Decorative sheet

Abstract

To provide a decorative sheet that is excellent in scratch resistance and gives a unique feel. [Solution] The decorative sheet 1 comprises an original fabric layer 2 and a surface protection layer 5 provided on one surface of the original fabric layer 2, the surface protection layer 5 containing a cured resin and having an uneven structure on its surface including a plurality of ridge-like portions each protruding in a ridge-like shape, the uneven structure having an aspect ratio Str of the surface texture of 0.8 or more and a load area ratio Smr1 separating the protruding ridge portion from the core portion of 14% or more.

Description

[Technical Field]

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

[0002] Decorative sheets are used for the purpose of decorating the surfaces of interior and exterior materials such as building fixtures, furniture, fixtures, and flooring, i.e., for the purpose of imparting design and durability to these components. 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. Furthermore, 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 Patent Document 1, for example. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2019-119138 Summary of the Invention [Problem to be solved by the invention]

[0010] The object of the present invention is to provide a decorative sheet that is excellent in scratch resistance and provides a unique feel to the touch. [Means for solving the problem]

[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, wherein the surface protective layer contains a cured resin and has an uneven structure on its surface including a plurality of ridge-like portions each protruding in a ridge-like shape, wherein the uneven structure has a surface aspect ratio Str of 0.8 or more and a load area ratio Smr1 separating the protruding ridge portions from the core portion of 14% or more.

[0012] According to another aspect of the present invention, there is provided a decorative sheet according to the above aspect, in which the specular gloss GS(60°) of the portion corresponding to the uneven structure is 5% 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 surface protective layer has a thickness of 12 μm or less.

[0014] 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 an ionizing radiation curable resin.

[0015] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the resin is an acrylate.

[0016] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the acrylate includes a polyfunctional acrylate containing a repeating structure.

[0017] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the resin contains a trifunctional acrylate containing a repeating unit and a difunctional acrylate containing a repeating unit.

[0018] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the proportion of the trifunctional acrylate in the resin is in the range of 40% by mass or more and 95% by mass or less, and the proportion of the difunctional acrylate is in the range of 5% by mass or more and 60% by mass or less.

[0019] 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 number of repetitions of the repeating structure contained in the bifunctional acrylate is less than the number of repetitions of the repeating structure contained in the trifunctional acrylate.

[0020] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the number of repetitions of the repeating structure contained in the trifunctional acrylate is within the range of 9 or more and 15 or less, and the number of repetitions of the repeating structure contained in the bifunctional acrylate is within the range of 3 or more and 9 or less.

[0021] 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 surface protective layer further comprises particles dispersed in the cured product.

[0022] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the amount of the particles is within the range of 3 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cured product.

[0023] 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.

[0024] 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. [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a decorative sheet that is excellent in scratch resistance and provides a unique feel to the touch. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view of the surface protective layer included in the decorative sheet of FIG. [Figure 3] FIG. 3 is a microscope image of a surface protective layer included in a decorative sheet according to one example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0027] 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.

[0028] 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.

[0029] 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.

[0030] <1> Decorative materials and decorative sheets 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.

[0031] The cross section shown in Fig. 2 is a cross section along the thickness direction of the surface protection layer. The micrograph in Fig. 3 is a plan view photograph obtained by a laser microscope (OLS-4000 manufactured by Olympus Corporation).

[0032] The decorative material 11 shown in FIG. 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.

[0033] 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.

[0034] 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 masking 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 masking 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 masking layer 8 may be omitted. The elements included in the decorative sheet 1 will be explained below in order.

[0035] <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 fabrics include organic and inorganic nonwoven fabrics. Examples of metals for the metal foil include aluminum, iron, gold, and silver.

[0036] 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.

[0037] <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.

[0038] 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.

[0039] <1.3> Hiding layer To impart the decorative sheet 1 with the ability to conceal the substrate B, for example, a colored sheet can be used as the base layer 2, or an opaque concealing layer 8 can be 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 concealment, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide, or the like, as the pigment. Furthermore, to enhance the concealing ability, 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.

[0040] <1.4> Picture 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 products 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 that includes a curing agent. The design layer 3 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 3 may further contain, in addition to the binder, pigments, colorants such as dyes, extender pigments, solvents, and various additives, which 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.

[0041] 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.

[0042] <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.

[0043] The resin material for the adhesive layer 7 is not particularly limited, and may be appropriately selected from acrylic, polyester, polyurethane, epoxy, and other resin materials. Alternatively, an ethylene-vinyl acetate copolymer resin adhesive may be used as the resin material for the adhesive layer 7. The coating method may 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, followed by lamination of the transparent resin layer 4. The adhesive layer 7 may be omitted if sufficient adhesive strength is obtained between the transparent resin layer 4 and the design layer 3.

[0044] <1.6>Transparent resin layer An olefin-based resin is preferably used as the resin material of 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 (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.

[0045] 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 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 as needed. Generally, phenol-based, sulfur-based, phosphorus-based, and hydrazine-based heat stabilizers are used, and hindered amine-based and other light stabilizers are used, each added in any combination.

[0046] <1.7>Surface protective layer The surface of the surface protection layer 5 has an uneven structure including a plurality of ridge portions 5B each protruding in a ridge shape. Here, the surface protection layer 5 includes a base portion 5A and a plurality of ridge portions 5B each protruding in a ridge shape from one surface of the base portion 5A. These ridge portions 5B form the uneven structure.

[0047] 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 or may not be branched 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 structure provided on the surface of the surface protective layer 5, and the base portion 5A refers to the portion of the surface protective layer 5 excluding the ridge portions 5B.

[0048] 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.

[0049] The uneven structure formed by the ridge portions 5B has a surface texture aspect ratio Str of 0.8 or more. Here, the surface texture aspect ratio Str is a surface texture parameter defined in ISO 25178. The surface texture aspect ratio Str is preferably 0.8 or more, and more preferably 0.85 or more. The surface texture aspect ratio Str is at most 1, but in one example it is 0.94 or less, and in another example it is 0.93 or less.

[0050] The uneven structure formed by the ridge portions 5B has an areal surface area ratio Smr1 (hereinafter sometimes abbreviated as "areal surface area ratio Smr1") separating the protruding peaks from the core portion of the sheet of paper of 14% or more. Here, the areal surface area ratio Smr1 separating the protruding peaks from the core portion of the sheet of paper of 14% or more is a surface texture parameter defined in ISO 25178. The areal surface area ratio Smr1 is preferably 14% or more, and more preferably 18% or more. In one example, the areal surface area ratio Smr1 is 35% or less, and in another example, 27% or less.

[0051] The aspect ratio Str and area load ratio Smr1 of the surface texture are each one of the characteristics of the surface protective layer 5 that affect the feel of the decorative sheet 1.

[0052] The surface protection layer 5 having a concave-convex structure with a large aspect ratio Str on its surface provides the user with substantially the same tactile sensation when the user presses the skin against the concave-convex structure and slides their skin over the concave-convex structure, for example, when the user presses the concave-convex structure with their finger and slides their finger over the concave-convex structure, regardless of the direction in which the finger is slid. In other words, the concave-convex structure with a large aspect ratio Str on its surface provides the user with an isotropic tactile sensation.

[0053] When a user presses a concave-convex structure with a large surface area load ratio Smr1 with their skin, for example, when they press the concave-convex structure with their finger, the finger comes into contact with the convex portions over a large area. In this situation, the tactile sensation that the concave-convex structure gives to the user is similar to the tactile sensation that a concave-convex structure made up of rough convex portions gives to the user (hereinafter referred to as a rough convex sensation).

[0054] When the uneven structure gives the user an isotropic tactile sensation, and this tactile sensation is similar to the tactile sensation given to the user by an uneven structure consisting of rough convex portions, the user perceives a tactile sensation similar to the tactile sensation given to the user by a layer in which rough spherical particles are uniformly dispersed and these spherical particles are partially exposed on the surface (hereinafter referred to as a coarse grain sensation).

[0055] The thickness of the surface protective layer 5 is preferably 12 μm or less, more preferably 8 μm or less, and even more preferably 5 μm or less. The thickness of the surface protective layer 5 is preferably 3 μm or more, and more preferably 4 μm or more.

[0056] Here, the thickness of the surface protective layer 5 is the thickness of a layer that has the same apparent area and volume as the surface protective layer 5 and a flat surface. The thickness of the surface protective layer 5 is determined, for example, by the following method. First, a cross section parallel to the thickness direction of the surface protective layer 5 and perpendicular to the length direction of the ridge portions 5B is imaged. Next, from this cross-sectional image, the dimension of the surface protective layer 5 in the width direction of the ridge portions 5B and the area of ​​the cross section of the surface protective layer 5 are determined. The thickness of the surface protective layer 5 is a value obtained by dividing this area by the above dimension. Note that 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.

[0057] If the coating film is made thicker, the cured film is more likely to expand in the in-plane direction during the first irradiation step described below, which makes it more likely that wrinkles corresponding to the ridge portions 5B will form on the coating film surface. However, if the coating film is made too thick, for example, the number of wrinkles per unit area may remain small, and individual wrinkles may grow. For this reason, if the thickness of the surface protection layer 5 is made too thick, the area load ratio Smr1 will increase, but the aspect ratio Str of the surface texture may decrease.

[0058] The surface protective layer 5 contains a cured resin. In one embodiment, the surface protective layer 5 further contains particles dispersed in the cured resin.

[0059] The cured resin contained in the surface protective layer 5 is preferably a cured product of an ionizing radiation curable resin. Here, "ionizing radiation" refers to a charged particle beam such as an electron beam. An ionizing radiation curable resin is cured by irradiation with ionizing radiation. An 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.

[0060] 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. 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.

[0061] 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% by mass or more of the ionizing radiation curable resin. The ionizing radiation curable resin preferably contains 70% by mass or more of acrylate, more preferably 80% by mass or more. The ionizing radiation curable resin is more preferably an acrylate.

[0062] The acrylate is preferably a difunctional or higher acrylate, and more preferably contains 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.

[0063] To obtain a surface protective layer 5 with excellent scratch resistance, the acrylate preferably contains a tri- or higher functional acrylate. The acrylate preferably contains a tri- or lower functional acrylate. For example, such an acrylate is a trifunctional acrylate, and for another example, it is a combination of a trifunctional acrylate and a difunctional acrylate.

[0064] The total proportion of the trifunctional acrylate and difunctional acrylate in the ionizing radiation curable resin is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass.

[0065] The proportion of the trifunctional acrylate in the ionizing radiation curable resin is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more, and this proportion may be 100% by mass.

[0066] 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 a ring-opened state and interposed between the acryloyl group and the methylol group.

[0067] 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. In other words, the number of repetitions can affect the surface properties of the surface protective layer 5. However, if the number of repetitions is increased, the crosslink density decreases, and the scratch resistance of the surface protective layer 5 decreases.

[0068] The proportion of the total acrylate containing a repeating unit in the ionizing radiation curable resin is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. This proportion may be 100% by mass. If this proportion is increased, expansion of the cured film in the in-plane direction becomes more likely to occur in the first irradiation step. In other words, this proportion may affect the surface properties of the surface protective layer 5.

[0069] In a preferred embodiment, the ionizing radiation curable resin is a trifunctional acrylate containing a repeating unit.

[0070] In yet another preferred embodiment, the ionizing radiation curable resin is a combination of a trifunctional acrylate containing a repeating unit and a bifunctional acrylate containing a repeating unit. In this case, the proportion of the trifunctional acrylate containing a repeating unit in the ionizing radiation curable resin is preferably 40% by mass to 95% by mass, more preferably 80% by mass to 95% by mass. Furthermore, the proportion of the bifunctional acrylate containing a repeating unit in the ionizing radiation curable resin is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 25% by mass.

[0071] In yet another preferred embodiment, the ionizing radiation curable resin is a combination of a trifunctional acrylate containing a repeating unit and a bifunctional acrylate not containing a repeating unit, such as tricyclodecane dimethanol diacrylate. In this case, the proportion of the trifunctional acrylate containing a repeating unit in the ionizing radiation curable resin is preferably 60% by mass to 95% by mass, more preferably 80% by mass to 95% by mass. Furthermore, the proportion of the bifunctional acrylate not containing a repeating unit in the ionizing radiation curable resin is preferably 5% by mass to 40% by mass, more preferably 10% by mass to 25% by mass.

[0072] Examples of trifunctional acrylates containing repeating units include EO-modified, PO-modified, or CL-modified trimethylolpropane triacrylate, glycerin triacrylate, isocyanurate triacrylate, or pentaerythritol triacrylate. In trifunctional acrylates containing repeating units, the number of repeating units is preferably in the range of 4 to 15, and more preferably in the range of 9 to 15. The molecular weight of the trifunctional acrylates containing repeating units is, for example, in the range of 296 to 1174.

[0073] The bifunctional acrylate containing a repeating unit is, for example, polyethylene glycol diacrylate or polypropylene glycol diacrylate, and may contain a caprolactone structure. In the bifunctional acrylate containing a repeating unit, the number of repeating units is preferably in the range of 4 to 14, and more preferably in the range of 4 to 9. The molecular weight of the bifunctional acrylate containing a repeating unit is, for example, in the range of 170 to 1139, and in another example, in the range of 184 to 1391.

[0074] When a trifunctional acrylate containing a repeating unit and a bifunctional acrylate containing a repeating unit are used in combination, the number of repeating units in the bifunctional acrylate is preferably smaller than the number of repeating units in the trifunctional acrylate. For example, when the number of repeating units in the trifunctional acrylate is within the range of 9 to 15, the number of repeating units in the bifunctional acrylate is preferably within the range of 3 to 9. Reducing the number of repeating units in the bifunctional acrylate reduces the ease of molecular movement in the surface protective layer 5, which increases the hardness of the surface protective layer and tends to improve its scratch resistance.

[0075] 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.

[0076] In one embodiment, the surface protective layer 5 may contain particles dispersed in a cured resin. Examples of the particles contained in the surface protective layer 5 include particles made of organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads, and particles made of inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.

[0077] The particles preferably have an average particle size (D50) in the range of 3 μm to 8 μm, more preferably in the range of 4 μm to 8 μm, and even more preferably in the range of 5 μm to 8 μm.

[0078] When the surface protective layer 5 contains particles, wrinkles can be more uniformly formed on the coating surface in the first irradiation step described below. If the average particle size (D50) of the particles is large, the particles tend to fall off from the surface protective layer 5, which may make it difficult to achieve high scratch resistance. If the particles are small, the effect of forming wrinkles uniformly is small.

[0079] Here, the "average particle size" or "average particle size (D50)" refers to the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. If 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 essentially 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.

[0080] In a preferred embodiment, the resin contained in the surface protective layer 5 to which the particles are added is a combination of a trifunctional acrylate containing a repeating unit and a bifunctional acrylate containing a repeating unit. In a more preferred embodiment, the number of repeating units contained in the bifunctional acrylate in this case is less than the number of repeating units contained in the trifunctional acrylate. In this case, the role of the trifunctional acrylate is to generate wrinkles on the coating film surface, while the role of the bifunctional acrylate not only generates wrinkles but also reduces the viscosity of the acrylate monomer coating solution without changing the ease of molecular mobility, which affects scratch resistance, thereby improving coatability during production.

[0081] As described above, the addition of particles to the surface protective layer 5 contributes to more uniform wrinkle formation on the coating film surface in the first irradiation step described below. However, when the resin contained in the surface protective layer 5 is a monopolymer of a polyfunctional acrylate containing a repeating unit, adding particles thereto may result in a surface texture that does not have the desired rough convexity / concave structure. For example, when the resin is a monopolymer of a trifunctional acrylate with a repeating unit having 9 or more repeating units, adding particles thereto tends to result in a surface texture that has a fine convexity / concave structure. In contrast, by using a combination of the above two types of acrylate as the resin contained in the surface protective layer 5, it is possible to obtain the above-mentioned effects of adding particles while also obtaining a surface texture that has the desired rough convexity / concave structure.

[0082] In a more preferred embodiment, the resin contained in the surface protection layer 5 to which the particles are added has a repeating number of the repeating structure contained in the trifunctional acrylate in the range of 9 to 15, and a repeating number of the repeating structure contained in the bifunctional acrylate in the range of 3 to 9. In this case, as described above, scratch resistance is further improved.

[0083] The amount of particles in the surface protective layer 5 is preferably in the range of 3 to 10 parts by mass, more preferably 5 to 10 parts by mass, per 100 parts by mass of the cured resin.

[0084] When the amount of particles added is within the above range, the effect of generating wrinkles uniformly is particularly large. If the amount of particles added is too large, the particles are likely to fall off from the surface protective layer 5, which may make it difficult to achieve high scratch resistance. If the amount of particles added is too small, it may be difficult to provide the user with an isotropic tactile sensation on the surface of the surface protective layer 5.

[0085] The decorative sheet 1 preferably has a specular gloss GS(60°) of 10% or less, more preferably 7% or less, and even more preferably 5% or less in the area corresponding to the uneven structure. Here, "specular gloss GS(60°)" is the measured value measured at an incident angle of 60 degrees using a glossmeter conforming to JIS Z8741:1997. The specular gloss GS(60°) of the area corresponding to the uneven structure is at least 0%, and in one example is 0.1% or more.

[0086] <2> Manufacturing method of decorative sheet The decorative sheet 1 is produced, for example, by the following method: For the sake of brevity, explanations regarding the design layer 3, transparent resin layer 4, primer layer 6, adhesive layer 7, and hiding layer 8 will be omitted here.

[0087] 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.

[0088] The coating liquid for the surface protective layer contains the resin and the particles 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 an ultraviolet absorber and a light stabilizer. 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 5 having low gloss can be formed without a gloss adjuster (matt additive).

[0089] 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, 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.

[0090] 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 nm 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 coating film uncured.

[0091] The coating film after the first irradiation step has wrinkles on its surface that correspond 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.

[0092] As described above, the first radiation can only reach a position several tens to several hundreds of nanometers from the outermost surface of the coating film. In other words, the crosslinking reaction of the ionizing radiation-curable resin occurs only on the surface of the coating film, and highly fluid uncured resin is present in regions more than several tens to several hundreds of nanometers from the outermost surface. The molecules contained in the highly fluid resin swell the cured film, increasing its volume. This increase in volume in the in-plane direction generates in-plane compressive stress in the cured film, which in turn buckles the cured film and causes wrinkles on the surface of the coating film.

[0093] The first radiation can be extracted from excimer VUV (Vacuum Ultra Violet) light. Excimer VUV light can be produced 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 the atoms of the discharge gas (rare gas), which momentarily enters an excimer state. When returning from this excimer state to the ground state, light is emitted in a wavelength range specific to that excimer.

[0094] 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).

[0095] 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.

[0096] The first irradiation step is performed 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 performed in, for example, a nitrogen gas atmosphere. 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 film surface. Therefore, changing the residual oxygen concentration in the reaction atmosphere can also change the surface properties of the surface protection layer 5. The oxygen concentration in the gas phase during the first irradiation step, i.e., the residual oxygen concentration in the reaction atmosphere, is preferably 250 ppm or less, more preferably 50 ppm or less.

[0097] In the first irradiation step, the distance from the light source to the coating film (hereinafter referred to as irradiation distance) is preferably 40 mm or less, more preferably 15 mm or less. The irradiation distance is, for example, 7 mm or more. If the irradiation distance is increased, the absorption of light of 200 nm or less by oxygen increases.

[0098] The cumulative light intensity of the first radiation is 0.6 mJ / cm 2 More than 220mJ / cm 2 It is preferable that the dose is 1.2 mJ / cm or less. 2 More than 120mJ / cm 2 More preferably, it is 4 mJ / cm or less. 2 More than 55mJ / cm 2 It is more preferable that the integrated light amount is less than 1000 W. When the integrated light amount is less, the expansion of the cured film in the in-plane direction is reduced. When the integrated light amount is greater, the surface condition of the coating film is deteriorated. deteriorates.

[0099] In the first irradiation step, the temperature of the coating film made of the coating liquid for the surface protective layer is preferably controlled within a range of 20°C to 65°C. Increasing the temperature of the coating film reduces the viscosity of the coating liquid for the surface protective layer and increases its fluidity. Increasing the temperature of the coating film also increases the flexibility of the cured film. Therefore, the temperature of the coating film affects the formation of wrinkles on the coating film surface. Therefore, by changing the temperature, the surface properties of the surface protective layer 5 can be changed.

[0100] 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.

[0101] 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.

[0102] When ionizing radiation is used as the second radiation, the dose of the second radiation is preferably 4 kGy or more and 60 kGy or less, and more preferably 6 kGy or less. 2 If the dose is too low, curing will be insufficient, and if the dose is too high, the ionizing radiation is more likely to induce embrittlement of the decorative sheet.

[0103] When ultraviolet light is used as the secondary radiation, the cumulative light intensity of the secondary radiation is 15 mJ / cm 2 More than 600mJ / cm 2 It is preferable that the dose is 60 mJ / cm or less. 2 More than 420mJ / cm 2 More preferably, it is 120 mJ / cm or less. 2 More than 320mJ / cm 2 It is more preferable that:

[0104] In this method, the surface protective layer 5 is formed so that its uneven structure has the above-described surface texture. As described above, this surface texture is affected by the composition of the coating liquid for the surface protective layer, the thickness of the coating film made from this coating liquid, and various conditions in the first irradiation step. Therefore, for example, to form a surface protective layer 5 having a desired composition, thickness, and surface texture, various conditions in the first irradiation step, such as the temperature of the coating film, the oxygen concentration in the atmosphere, the irradiation distance, and the integrated light amount of the first radiation, are appropriately set so as to obtain the above-described surface texture.

[0105] The decorative sheet 1 may also be manufactured by other methods. For example, a plate may be formed using the method described above for the surface protective layer 5, and this plate may be used to form the surface protective layer 5 having a concave-convex structure on its surface. For example, a plate for primary transfer may be formed using the method described above for the surface protective layer 5, a plate for secondary transfer may be formed by transfer using this primary transfer plate, and a surface protective layer 5 having a concave-convex structure on its surface may be formed by transfer using this secondary transfer plate.

[0106] <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 texture. Such a decorative sheet 1 provides an isotropic tactile sensation to a user when the user presses the uneven structure on the surface of the surface protective layer 5 and slides their skin over the uneven structure. Furthermore, the tactile sensation provided to a user when the above uneven structure presses their skin is similar to the tactile sensation (rough convex sensation) provided to a user by an uneven structure consisting of rough convex portions. The combination of the isotropic tactile sensation and the rough convex sensation allows the user to perceive a tactile sensation similar to the tactile sensation (rough graininess) provided to a user by a layer in which coarse spherical particles are uniformly dispersed and these spherical particles are partially exposed on the surface. In other words, the decorative sheet 1 provides a unique tactile sensation to a user who touches the uneven structure on the surface of its surface protective layer 5.

[0107] Furthermore, this decorative sheet 1 has excellent scratch resistance, as will be explained below. A surface protective layer having a textured surface can also be obtained by forming a layer containing particles and a binder resin so that convex portions corresponding to the shape of the particles or their aggregates are formed on the surface. However, such a surface protective layer has a large number of particles exposed on its surface, making it prone to particle shedding due to abrasion, etc. Moreover, in a surface protective layer with such a structure, the particles or their aggregates themselves constitute the convex portions, and particle shedding significantly changes the optical properties of the surface protective layer. Therefore, when a certain portion of the surface protective layer is abraded, a large number of particles are shed from that portion, and the optical properties of that portion become significantly different from the optical properties of other portions. As a result, the abraded portion becomes easily recognized as, for example, a scratch.

[0108] In contrast, in the decorative sheet 1, the uneven structure provided on the surface of the surface protective layer 5 is obtained by creating wrinkles on the surface of the coating film. This surface protective layer 5 may contain particles, but these particles are not essential.

[0109] Furthermore, in the decorative sheet 1, even if the surface protective layer 5 contains particles, these particles are intended to cause uniform and dense buckling of the cured film. Therefore, the number of particles per surface area of ​​the surface protective layer 5 can be small. Furthermore, particles that may fall off due to abrasion are limited to those located near the tops of the ridge portions 5B.

[0110] Furthermore, the ridge portions 5B are mostly made of a cured resin, so even if particles fall off, the effect of this falling on the optical properties of the surface protection layer 5 is small.

[0111] Therefore, even if a portion of the surface protective layer 5 of the decorative sheet 1 is scratched, the optical properties of that portion change only slightly. Therefore, with this decorative sheet 1, it is unlikely that the scratched portion will be easily recognized as a scratch, for example. In other words, the decorative sheet 1 has excellent scratch resistance. [Example]

[0112] Examples of the present invention are described below. The "particle size" described below is the above-mentioned "average particle size (D50)."

[0113] <Example 1: Working Example> The decorative sheet 1 described with reference to Figures 1 to 3 was produced by the following method: In this example, the transparent resin layer 4, primer layer 6, adhesive layer 7 and masking layer 8 were omitted.

[0114] 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 picture layer 3 was formed using an oil-based nitrocellulose resin gravure printing ink (PCNT (PCRNT) various colors, manufactured by Toyo Ink Co., Ltd.).

[0115] Next, a coating liquid for a surface protective layer was applied onto the design layer 3. The following ionizing radiation curable resin A was used as the coating liquid for the surface protective layer. ·Ionizing radiation curable resin A Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer) The coating film made of the coating liquid for the surface protective layer was formed to a thickness of 5 μm.

[0116] Thereafter, the first irradiation step was carried out. Specifically, under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm, ultraviolet rays having a wavelength of 172 nm were 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 7 mJ / cm. 2 Here, the distance from the Xe excimer lamp to the coating film (irradiation distance) was set to 10 mm. In addition, the temperature of the raw fabric layer 2 was controlled so that the temperature of the coating film was 25°C. This caused wrinkles to form on the surface of the coating film.

[0117] Subsequently, the second irradiation step was carried out. Specifically, the coating film was irradiated with ionizing radiation to cure the entire coating film, thereby forming a surface protective layer 5. In this manner, a decorative sheet 1 was obtained.

[0118] <Example 2: Comparative Example> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the coating liquid for the surface protective layer was prepared by blending the following particles with the following ionizing radiation curable resin A. ·Ionizing radiation curable resin A Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer) Blend: 100 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 5 parts by mass In this example, the coating film made of the coating liquid for the surface protective layer was formed to a thickness of 10 μm. In this manner, a decorative sheet 1 was obtained.

[0119] <Example 3: Comparative Example> Decorative sheet 1 was produced in the same manner as in Example 2, except for the following points: In this example, in the first irradiation step, the temperature of raw fabric layer 2 was controlled so that the temperature of the coating film was 65° C. In this manner, decorative sheet 1 was obtained.

[0120] <Example 4: Comparative Example> Decorative sheet 1 was produced in the same manner as in Example 2, except for the following points. That is, in this example, the coating film made from the coating liquid for surface protective layer was formed so as to have a thickness of 5 μm. In this manner, decorative sheet 1 was obtained.

[0121] <Example 5: Comparative Example> Decorative sheet 1 was produced in the same manner as in Example 4, except for the following points: In this example, the temperature of raw fabric layer 2 was controlled in the first irradiation step so that the temperature of the coating film was 65° C. In this manner, decorative sheet 1 was obtained.

[0122] <Example 6: Comparative Example> A decorative sheet 1 was produced in the same manner as in Example 4, except for the following points: In this example, the irradiation distance in the first irradiation step was set to 15 mm. In this manner, a decorative sheet 1 was obtained.

[0123] <Example 7: Comparative Example> 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 liquid for the surface protective layer was used which was a mixture of the following ionizing radiation curable resin A, ionizing radiation curable resin B, and particles. ·Ionizing radiation curable resin A Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer) Blend: 40 parts by mass ·Ionizing radiation curable resin B Type: Polyethylene glycol diacrylate (EO 4 moles added) Product name: Light Acrylate 14EG-A (Kyoeisha Chemical Co., Ltd.) Blend: 60 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 5 parts by mass In this manner, a decorative sheet 1 was obtained.

[0124] <Example 8: Working Example> Decorative sheet 1 was produced in the same manner as in Example 7, except for the following points: In this example, the temperature of raw fabric layer 2 was controlled in the first irradiation step so that the temperature of the coating film was 65° C. In this manner, decorative sheet 1 was obtained.

[0125] <Example 9: Comparative Example> 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 liquid for the surface protective layer was used which was a mixture of the following ionizing radiation curable resin A, ionizing radiation curable resin C, and particles. ·Ionizing radiation curable resin A Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer) Blend: 40 parts by mass ·Ionizing radiation curable resin C Type: Polyethylene glycol diacrylate (EO 14 moles added) Product name: Light Acrylate 14EG-A (Kyoeisha Chemical Co., Ltd.) Blend: 60 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 5 parts by mass In this manner, a decorative sheet 1 was obtained.

[0126] <Example 10: Working Example> Decorative sheet 1 was produced in the same manner as in Example 9, except for the following points: In this example, in the first irradiation step, the temperature of raw fabric layer 2 was controlled so that the temperature of the coating film was 65° C. In this manner, decorative sheet 1 was obtained.

[0127] <Example 11: Comparative Example> 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 liquid for the surface protective layer was used which was a mixture of the following ionizing radiation curable resin A, ionizing radiation curable resin D, and particles. ·Ionizing radiation curable resin A Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer) Blend: 40 parts by mass ·Ionizing radiation curable resin D Type: Tricyclodecane dimethanol diacrylate Product name: Light Acrylate DCP-A (Kyoeisha Chemical Co., Ltd.) Blend: 60 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 5 parts by mass In this manner, a decorative sheet 1 was obtained.

[0128] <Example 12: Comparative Example> A decorative sheet 1 was produced in the same manner as in Example 11, except for the following points: In this example, the temperature of the raw fabric layer 2 was controlled in the first irradiation step so that the temperature of the coating film was 65° C. In this manner, a decorative sheet 1 was obtained.

[0129] <Example 13: Comparative Example> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the coating liquid for the surface protective layer was prepared by blending the following particles with the following ionizing radiation curable resin A. ·Ionizing radiation curable resin A Type: Trimethylolpropane EO-modified triacrylate (EO 15 moles added) Product name: SR9035 (Sartomer) Blend: 100 parts by mass ·particle Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 5 parts by mass In this example, the first irradiation step was omitted. In this manner, a decorative sheet 1 was obtained.

[0130] <Example 14: Comparative Example> Decorative sheet 1 was produced in the same manner as in Example 13, except for the following points: In this example, the amount of particles was 13 parts by mass per 100 parts by mass of ionizing radiation curable resin A. In this manner, decorative sheet 1 was obtained.

[0131] <Evaluation> Each of the above decorative sheets was subjected to the following evaluations.

[0132] (1) Shape of the convex part For each of the decorative sheets, the surface protective layer was observed under a microscope to confirm the shape of the protrusions. "Protrusions" in Tables 1 and 2 below refer to the shape of these protrusions.

[0133] (2) Surface texture The surface texture of each of the decorative sheets was measured, and the aspect ratio Str and area load ratio Smr1 of the surface texture were determined.

[0134] (3) Thickness of the surface protection layer The thickness of the surface protective layer for each of the decorative sheets was measured using the same method as described above. Specifically, the decorative sheet 1 was embedded in a resin such as a cold-curing epoxy resin or a UV-curable resin, and the resin was allowed to fully harden. The decorative sheet 1 was then cut to reveal its cross section, and mechanically polished to obtain a measurement surface. The cross section of the surface protective layer was then imaged using a SIGMA 500 scanning electron microscope manufactured by Carl Zeiss Microscopy. The imaging was performed at an acceleration voltage of 0.5 keV (low acceleration voltage), in SE2 mode, and at a magnification of 2000x. No sputtering was performed on the measurement sample. The dimensions of the surface protective layer in the width direction of the ridges and the area of ​​the cross section of the surface protective layer were then calculated from the cross-sectional image. The "thickness of the surface protective layer" was calculated by dividing this area by the above dimensions. The "thickness of the surface protective layer" obtained in this manner was equal to the thickness of the coating film made from the surface protective layer coating liquid.

[0135] (4) Glossiness The specular gloss (GS60°) of each of the above decorative sheets was measured using a Rhopoint IQ (manufactured by Konica Minolta, Inc.) The "gloss" in Tables 1 and 2 below represents this specular gloss (GS60°).

[0136] (5) Isotropy of tactile sensation For each of the decorative sheets described above, the isotropy of the tactile feel of the surface protective layer was evaluated by the following method.

[0137] First, we conducted advance preparations to ensure that the evaluation criteria were consistent across evaluators. Specifically, standard test specimens with different surface textures were prepared. These standard test specimens included those with different surface texture aspect ratios (Str). Next, five evaluators, while blindfolded, were asked to gently press their finger against the surface of the standard test specimen and slide their fingertip linearly across the surface. Each evaluator was then asked to classify the standard test specimens into the following three groups based on the change in tactile sensation depending on the direction of the finger slide. Group 1: They felt a large change in the tactile sensation depending on the direction they slid their finger. Group 2: They felt a slight change in the tactile sensation depending on the direction they slid their finger. Group 3: No change in tactile sensation was felt depending on the direction of the finger movement.

[0138] The above procedure was repeated until the ratings by each rater were consistent for three or more consecutive times, and the ratings between raters were consistent for three consecutive times.

[0139] Next, for each of the decorative sheets, each of the evaluators was blindfolded and asked to gently press the surface of the surface protective layer with a finger and slide their fingertip in a straight line across the surface, and to classify the decorative sheets into one of the three groups based on the magnitude of change in tactile sensation depending on the direction of the finger slide. This procedure was then repeated until the evaluations by each evaluator were consistent for three or more consecutive evaluations, and the evaluation results between evaluators were consistent for three consecutive evaluations. From these results, the tactile isotropy was evaluated according to the following criteria. AA: Group 3 A: Group 2 B: Group 1 In addition, "isotropy" in Tables 1 and 2 below indicates this isotropy of the tactile sensation.

[0140] (6) Rough convex texture Each of the decorative sheets was evaluated for roughness and projection of the surface protective layer by the following method.

[0141] First, advance preparations were made to ensure that the evaluation criteria were consistent across evaluators. Specifically, standard test pieces with different surface textures were prepared. These standard test pieces included those with different areal load ratios (Smr1). Next, five evaluators were blindfolded and asked to lightly press the surface of the standard test pieces with their finger and, based on the tactile sensation they perceived, to classify the standard test pieces into the following three groups. Group 1: They felt the presence of an uneven structure consisting of rough protrusions. Group 2: perceived a texture intermediate between that of Group 1 and Group 2. Group 3: The presence of an uneven structure consisting of minute protrusions was felt.

[0142] The above procedure was repeated until the ratings by each rater were consistent for three or more consecutive times, and the ratings between raters were consistent for three consecutive times.

[0143] Next, for each of the decorative sheets, each of the evaluators was asked to lightly press the surface of the surface protective layer with a finger while blindfolded, and to classify the decorative sheets into one of the three groups based on the tactile sensation they perceived. This procedure was then 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 roughness of the convex texture was evaluated according to the following criteria. AA: Group 1 A: Group 2 B: Group 3

[0144] (7) Coarse grain Each of the decorative sheets was evaluated for rough graininess of the surface protective layer by the following method.

[0145] First, advance preparations were made to ensure that the evaluation criteria were consistent across evaluators. Specifically, standard test specimens with different surface textures were prepared. These standard test specimens included those with different surface texture aspect ratios (Str) and areal mass ratios (Smr1). Next, five evaluators were blindfolded and asked to gently press their fingers against the surface of the standard test specimens while moving their fingertips in small circles. Based on the tactile sensations they perceived, they were asked to classify the standard test specimens into the following three groups. Group 1: In the process of moving their fingertips in a circular motion, they felt the presence of an uneven structure consisting of rough protrusions. Group 2: In the process of moving their fingertips in a circular motion, they did not feel the presence of a rough, uneven structure made up of rough protrusions, but they felt a significant change in the sensation of touch, or they felt the presence of a rough, uneven structure made up of protrusions between coarse and fine. Group 3: In the process of moving their fingertips in a circular motion, they felt a slight change in the sensation of touch or sensed the presence of an uneven structure made up of minute protrusions.

[0146] The above procedure was repeated until the ratings by each rater were consistent for three or more consecutive times, and the ratings between raters were consistent for three consecutive times.

[0147] Next, for each of the decorative sheets, each of the evaluators was asked, while blindfolded, to gently press the surface of the surface protective layer with their fingertips in a circular motion, and to classify the decorative sheets into one of the three groups based on the tactile sensation they perceived. This procedure was then 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 coarse graininess was evaluated according to the following criteria: AA: Group 1 A: Group 2 B: Group 3

[0148] (8) 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 the surface of the decorative sheet was visually inspected for scratches and changes in gloss.

[0149] The evaluation criteria were as follows: AA: No scratches or changes in gloss occurred on the surface. A: Minor scratches or changes in gloss have occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.

[0150] (9) Overall rating Each of the decorative sheets was comprehensively evaluated based on the coarse grain and scratch resistance. The evaluation criteria were as follows: AA: Both the roughness and scratch resistance were rated "AA." A: Either the roughness or scratch resistance was rated "A", and the other was rated "AA" or "A". B: At least one of the roughness and scratch resistance was evaluated as "B".

[0151] The evaluation results are shown in Tables 1 and 2.

[0152] [Table 1]

[0153] [Table 2]

[0154] As shown in Tables 1 and 2, the decorative sheets of Examples 1, 8, and 10 gave the evaluators a rough grain feeling. The decorative sheets of Examples 1, 8, and 10 also had excellent scratch resistance, with the decorative sheets of Examples 1 and 8 having particularly excellent scratch resistance. The decorative sheets of Examples 1, 8, and 10 also had low gloss.

[0155] In contrast, the decorative sheets of Examples 2 to 7, 9, 11, and 12 had excellent scratch resistance but did not give the evaluators a rough grain feeling. The decorative sheet of Example 13 did not give the evaluators a rough grain feeling and also had poor scratch resistance. The decorative sheet of Example 14 gave the evaluators a rough grain feeling but had poor scratch resistance. [Explanation of symbols]

[0156] 1...decorative sheet, 2...raw material layer, 3...pattern layer, 4...transparent resin layer, 5...surface protection layer, 5A...base, 5B...ridged portion, 6...primer layer, 7...adhesive layer, 8...hiding layer, 11...decorative material, B...base material.

Claims

1. A substrate layer and a surface protective layer provided on one surface of the substrate layer, the surface protection layer includes a cured resin and has a concave-convex structure including a plurality of ridge-like portions on a surface thereof, each of the ridge-like portions protruding from the surface; The decorative sheet has a surface texture aspect ratio Str of 0.8 or more, and a load area ratio Smr1 separating the protruding peaks from the core portion is 14% or more.

2. 2. The decorative sheet according to claim 1, wherein the specular gloss GS(60°) of the portion corresponding to said uneven structure is 5% or less.

3. 2. The decorative sheet according to claim 1, wherein said surface protective layer has a thickness of 12 μm or less.

4. 2. The decorative sheet according to claim 1, wherein said resin is an ionizing radiation curable resin.

5. 5. The decorative sheet according to claim 4, wherein said resin is an acrylate.

6. The decorative sheet according to claim 5 , wherein the acrylate comprises a polyfunctional acrylate containing a repeating structure.

7. 5. The decorative sheet according to claim 4, wherein the resin contains a trifunctional acrylate containing a repeating unit and a difunctional acrylate containing a repeating unit.

8. 8. The decorative sheet according to claim 7, wherein the proportion of said trifunctional acrylate in said resin is in the range of 40% by mass or more and 95% by mass or less, and the proportion of said bifunctional acrylate is in the range of 5% by mass or more and 60% by mass or less.

9. The decorative sheet according to claim 7, wherein the number of repetitions of the repeating structure contained in the bifunctional acrylate is less than the number of repetitions of the repeating structure contained in the trifunctional acrylate.

10. The decorative sheet according to claim 9, wherein the number of repetitions of the repeating structure contained in the trifunctional acrylate is in the range of 9 to 15, and the number of repetitions of the repeating structure contained in the bifunctional acrylate is in the range of 3 to 9.

11. The decorative sheet according to claim 7 , wherein the surface protective layer further comprises particles dispersed in the cured product.

12. 12. The decorative sheet according to claim 11, wherein the amount of said particles is in the range of 3 parts by mass to 10 parts by mass per 100 parts by mass of said cured product.

13. 2. The decorative sheet according to claim 1, further comprising a pattern layer between said base layer and said surface protective layer.

14. The decorative sheet according to any one of claims 1 to 13; a substrate to which the decorative sheet is attached; A cosmetic material comprising:

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