 20 or more and 35 or less; The decorative sheet according to claim 6.

9. The pattern layer has a wood grain pattern. The decorative sheet according to claim 1 or 2.

10. The decorative sheet according to claim 1 or 2; a substrate to which the decorative sheet is bonded; Equipped with A primer layer is provided between the decorative sheet and the substrate. Cosmetic materials.

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