Decorative sheet

Abstract

A decorative sheet (1) comprises an original fabric layer (2) and a surface protective layer (5) disposed on one surface of the original fabric layer (2). The surface protective layer (5) has disposed on a surface thereof a projection / recess structure that includes a plurality of ridges each protruding in a ridge-like shape. In the projection / recess structure of the surface protective layer (5), the ratio Rdc / t of a cross-sectional level difference Rdc to the thickness t of the surface protective layer (5) is 0.1-0.2. The thickness t of the surface protective layer (5) is 2-18 μm. The surface protective layer (5) contains a cured product of a resin and particles. The particles have an average particle diameter of 3 μm or more. The surface protective layer (5) contains the particles in an amount of 3-11 parts by mass with respect to 100 parts by mass of the resin. The surface protective layer (5) has a glossiness of less than 10.

Description

Decorative sheet

[0001] The present invention relates to a decorative sheet.

[0002] Decorative sheets are used for the purpose of imparting design and durability to the surface decoration of interior and exterior materials such as building fixtures, furniture, fixtures, and flooring materials. Decorative sheets are generally widely used as decorative panels that are attached via an adhesive or the like to the surface of substrates such as wood, wood boards, metal plates, non-combustible boards, paper substrates, and resin substrates.

[0003] Designs can be added by forming patterns such as wood grain or stone grain using various printing methods. Plain decorative sheets without patterns are sometimes preferred. The choice of whether to have a pattern or not and the type of pattern vary depending on the application and preference.

[0004] The glossiness of the surface is also important for the design of decorative sheets. There are a variety of decorative sheets to choose from depending on the application and preference, ranging from high gloss like a mirror to low gloss that does not reflect light at all.

[0005] As mentioned above, durability is an important function of decorative sheets, along with providing design. Durability is a comprehensive assessment of scratch resistance, stain resistance, and whether these can be maintained over a long period of time. Requirements vary depending on the environment and situation in which the decorative sheet is used, but decorative sheets with high performance are always in demand.

[0006] To impart durability, a surface protective layer is generally formed on the outermost surface of the decorative sheet, and to adjust the aforementioned gloss, particularly to achieve low gloss, a gloss adjuster (matt additive) is generally added to the surface protective layer.

[0007] Furthermore, decorative sheets are generally subjected to processes such as cutting and bending in order to form decorative materials such as decorative plates, and therefore it is preferable that the decorative sheets have processability that can withstand these processes.

[0008] As such, a decorative sheet that takes into consideration design (low gloss), scratch resistance, and stain resistance is disclosed in, for example, Patent Document 1.

[0009] Japanese Patent Application Publication No. 2019-119138

[0010] The object of the present invention is to provide a decorative sheet that gives a moist feel to the touch.

[0011] According to one aspect of the present invention, there is provided a decorative sheet comprising: an original fabric layer; and a surface protective layer provided on one surface of the original fabric layer; the surface of the surface protective layer is provided with an uneven structure including a plurality of ridge-like portions each protruding in a ridge-like shape; the uneven structure of the surface protective layer has a ratio Rdc / t of the cut level difference Rdc to the thickness t of the surface protective layer of 0.1 or more and 0.2 or less; the thickness t of the surface protective layer is 2 μm or more and 18 μm or less; the surface protective layer comprises a cured resin and particles, the particles having an average particle size of 3 μm or more, and the particles are contained in the surface protective layer in an amount of 3 parts by mass or more and 11 parts by mass or less per 100 parts by mass of the resin; and the gloss of the surface protective layer is less than 10.

[0012] According to another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the average particle size of the particles is 3 μm or more and 11 μm or less.

[0013] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the resin is an ionizing radiation curable resin.

[0014] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the resin is an acrylate.

[0015] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the resin is a trifunctional acrylate containing a repeating structure, and the number of repetitions of the repeating structure is 3 or more and 20 or less.

[0016] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the resin is a tetrafunctional acrylate containing a repeating structure, and the number of repetitions of the repeating structure is 20 or more and 35 or less.

[0017] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, further comprising a design layer between the base layer and the surface protective layer.

[0018] According to yet another aspect of the present invention, there is provided a decorative material comprising a decorative sheet according to any one of the above aspects and a substrate to which the decorative sheet is attached.

[0019] According to the present invention, it is possible to provide a decorative sheet that provides a moist feel to the touch.

[0020] Fig. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. Fig. 2 is a cross-sectional view of a surface protective layer included in the decorative sheet of Fig. 1. Fig. 3 is a microscope image of a surface protective layer included in a decorative sheet according to one example of the present invention.

[0021] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The embodiments described below are more specific embodiments of any of the above aspects. The following items can be incorporated into each of the above aspects, either singly or in combination.

[0022] 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 by the materials, shapes, structures, etc. of the components described below. Various modifications can be made to the technical idea of ​​the present invention within the technical scope defined by the claims.

[0023] In the drawings, elements having the same or similar functions are denoted by the same reference numerals, and redundant explanations will be omitted. Furthermore, the drawings are schematic, and the relationship between dimensions in one direction and dimensions in another direction, and the relationship between the dimensions of one member and the dimensions of another member, etc. may differ from the actual relationship.

[0024] <1> Decorative material and decorative sheet Fig. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. Fig. 2 is a cross-sectional view of a surface protective layer included in the decorative sheet of Fig. 1. Fig. 3 is a micrograph of a surface protective layer included in a decorative sheet according to one example of the present invention.

[0025] The cross section shown in Fig. 2 is a cross section along the thickness direction of the surface protection layer, and the micrograph in Fig. 3 is a plan view photograph obtained by a laser microscope (OLS-4000 manufactured by Olympus Corporation).

[0026] The decorative material 11 shown in Figure 1 includes a substrate B and a decorative sheet 1 attached thereto. Here, the decorative material 11 is a decorative board. The decorative board may be a flat plate, or may be curved or folded. The decorative material 11 may have a shape other than a plate.

[0027] Here, the substrate B is a plate material. The plate material is, for example, a wood board, an inorganic board, a metal plate, or a composite board made of multiple materials. The substrate B may have a shape other than a plate.

[0028] The decorative sheet 1 includes a base fabric layer 2, a design layer 3, a transparent resin layer 4, a surface protective layer 5, an adhesive layer 7, a primer layer 6, and a concealing layer 8. The design layer 3, adhesive layer 7, transparent resin layer 4, and surface protective layer 5 are provided in this order from the base fabric layer 2 side on the surface of the base fabric layer 2 opposite the surface facing the substrate B. The concealing layer 8 and primer layer 6 are provided in this order from the base fabric layer 2 side on the surface of the base fabric layer 2 facing the substrate B. One or more of the design layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and concealing layer 8 may be omitted. Below, the elements included in the decorative sheet 1 will be explained in order.

[0029] <1.1> Raw Fabric Layer The raw fabric layer 2 or its material can be any material selected from, for example, paper, synthetic resin, synthetic resin foam, rubber, nonwoven fabric, synthetic paper, metal foil, etc. Examples of paper include tissue paper, titanium paper, and resin-impregnated paper. Examples of synthetic resins 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.

[0030] The thickness of the raw fabric layer 2 is preferably within the range of 20 μm to 250 μm, taking into consideration the ease of printing and costs.

[0031] <1.2> Primer Layer When an olefin-based resin is used as the material of the raw fabric layer 2, the surface of the raw fabric layer 2 is often in an inactive state. Therefore, in this case, it is preferable to provide a primer layer 6 between the raw fabric layer 2 and the substrate B. When the raw fabric layer 2 is made of an olefin-based material, the primer layer 6 may be omitted, and the raw fabric layer 2 may be subjected to a surface modification treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, or dichromate treatment in order to improve the adhesion between the raw fabric layer 2 and the substrate B.

[0032] Materials that can be used for the primer layer 6 include, for example, the materials described below for the design layer 3. Since the primer layer 6 is applied to the back surface of the decorative sheet 1, and considering that the decorative sheet 1 will be wound up in web form, an inorganic filler may be added to the primer layer 6 to avoid blocking and increase adhesion to the adhesive. Examples of inorganic fillers include silica, alumina, magnesia, titanium oxide, and barium sulfate.

[0033] <1.3> Concealing Layer To provide the decorative sheet 1 with concealing properties for the substrate B, for example, a colored sheet is used as the base layer 2, or an opaque concealing layer 8 is provided. The concealing layer 8 can be made of, for example, the same material as that used for the design layer 3, which will be described later. However, since the purpose of the concealing layer 8 is to provide concealing properties, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide, or the like, as the pigment. Furthermore, to improve concealing properties, metals such as gold, silver, copper, and aluminum can also be added to the material of the concealing layer 8. Generally, flake-shaped aluminum pieces are often added.

[0034] <1.4> Design Layer The design layer 3 is a layer formed by printing a design onto the base layer 2 using ink. Examples of ink binders include soluble nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyesters, and modified versions thereof, either alone or in combination. The binder may be aqueous, solvent-based, or emulsion-based, and may be a one-component type or a two-component type incorporating a curing agent. The design layer 3 may be formed by curing a layer formed with a curable ink by exposure to 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 3 may further contain, in addition to the binder, pigments and colorants such as dyes, extender pigments, solvents, and various additives typically 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.

[0035] In addition to applying ink, it is also possible to apply a design to the pattern layer 3 by vapor deposition or sputtering of various metals. In particular, it is preferable that a light stabilizer be added to the ink. This 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.

[0036] <1.5> Adhesive Layer The adhesive layer 7 is also called a heat-sensitive adhesive layer, an anchor coat layer, or a dry lamination adhesive layer.

[0037] The resin material for the adhesive layer 7 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 the adhesive layer 7 is formed on the upper surface of the design layer 3 by gravure coating, and then the transparent resin layer 4 is laminated. The adhesive layer 7 can be omitted if sufficient adhesive strength can be obtained between the transparent resin layer 4 and the design layer 3.

[0038] <1.6> Transparent Resin Layer An olefin-based resin is preferably used as the resin material for the transparent resin layer 4. 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 such as 9-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene, or copolymers of two or more of these, as well as 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.

[0039] Furthermore, in order to improve the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene as the resin for the transparent resin layer 4. Note that, if necessary, various additives such as heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters can also be added to the transparent resin layer 4. 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.

[0040] <1.7> Surface Protection Layer The surface protection layer 5 includes a core portion 5A and a plurality of ridge portions 5B each protruding in a ridge shape from one surface of the core portion 5A. These ridge portions 5B form a concave-convex structure.

[0041] Here, in the decorative sheet 1 according to this embodiment, the term "ridge-like" refers to a convex shape that is linear in plan view. The ridge portions 5B may be curved or linear in plan view, but are preferably curved in view of the fingerprint resistance of the decorative sheet 1. Each ridge portion 5B may be branched or unbranched in plan view. In addition, in the present disclosure, the ridge portions 5B refer to, for example, the portion from the lowest point to the tip of the uneven shape provided on the surface of the surface protective layer 5, and the core portion 5A refers to the portion of the surface protective layer 5 excluding the ridge portions 5B.

[0042] The ridge portions 5B are curved, and at least some of them are adjacent to each other in the width direction, as shown in Fig. 3. At a position where at least some of the ridge portions 5B are adjacent to each other in the width direction, the cross section of the surface protective layer 5 parallel to the width direction and the thickness direction of the surface protective layer 5 has a wave shape, such as a sine wave shape, in the portion where the uneven structure is provided, as shown in Fig. 2.

[0043] The uneven structure of the surface protective layer 5 has a ratio Rdc / t (hereinafter simply referred to as "ratio Rdc / t") of the cutting level difference Rdc to the thickness t of the surface protective layer 5 of 0.1 to 0.2. The ratio Rdc / t is preferably 0.11 to 0.19.

[0044] The "cut level difference Rdc" is a surface texture parameter defined in JIS B0601:2013. The cut level difference Rdc indicates the cut level difference of a roughness curve and expresses the steepness of the uneven shape. Here, the position of the highest peak of the roughness curve is used as the reference for the cut level c. Furthermore, here, c(Rmr1) is defined as the cut level when the load length ratio Rmr of the roughness curve is 10%, and c(Rmr2) is defined as the cut level when the load length ratio Rmr of the roughness curve is 25%. The cut level difference Rdc (μm) of the roughness curve is the difference between the cut level c(Rmr1) and the cut level c(Rmr2). The ratio Rdc / t, obtained by dividing the cut level difference Rdc by the thickness t of the surface protective layer 5, can express the steepness of the uneven shape per unit thickness of the surface protective layer 5. Note that the region of the surface of the surface protective layer corresponding to the portion of the roughness curve where the load length ratio Rmr is less than 10% is the region that the fingertip first comes into contact with when pressing the surface protective layer with the fingertip. The moist tactile sensation is not greatly affected by the region of the surface of the surface protective layer where the fingertip first comes into contact with the surface protective layer when the fingertip applies extremely large pressure to the surface protective layer. The moist tactile sensation is greatly affected by the slope of the region of the surface of the surface protective layer where the fingertip first comes into contact when the fingertip applies a certain amount of pressure to the surface protective layer. This region corresponds to the region of the roughness curve where the load length ratio Rmr is in the range of 10% to 25%.

[0045] When the ratio Rdc / t is 0.1 or more and 0.2 or less, the slope of the uneven shape is relatively gentle. In this case, when the surface of the decorative sheet is pressed with a finger and then slid across the surface, the resistance to pressure due to contact between the finger and the surface is small, and the contact area between the finger and the surface of the convex portions gradually increases, resulting in a tactile sensation as if the surface of the decorative sheet is sticking to the finger. This tactile sensation can be associated with a "moist tactile sensation."

[0046] On the other hand, when the ratio Rdc / t is greater than 0.2, the slope of the uneven shape becomes steep. In this case, when a finger is pressed against the surface of the decorative sheet and slid across the surface, the indentation resistance due to contact between the finger and the surface is large, and the presence of the unevenness is felt. This tactile sensation can be associated with a "rough tactile sensation." Furthermore, when the ratio Rdc / t is less than 0.1, the slope of the uneven shape is fairly gentle. In this case, when a finger is pressed against the surface of the decorative sheet and slid across the surface, the indentation resistance due to contact between the finger and the surface is small, and the contact area between the finger and the convex surface is large from the start of the pressing action, and the increase in this contact area with the pressing action is fairly gradual. Therefore, in this case, the surface of the decorative sheet feels as if it is sticking to the finger, and because the slope of the uneven shape is fairly gentle, a smooth tactile sensation is obtained compared to the above-mentioned "moist tactile sensation," and overall, the impression of a smooth tactile sensation is stronger. This tactile sensation can be associated with a "smooth tactile sensation."

[0047] The thickness t of the surface protective layer 5 is 2 μm or more and 18 μm or less. The thickness t of the surface protective layer 5 is preferably 3 μm or more and 10 μm or less. Increasing the thickness of the surface protective layer 5 tends to increase the value of the ratio Rdc / t. Therefore, if the thickness of the surface protective layer 5 is too small or too large, it becomes difficult to achieve a "moist tactile feel." Furthermore, reducing the thickness of the surface protective layer 5 makes it difficult to achieve a low gloss level. Here, the thickness of the surface protective layer 5 is determined by observing the cross section with a scanning electron microscope and averaging 25 points. Specifically, the thickness of the surface protective layer 5 can be determined as described in the Examples below. When the coating liquid for the surface protective layer described below does not contain a solvent, the thickness of the coating film made of the coating liquid for the surface protective layer is equal to the thickness of the surface protective layer 5.

[0048] The surface protective layer 5 contains a cured resin and particles. The resin contained in the surface protective layer 5 is preferably 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 irradiation with 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 large absorption coefficient for this light.

[0049] The amount of the cured ionizing radiation curable resin in the surface protective layer 5 is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. As the ionizing radiation curable resin, known resins such as various monomers and commercially available oligomers can be used, 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.

[0050] 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.

[0051] The acrylate is preferably a difunctional or higher acrylate, more preferably a trifunctional or higher acrylate. In order to obtain a surface protective layer 5 having 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 lower.

[0052] 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 present between the acryloyl group and the methylol group in an open ring state.

[0053] The number of repetitions of the repeating structure is preferably 3 or more. If an acrylate with a large number of repetitions is used, the cured film is more likely to expand in the in-plane direction during the first 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 large number of repetitions is used, the ratio Rdc / t tends to increase. However, if the number of repetitions is increased, the crosslinking density decreases, and the scratch resistance of the surface protective layer decreases.

[0054] 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 3 or more, more preferably 3 to 30, and even more preferably 3 to 20.

[0055] 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 12 or more, more preferably 12 to 50, even more preferably 20 to 50, and even more preferably 20 to 35.

[0056] The number of repetitions of the repeating structure can be analyzed using MALDI-TOF-MS. Ionizing radiation curable resins may have a molecular weight distribution. When a molecular weight distribution exists, the number of repetitions is determined to be the number of repetitions corresponding to the molecular weight having the strongest peak in the MALDI-TOF-MS mass spectrum.

[0057] The particles contained in the surface protection layer 5 may be, for example, particles made of organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads, or particles made of inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.

[0058] The particles have an average particle size (D50) of 3 μm or more, preferably 3 μm or more and 11 μm or less, and more preferably 4 μm or more and 10 μm or less.

[0059] When the surface protective layer 5 contains particles, wrinkles can be more uniformly generated on the coating surface in the first irradiation step described below. As the average particle size (D50) of the particles increases, the value of the ratio Rdc / t tends to decrease. Therefore, if the average particle size (D50) is too small or too large, it becomes difficult to achieve a "moist tactile feel." Furthermore, when large particles are used, the particles are likely to fall off from the surface protective layer 5, making it difficult to achieve high scratch resistance. When the particles are small, the effect of generating wrinkles uniformly is small.

[0060] Here, the "average particle size (D50)" refers to the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. When the coating liquid for the surface protective layer contains particles, the surface protective layer 5 obtained from this coating liquid will also contain particles. The average particle size of the particles contained in the surface protective layer 5 can be determined by observing the cross section of the layer and averaging the particle sizes of multiple particles. The value obtained in this manner is substantially the same as the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. Therefore, the above-mentioned range of average particle size can also be interpreted as the range of average particle sizes of the particles contained in the surface protective layer 5.

[0061] The particles are contained in the surface protective layer 5 in an amount of 3 to 11 parts by mass per 100 parts by mass of resin. The amount of particles added is preferably 4 to 10 parts by mass per 100 parts by mass of resin. Note that "100 parts by mass of resin" refers to the parts by mass of the solid content of the resin.

[0062] When the amount of particles added is within the above range, the effect of uniformly forming wrinkles is particularly large. As the amount of particles added increases, the value of the ratio Rdc / t tends to decrease. Therefore, if the amount of particles added is too small or too large, it becomes difficult to achieve a "moist tactile feel." Furthermore, if the amount of particles added is large, the particles are likely to fall off from the surface protective layer 5, making it difficult to achieve high scratch resistance. If the amount of particles added is small, the effect of uniformly forming wrinkles is small.

[0063] The glossiness of the surface protective layer 5 is less than 10.0. The glossiness of the surface protective layer 5 is preferably 5 or less. Here, the "glossiness" is a measured value measured at an incident angle of 60 degrees using a glossmeter in accordance with JIS Z8741:1997.

[0064] <2> Manufacturing Method of Decorative Sheet The decorative sheet 1 is manufactured, for example, by the following method. For the sake of brevity, explanations of the design layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and hiding layer 8 are omitted here.

[0065] First, a coating film made of a coating liquid for the surface protective layer is formed on one surface of the raw fabric layer 2. 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.

[0066] The coating liquid for the surface protective layer contains the above-mentioned resin and the above-mentioned particles. 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 an antibacterial agent and an antifungal agent. The coating liquid for the surface protective layer may further contain other additives such as an ultraviolet absorber and a light stabilizer. Examples of the ultraviolet absorber that can be used include benzotriazoles, benzoates, benzophenones, and triazines. Examples of the light stabilizer that can be used include hindered amines. Note that, according to the method described herein, a surface protective layer 5 having a low gloss can be formed without a gloss adjuster (matt additive).

[0067] In the second irradiation step described below, when the entire coating film made of the coating liquid for surface protective layer is cured by ultraviolet irradiation, it is preferable that the coating liquid for surface protective layer 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.

[0068] After forming a coating film made from the coating liquid for a 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 200 nm or less (hereinafter referred to as first radiation). The ionizing radiation curable resin contained in the coating liquid for a surface protective layer has a large absorption coefficient for the first radiation. Therefore, the first radiation incident on the coating film can only reach a position several tens to several hundreds of nanometers away from the outermost surface. Therefore, in the first irradiation step, a 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 other regions uncured.

[0069] The coating film after the first irradiation step has wrinkles on its surface corresponding to the ridge portions 5 B. The present inventors believe that the reason why wrinkles are formed on the coating film surface by the first irradiation step is as follows.

[0070] As described above, the first radiation can only reach a position tens to hundreds of nanometers away from the outermost surface of the coating film. That is, the crosslinking reaction of the ionizing radiation curable resin occurs only on the surface of the coating film, and regions more than tens to hundreds of nanometers away from the outermost surface are uncured and contain 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.

[0071] The first radiation can be extracted from excimer VUV (Vacuum Ultra Violet) light. Excimer VUV light can be generated from a lamp using a rare gas or a rare gas halide compound. When high-energy electrons are externally applied to a lamp filled with a rare gas or a rare gas halide compound, a large number of discharge plasmas (dielectric barrier discharges) are generated. This plasma discharge excites atoms of the discharge gas (rare gas), which momentarily transition to an excimer state. When returning from this excimer state to the ground state, light is emitted in a wavelength range specific to the excimer.

[0072] The gas used in the excimer lamp may be any conventional gas that emits light of 200 nm or less. Examples of the gas include rare gases such as Xe, Ar, and Kr, and mixtures of rare gases such as ArBr and ArF with halogen gases. The wavelength (center wavelength) of excimer lamps varies depending on the gas, and examples include wavelengths of approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).

[0073] 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.

[0074] The first 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 first irradiation step is preferably carried out in, for example, a nitrogen gas atmosphere. The oxygen concentration in the gas phase in the first 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.

[0075] 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 5.

[0076] The integrated light amount of the first 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 More preferably, it is 5 mJ / cm or less. ２ 30mJ / cm or more 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.

[0077] 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 a second radiation to cure the entire coating film. In this way, the surface protective layer 5 is obtained.

[0078] The second radiation is ionizing radiation such as an electron beam, or ultraviolet radiation having a longer wavelength than the first radiation. When ultraviolet radiation is used as the second radiation, the ultraviolet radiation has a wavelength at which the ionizing radiation curable resin exhibits a smaller absorption coefficient.

[0079] The cumulative amount of the second 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 ２More preferably, it is 100 mJ / cm or less. ２ More than 300mJ / cm ２ It is more preferable that the following is the case. The decorative sheet 1 can be produced, for example, by the above-mentioned method. The decorative sheet 1 may also be produced by other methods. For example, a plate may be formed using the method described above for the surface protective layer 5, and the surface protective layer 5 having a concave-convex structure on its surface may be formed by transfer using this plate.

[0080] <3> Effect The decorative sheet 1 described with reference to Figures 1 to 3 has a surface protective layer 5 with the above-mentioned surface properties. Such a decorative sheet 1 provides a moist tactile sensation to the user when the user presses the surface of the surface protective layer 5 with their skin and slides their finger across the surface, for example, when pressing the surface of the surface protective layer 5 with their finger and sliding their finger across the surface. That is, because the slope of the uneven shape on the surface of this decorative sheet 1's surface protective layer 5 is relatively gentle, when touched in this manner, the contact area between the finger and the convex surface can be gradually increased while keeping the pressure resistance due to contact between the finger and the surface small. This results in a tactile sensation as if the surface of the decorative sheet is sticking to the finger.

[0081] The moist feel gives a sense of comfort and warmth to anyone who touches the decorative sheet 1. The moist feel also gives a sense of luxury to the decorative sheet 1. Therefore, the decorative sheet 1 that gives the user a moist feel is suitable for use in applications where it frequently comes into contact with the user's skin or where it will be in contact with the user's skin for long periods of time, such as table tops, chair arms, and handrails on stairs and in corridors.

[0082] Because the surface protective layer 5 of the decorative sheet 1 has the above-described surface properties, it can achieve a low gloss even without containing a gloss adjuster (matt additive). Because gloss adjusters reduce the oil repellency of layers formed from resin materials, surface protective layers 5 containing gloss adjusters are prone to fingerprints. Surface protective layers 5 that do not contain gloss adjusters are less likely to absorb oil and therefore less likely to be marked with fingerprints. Furthermore, surface protective layers 5 with excellent oil repellency are less likely to develop oil stains or adsorb contaminants. Furthermore, surface protective layers 5 that do not contain gloss adjusters do not lose gloss adjuster particles when their surface is scratched, and therefore decorative sheets 1 containing such surface protective layers 5 are less likely to develop gloss changes or scratches.

[0083] The reason why the surface protection layer 5 having the above-described surface properties can be obtained by the above-described method is as follows.

[0084] Oxygen in the gas phase not only absorbs short-wavelength ultraviolet rays but also inhibits radical polymerization. The effect of oxygen contained in the gas phase on radical polymerization is greatest in the portion of the coating film made of an ionizing radiation-curable resin 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 in the first irradiation step, it is possible to change the relationship between the distance from the coating film surface and the progress of the crosslinking reaction.

[0085] If this relationship changes, the thickness of the cured film formed on the surface of the coating film by the first irradiation step and the degree of in-plane expansion of the cured film according to the progress of the crosslinking reaction will change. The integrated light amount in the first irradiation step also affects the thickness of the cured film and the degree of in-plane expansion of the cured film. The thickness of the cured film and the degree of in-plane expansion of the cured film also affect the surface properties of the surface protective layer. Furthermore, the particle size and amount of particles added in the coating film, as well as the thickness of the coating film, also affect the formation of wrinkles.

[0086] Therefore, for example, by appropriately setting the composition of the ionizing radiation curable resin, the particle size and amount of added particles, the thickness of the coating film, the oxygen concentration in the gas phase in the first irradiation step, and the integrated light amount in the first irradiation step, it is possible to obtain a surface protection layer having the desired surface properties.

[0087] The following describes examples of the present invention.

[0088] 1 to 3 was produced by the following method. In this example, the transparent resin layer 4, primer layer 6, adhesive layer 7, and hiding layer 8 were omitted.

[0089] First, the basis weight is 50 g / m ２ An impregnated paper (GFR-506, manufactured by Kojin Co., Ltd.) was prepared as the raw fabric layer 2. On one side of the raw fabric layer 2, a design layer 3 was formed using an oil-based nitrocellulose resin gravure printing ink (PCNT (PCRNT) various colors, manufactured by Toyo Ink Co., Ltd.).

[0090] Next, a coating liquid for a surface protective layer was applied onto the design layer 3. The coating liquid for the surface protective layer was a mixture of the following ionizing radiation curable resin and the following particles: Ionizing radiation curable resin Type: trimethylolpropane EO-modified triacrylate (15 moles of EO added) Product name: SR9035 (manufactured by Sartomer) Blend: 100 parts by mass Particles Product name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 5 μm Blend: 5 parts by mass A coating film made of the coating liquid for the surface protective layer was formed to a thickness of 5 μm.

[0091] Thereafter, the first irradiation step was carried out. Specifically, under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 500 ppm, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for surface protective layer using a Xe excimer lamp at an integrated light intensity of 50 mJ / cm. ２ This caused wrinkles to form on the surface of the coating film.

[0092] Subsequently, the second irradiation step was carried out. Specifically, the coating film was irradiated with ionizing radiation to cure the entire film, thereby forming a surface protective layer 5. In this manner, a decorative sheet 1 was obtained.

[0093] <Comparative Example 1> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, particles were not blended. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0094] <Comparative Example 2> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 2 parts by mass. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 90 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0095] <Example 2> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 3 parts by mass. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 250 ppm under atmospheric pressure, with an integrated light amount of 70 mJ / cm. ２ The irradiation was carried out so that

[0096] <Example 3> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 4 parts by mass. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 60 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 400 ppm. ２ The irradiation was carried out so that

[0097] <Example 4> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 10 parts by mass. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 750 ppm under atmospheric pressure, with an integrated light amount of 40 mJ / cm. ２ The irradiation was carried out so that

[0098] <Example 5> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 11 parts by mass. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 750 ppm under atmospheric pressure, with an integrated light amount of 40 mJ / cm. ２ The irradiation was carried out so that

[0099] <Comparative Example 3> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 12 parts by mass. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 750 ppm under atmospheric pressure, with an integrated light intensity of 40 mJ / cm. ２ The irradiation was carried out so that

[0100] <Comparative Example 4> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, a coating film made of a coating liquid for a surface protective layer was formed to a thickness of 1 μm. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated to the surface of the coating film made of the coating liquid for a surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm under atmospheric pressure, with an integrated light intensity of 100 mJ / cm. ２ The irradiation was carried out so that

[0101] <Example 6> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, a coating film made of a coating liquid for a surface protective layer was formed to a thickness of 2 μm. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for a surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm under atmospheric pressure, with an integrated light intensity of 80 mJ / cm. ２ The irradiation was carried out so that

[0102] <Example 7> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, a coating film made of a coating liquid for a surface protective layer was formed to a thickness of 3 μm. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for a surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm under atmospheric pressure, with an integrated light intensity of 70 mJ / cm. ２ The irradiation was carried out so that

[0103] <Example 8> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, a coating film made of a coating liquid for a surface protective layer was formed to a thickness of 10 μm. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for a surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 700 ppm under atmospheric pressure, with an integrated light intensity of 20 mJ / cm. ２ The irradiation was carried out so that

[0104] <Example 9> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, a coating film made of a coating liquid for a surface protective layer was formed to a thickness of 18 μm. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for a surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 700 ppm under atmospheric pressure, with an integrated light intensity of 10 mJ / cm. ２ The irradiation was carried out so that

[0105] <Comparative Example 5> A decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, a coating film made of a coating liquid for a surface protective layer was formed to a thickness of 20 μm. Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for a surface protective layer using a Xe excimer lamp in a nitrogen gas atmosphere with an oxygen concentration of 700 ppm under atmospheric pressure, with an integrated light intensity of 5 mJ / cm. ２ The irradiation was carried out so that

[0106] <Comparative Example 6> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following particles were used: Particles Product name: Sylysia 310P (manufactured by Fuji Silysia Ltd.) Particle size: 2 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 40 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 600 ppm. ２ The irradiation was carried out so that

[0107] <Example 10> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following particles were used: Particles Product name: Sylysia 420 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 3 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 45 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 550 ppm. ２ The irradiation was carried out so that

[0108] <Example 11> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following particles were used: Particles Product name: Sylysia 430 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 4 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 45 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 550 ppm. ２ The irradiation was carried out so that

[0109] <Example 12> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following particles were used: Particles Product name: Sylysia 450 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 8 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 80 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 400 ppm. ２ The irradiation was carried out so that

[0110] <Example 13> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following particles were used: Particles Product name: Sylysia 882 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 10 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated to the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0111] <Example 14> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following particles were used: Particles Product name: Sylysia 780 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 11 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated to the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0112] <Example 15> Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. That is, in this example, the following particles were used: Particles Product name: sicastar 43-00-154 (manufactured by Corefront Co., Ltd.) Particle size: 14 μm Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated to the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0113] Comparative Example 7 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: Trimethylolpropane triacrylate Product name: NK Ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) In the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0114] <Example 16> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (3 EO moles added) Product name: Miramer M3130 (manufactured by Miwon Co., Ltd.) The first irradiation step involved irradiating the surface of the coating film made of the surface protective layer coating liquid with ultraviolet light having a wavelength of 172 nm at an integrated light intensity of 100 mJ / cm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0115] <Example 17> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (6 EO moles added) Product name: Miramer M3160 (manufactured by Miwon Co., Ltd.) The first irradiation step involved irradiating the surface of the coating film made of the surface protective layer coating liquid with ultraviolet light having a wavelength of 172 nm at an integrated light intensity of 100 mJ / cm using a Xe excimer lamp under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0116] <Example 18> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following ionizing radiation curable resin was used: Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (9 moles of EO added) Product name: SR502 (manufactured by Sartomer Corporation) The first irradiation step involved irradiating the surface of the coating film made of the surface protective layer coating liquid with ultraviolet light at a wavelength of 172 nm using a Xe excimer lamp at an integrated light intensity of 80 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 200 ppm. ２ The irradiation was carried out so that

[0117] <Example 19> Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (20 moles of EO added) Product name: NK Ester AT-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) The first irradiation step involved irradiating the surface of the coating film made of the surface protective layer coating liquid with ultraviolet light at a wavelength of 172 nm using a Xe excimer lamp at an integrated light intensity of 45 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 600 ppm. ２ The irradiation was carried out so that

[0118] <Example 20> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: Ethoxylated pentaerythritol tetraacrylate (20 moles of EO added) Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 45 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 600 ppm. ２ The irradiation was carried out so that

[0119] <Example 21> Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. That is, in this example, the following ionizing radiation curable resin was used: Ionizing radiation curable resin Type: Ethoxylated pentaerythritol tetraacrylate (35 moles of EO added) Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) The first irradiation step involved irradiating the surface of the coating film made of the surface protective layer coating liquid with ultraviolet light at a wavelength of 172 nm using a Xe excimer lamp at an integrated light intensity of 40 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 650 ppm. ２ The irradiation was carried out so that

[0120] <Comparative Example 8> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the blending amount of particles was 15 parts by mass. The first irradiation step was not performed, and the coating film made of the coating liquid for surface protective layer was cured only by the second irradiation step.

[0121] Comparative Example 9 Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: ethylene glycol diacrylate (9 moles of EO added) Product name: Light Acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 40 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 550 ppm. ２ The irradiation was carried out so that

[0122] Comparative Example 10 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: Ethoxylated dipentaerythritol hexaacrylate (12 moles of EO added) Product name: NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) The first irradiation step involved irradiating the surface of the coating film made of the surface protective layer coating liquid with ultraviolet light at a wavelength of 172 nm using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２The irradiation was carried out so that

[0123] <Comparative Example 11> Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. That is, in this example, the following ionizing radiation curable resin was used. Ionizing radiation curable resin Type: pentaerythritol tetraacrylate Product name: NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) Then, in the first irradiation step, ultraviolet light having a wavelength of 172 nm was irradiated to the surface of the coating film made of the coating liquid for the surface protective layer using a Xe excimer lamp at an integrated light intensity of 100 mJ / cm under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm. ２ The irradiation was carried out so that

[0124] <Evaluation> Each of the decorative sheets described above was subjected to the following evaluations.

[0125] (1) Thickness of the Surface Protective Layer The thickness of the surface protective layer was measured as follows. After embedding the decorative sheet 1 in a resin such as a cold-curing epoxy resin or a UV-curable resin and allowing it to fully harden, the decorative sheet 1 was cut to reveal its cross section and mechanically polished to obtain a measurement surface. The thickness of the surface protective layer was then measured using a SIGMA 500 scanning electron microscope manufactured by Carl Zeiss Microscopy. Measurements were performed at 25 random points, and the average measurement value for the 25 points was defined as the "thickness t of the surface protective layer." The measurement conditions were an acceleration voltage of 0.5 keV (low acceleration voltage), an SE2 mode, and a magnification of 2000x. No sputtering was performed on the measurement sample. The "thickness t of the surface protective layer" was equal to the thickness of the coating film made from the surface protective layer coating liquid.

[0126] (2) Glossiness The glossiness was measured at 60 degrees using a Rhopoint IQ (manufactured by Konica Minolta, Inc.) The "60 degree glossiness value" in Tables 1 to 4 below represents this 60 degree glossiness.

[0127] (3) Skin Feel Skin feel was evaluated using the following method. First, advance preparation was performed to ensure that the evaluation criteria were consistent among the evaluators. Specifically, three standard test pieces with different surface properties were prepared. 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 tactile sensation into the following three groups. Group 1: Almost no resistance was felt when pressing, but the surface of the decorative sheet felt as if it was sticking to the finger, and a smooth tactile sensation was obtained. Overall, the impression of a smooth tactile sensation was strong. In other words, a smooth tactile sensation was obtained. Group 2: Almost no resistance was felt when pressing, but the surface of the decorative sheet felt as if it was sticking to the finger. However, the impression of a smooth tactile sensation was not felt. In other words, a moist tactile sensation was obtained. Group 3: Resistance to pressing was felt, and the presence of unevenness was also felt. In other words, a rough tactile sensation was obtained.

[0128] The above procedure was repeated until the evaluations by each evaluator coincided three or more times in succession and the evaluation results between the evaluators coincided three times in succession.

[0129] Next, for each of the decorative sheets, 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 sensation into one of the three groups. This procedure was repeated until the evaluations by each evaluator were consistent for three or more consecutive evaluations, and the evaluation results between the evaluators were consistent for three or more consecutive evaluations. From these results, the skin sensation was evaluated according to the following criteria: A (smooth): Group 1 B (moist): Group 2 C (rough): Group 3

[0130] (4) Fingerprint Resistance To evaluate fingerprint resistance, a fingerprint wiping property evaluation was performed. Specifically, first, the 60-degree glossiness of the surface of each decorative sheet was measured, and this 60-degree glossiness was defined as the initial glossiness. Next, a fingerprint resistance evaluation liquid was applied to the surface protective layer, and the fingerprint resistance evaluation liquid applied to the decorative sheet surface was wiped off. Here, a higher fatty acid was used as the fingerprint resistance evaluation liquid. Thereafter, the 60-degree glossiness of the portion from which the fingerprint resistance evaluation liquid had been wiped off was measured, and this 60-degree glossiness was defined as the glossiness after wiping.

[0131] The fingerprint wiping rate was calculated using the following formula: Fingerprint wiping rate (%) = (glossiness after wiping / initial glossiness) x 100

[0132] The evaluation criteria were as follows: AA: 70% or more and less than 250% A: 50% or more and less than 70%, or 250% or more and less than 300% B: Less than 50%, or 300% or more

[0133] (5) Stain Resistance To evaluate stain resistance, the Stain A test specified in the Japanese Agricultural Standards (JAS) was carried out. That is, 10 mm wide lines were drawn on the surface protective layer of each decorative sheet using blue ink, black quick-drying ink, and red crayon, and the sheets were left for 4 hours. Thereafter, the blue ink, black quick-drying ink, and red crayon lines were wiped off with a cloth soaked in ethanol.

[0134] The evaluation criteria were as follows: AA: Lines of each color could be easily wiped off. A: Part of the lines of each color could be wiped off, but some stains remained. B: Lines of each color could not be wiped off.

[0135] (6) Scratch Resistance Each decorative sheet was attached to wood substrate B using a urethane adhesive. A steel wool rubbing test was then conducted to evaluate scratch resistance. Specifically, the decorative sheet was rubbed back and forth 20 times with steel wool while applying a load of 100 g, and scratches and changes in gloss on the surface of the decorative sheet were visually confirmed.

[0136] The evaluation criteria were as follows: AA: No scratches or changes in gloss occurred on the surface. A: Minor scratches or changes in gloss occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.

[0137] (7) Processability The resulting decorative sheet was attached to wood substrate B using a urethane adhesive, with the surface of the base layer (i.e., the back surface of the decorative sheet) facing the wood substrate B. Thereafter, a V-shaped groove was made up to the boundary where the wood substrate B and the decorative sheet were bonded together, so as not to scratch the decorative sheet. Next, the wood substrate B was bent 90 degrees along the V-shaped groove so that the surface of the decorative sheet facing the surface protection layer (i.e., the surface of the decorative sheet) formed a mountain fold. The bent portion of the surface of the decorative sheet was observed using an optical microscope to determine whether whitening or cracks had occurred, and bending processability was evaluated.

[0138] The evaluation criteria were as follows: AA: No whitening or cracks were observed. A: Whitening was observed in some areas. B: Whitening was observed over the entire surface, or cracks were observed in some areas.

[0139] (8) Cutting Level Difference Rdc and Ratio Rdc / t The cutting level difference Rdc (μm) and the ratio Rdc / t were determined as described above in the detailed description.

[0140] The evaluation results are shown in Tables 1 to 4. In Tables 1 to 4, if the evaluation result of skin feel is A (smooth), this is indicated by entering the letter Y in the "A (smooth)" column, if the evaluation result of skin feel is B (moist), this is indicated by entering the letter Y in the "B (moist)" column, and if the evaluation result of skin feel is C (rough), this is indicated by entering the letter Y in the "C (rough)" column.

[0141]

[0142]

[0143]

[0144]

[0145] As shown in Tables 1 to 4, the decorative sheets according to Examples 1 to 21 provided evaluators with a moist feel. Furthermore, the decorative sheets according to Examples 1 to 21 had low gloss and were excellent in fingerprint resistance, stain resistance, and processability. Furthermore, the decorative sheets according to Examples 1 to 14 and 16 to 21 also had excellent scratch resistance.

[0146] Comparative Example 3 gave the evaluators a moist feel and had low gloss, but was poor in stain resistance, scratch resistance, and processability, as shown in Table 1. Comparative Example 8 gave the evaluators a moist feel, but had high gloss and was poor in fingerprint resistance, stain resistance, and scratch resistance, as shown in Table 4.

[0147] In contrast, as shown in Tables 1, 2, and 4, Comparative Examples 1, 2, 5, 6, and 9 did not give the evaluators a moist feel, but rather a rough feel. Also, as shown in Tables 2 to 4, Comparative Examples 4, 7, 10, and 11 did not give the evaluators a moist feel, but rather a smooth feel.

[0148] 1...decorative sheet, 2...base layer, 3...pattern layer, 4...transparent resin layer, 5...surface protection layer, 6...primer layer, 7...adhesive layer, 8...hiding layer, 11...decorative material, B...base material.

Claims

1. It comprises a raw material layer and a surface protection layer provided on one surface of the raw material layer, The surface of the aforementioned surface protective layer is provided with an uneven structure including a plurality of ridge-like portions, each of which protrudes in a ridge-like manner. The uneven structure of the surface protective layer has a ratio Rdc / t of the difference in cutting level Rdc to the thickness t of the surface protective layer, which is 0.1 or more and 0.2 or less. The thickness t of the surface protective layer is 2 μm or more and 18 μm or less. The surface protective layer comprises a cured resin and particles, the particles having an average particle size of 3 μm or more, and the particles are included in the surface protective layer in an amount of 3 parts by mass or more and 11 parts by mass or less per 100 parts by mass of the resin. The gloss level of the surface protective layer is less than 10 in this decorative sheet.

2. The decorative sheet according to claim 1, wherein the average particle size of the particles is 3 μm or more and 11 μm or less.

3. The decorative sheet according to claim 1, wherein the resin is an ionizing radiation-curable resin.

4. The decorative sheet according to claim 1, wherein the resin is acrylate.

5. The decorative sheet according to claim 1, wherein the resin is a trifunctional acrylate containing a repeating structure, and the number of repetitions of the repeating structure is 3 or more and 20 or less.

6. The decorative sheet according to claim 1, wherein the resin is a tetrafunctional acrylate containing a repeating structure, and the number of repetitions of the repeating structure is 20 or more and 35 or less.

7. The decorative sheet according to claim 1, further comprising a pattern layer between the base material layer and the surface protective layer.

8. A decorative sheet according to any one of claims 1 to 7, The base material to which the decorative sheet is attached and A decorative material that has the following features.