Decorative sheet

Abstract

The present invention provides a decorative sheet which gives a moist texture. This decorative sheet (1) is provided with a base layer (2) and a surface protection layer (5) that is provided on one surface of the base layer (2). The surface of the surface protection layer (5) is provided with a relief structure that includes a plurality of ridge-shaped parts each protruding in a ridge shape. The wrinkle area ratio of the surface of the surface protection layer (5) is 0.45 to 1.0 inclusive.

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 a raw fabric layer and a surface protective layer provided on one surface of the raw fabric layer, wherein the surface of the surface protective layer is provided with an uneven structure including a plurality of ridge-like portions, each of which protrudes in a ridge-like shape, and the wrinkle area ratio on the surface of the surface protective layer is 0.45 or more and 1.0 or less.

[0012] According to another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the surface protective layer contains a cured resin and particles.

[0013] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the particles have an average particle size of 3 μm or more.

[0014] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the particles have an average particle size of 3 μm or more and 11 μm or less.

[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 particles are contained in the surface protective layer in an amount of 3 to 11 parts by mass per 100 parts by mass of the resin.

[0016] 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.

[0017] 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.

[0018] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, 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.

[0019] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, 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.

[0020] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the surface protective layer further comprises a sliding property imparting agent, and the sliding property imparting agent is contained in the surface protective layer in an amount of 0.01 parts by mass or more and 0.03 parts by mass or less per 100 parts by mass of the resin.

[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 thickness t of the surface protective layer is 2 μm or more and 18 μm or less.

[0022] 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.

[0023] In the decorative sheet according to any one of the above aspects, the glossiness of the surface protective layer is less than 10.

[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.

[0025] According to yet another aspect of the present invention, there is provided a method for producing a decorative sheet, comprising: stirring a coating liquid containing an ionizing radiation curable resin and particles; forming a coating film made of the coating liquid on a base fabric layer; carrying out a first irradiation step of irradiating the coating film with light having a wavelength of 200 nm or less; and then carrying out a second irradiation step of irradiating the coating film with ionizing radiation or ultraviolet light having a wavelength longer than that of the light irradiated in the first irradiation step, wherein stirring the coating liquid and the first irradiation step are carried out such that the surface of the coating film after the second irradiation step has a wrinkle area ratio of 0.45 to 1.0.

[0026] According to the present invention, a decorative sheet that gives a moist feel to the touch is provided.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] <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.

[0032] 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).

[0033] 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.

[0034] 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.

[0035] 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.

[0036] <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.

[0037] 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.

[0038] <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.

[0039] 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.

[0040] <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.

[0041] <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.

[0042] 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.

[0043] <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.

[0044] 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.

[0045] <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.

[0046] 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.

[0047] <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 an uneven structure.

[0048] 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.

[0049] 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.

[0050] The surface of the surface protection layer 5 on which the concave-convex structure is provided has a wrinkled region ratio of 0.45 to 1.0, preferably 0.8 to 1.0.

[0051] Here, the wrinkled region ratio is a value obtained by the following method: First, a surface shape image is obtained using a laser microscope for the uneven structure provided on the surface of the surface protection layer 5. This surface shape image has brightness corresponding to the height.

[0052] An Olympus OLS-4000 laser microscope can be used. The surface profile image is obtained by setting the objective lens magnification to 10x and capturing an image of a square area with a side length of 1 mm. This image has 1024 pixels in both the vertical and horizontal directions.

[0053] The acquired image is then converted into an 8-bit grayscale image, where the pixel value of the highest pixel is set to 255 and the pixel value of the lowest pixel is set to 0.

[0054] Next, the resulting grayscale image is divided into a grid of 8 rows and 8 columns to obtain 64 divided images, each of which has 128 pixels in each direction.

[0055] Next, for each divided image, the arithmetic mean of the pixel values ​​of the 16,384 (128 x 128) pixels contained therein is calculated, and the obtained arithmetic mean is used as the threshold value.

[0056] Next, the number of pixels in each divided image that have a pixel value less than the threshold is calculated, and the obtained number is called the number of black pixels.

[0057] Next, a divided image having a number of black pixels equal to or greater than 0.55 times 16384, i.e., equal to or greater than 9012, is determined to be a wrinkled region, and a divided image having a number of black pixels less than 9012 is determined to be a non-wrinkled region.

[0058] Next, the wrinkled region ratio is obtained by calculating the ratio of the number of wrinkled regions to the total number of divided images, i.e., 64 images.

[0059] Incidentally, when a finger is pressed against the surface of the surface protective layer 5 and then slid across the surface, if the resistance to pressure is small and the contact area gradually increases with increasing pressure, the surface of the decorative sheet 1 feels as if it is sticking to the finger. This feeling can be associated with a "moist feeling."

[0060] If the wrinkles are arranged at an excessively large pitch, even a slight increase in pressure when pressing a finger against the surface will result in a large increase in the contact area, and a moist feel will not be obtained. Therefore, it is desirable that the surface of the surface protection layer 5 has wrinkles in many small areas.

[0061] Furthermore, if the area of ​​the upper surface of the wrinkled convex portions is large, there is a large resistance to pressing when a finger is pressed against it. Furthermore, in this case, even a slight increase in pressure when pressing a finger against it significantly increases the contact area. Therefore, a moist feel cannot be obtained. Therefore, it is desirable that the area of ​​the upper surface of the wrinkled convex portions be small.

[0062] The areas of the surface protective layer 5 that correspond to the divided images are sufficiently small. Furthermore, among these areas, those that correspond to the wrinkled areas have wrinkles and a small proportion of convex portions. This structure corresponds to the desirable structure described above. Therefore, when the surface of the surface protective layer 5 is pressed with a finger and then slid across the surface, the decorative sheet 1 has low resistance to pressure, and the contact area gradually increases as the pressure increases, providing a moist feel.

[0063] The thickness t of the surface protective layer 5 is preferably 2 μm or more and 18 μm or less. The thickness t of the surface protective layer 5 is more preferably 3 μm or more and 10 μm or less. 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, if the thickness of the surface protective layer 5 is too small, it becomes difficult to achieve a low gloss level. Furthermore, if the thickness of the surface protective layer 5 is too large, it becomes difficult to achieve high processability. Processability will be described later. Here, the thickness of the surface protective layer 5 is determined by observing the cross section with a scanning electron microscope and averaging the values ​​at 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.

[0064] The surface protective layer 5 preferably 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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 gloss value tends to decrease and the design tends to improve. However, if the number of repetitions is increased, the crosslinking density decreases, and the scratch resistance of the surface protective layer decreases. Furthermore, if an acrylate with a small number of repetitions is used, it may be difficult to achieve high processability.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] The particles contained in the surface protective layer 5 can 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. When the surface protective layer 5 contains particles, when the surface of the decorative sheet 1 is pressed with a finger and then slid across the surface, the user is likely to experience a tactile sensation as if the finger were sliding across the surface of the decorative sheet 1, while still feeling the unevenness. This tactile sensation can be associated with a "moist tactile sensation."

[0074] The particles preferably have an average particle size (D50) of 3 μm or more, more preferably 3 μm or more and 11 μm or less, and even more preferably 4 μm or more and 10 μm or less.

[0075] 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 user tends to feel a stronger sense of particle unevenness. Therefore, if the average particle size (D50) is too large, it can be difficult to achieve a "moist feel." Furthermore, when large particles are used, the particles are more likely to fall off from the surface protective layer 5, making it difficult to achieve high scratch resistance. Furthermore, when large particles are used, it can be difficult to achieve high processability. Furthermore, when particles are small, the effect of generating wrinkles uniformly tends to be reduced. Furthermore, when particles are small, the user may feel a "sticky feel" when sliding their fingers over the surface of the decorative sheet 1, due to the lack of a smooth feel.

[0076] 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.

[0077] The particles are preferably contained in the surface protective layer 5 in an amount of 3 to 11 parts by mass per 100 parts by mass of the resin. The amount of particles added is more preferably 4 to 10 parts by mass per 100 parts by mass of the resin. Note that "100 parts by mass of the resin" refers to the parts by mass of the solid content of the resin.

[0078] When the amount of particles added is within the above range, the effect of uniformly generating wrinkles is particularly significant. As a result, glossiness is reduced, and the effect of improving design is obtained. Furthermore, when a user touches the surface of the surface protection layer 5 with their finger and then moves their finger over the surface, the user is given a smooth tactile sensation. If the amount of particles added is too small, it may be difficult to give the user a smooth tactile sensation, making it difficult to achieve a "moist tactile sensation." In this case, the user may be given a sticky tactile sensation. In addition, in this case, the effect of uniformly generating wrinkles is likely to be reduced.

[0079] If the amount of particles added is large, when a user presses their finger against the decorative sheet 1, the user may feel a strong sense of unevenness due to the surface roughness, which may give the user a "rough feel." In this case, it becomes difficult to achieve a "moist feel." Furthermore, if the amount of particles added is large, particles are likely to fall off from the surface protective layer 5, which may make it difficult to achieve high scratch resistance and high processability. Furthermore, if the amount of particles added is large, it may become difficult to achieve high stain resistance.

[0080] The glossiness of the surface protective layer 5 is preferably less than 10.0. The glossiness of the surface protective layer 5 is more preferably equal to or less than 5. Here, the "glossiness" is a value measured at an incident angle of 60 degrees using a glossmeter conforming to JIS Z8741:1997.

[0081] Preferably, the surface protective layer 5 further contains a slidability imparting agent. The slidability imparting agent improves, for example, the ease with which a user slides their finger across the surface of the surface protective layer, i.e., improves slidability. When the surface protective layer 5 contains a slidability imparting agent, it can provide the user with an even more moist tactile sensation. The slidability imparting agent may be contained in the surface protective layer 5 as the above-described particles or as part of particles, or may be contained in the surface protective layer 5 in a dissolved state in a resin. In one example, the slidability imparting agent can be incorporated into the surface protective layer 5 by preparing a particulate slidability imparting agent and kneading it with a resin. In another example, the slidability imparting agent can be incorporated into the surface protective layer 5 by preparing an emulsion containing the slidability imparting agent and kneading it with a resin.

[0082] The sliding property-imparting agent includes, for example, a sliding property-imparting moiety with excellent sliding properties and a compatible moiety that is directly or indirectly bonded to the sliding property-imparting moiety and has excellent compatibility with the resin. The sliding property-imparting moiety is, for example, silicone. The compatible moiety is, for example, an acrylic group or a vinyl acetate group. An example of such a sliding property-imparting agent is an acrylic silicone resin. An acrylic silicone resin is a polymer compound having silicone as a main chain and acrylic groups as side chains. An acrylic silicone resin, for example, has a silicone core and an acrylic group as a shell that covers this core. With this structure, the acrylic group is exposed on the surface of the acrylic silicone resin, resulting in excellent compatibility with the resin. Therefore, bleeding out of the sliding property-imparting agent is unlikely to occur. Furthermore, with this structure, when shear force is applied, the silicone can also be exposed on the surface of the acrylic silicone resin, thereby improving sliding property. It should be noted that, for example, a fluorine-based resin can also be used as the sliding property-imparting agent.

[0083] The amount of the agent for imparting sliding properties contained in the surface protective layer 5 is preferably 0.01 parts by mass or more and 0.03 parts by mass or less per 100 parts by mass of the resin.

[0084] <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.

[0085] First, a coating liquid for the surface protective layer is prepared and stirred. The coating liquid for the surface protective layer contains, for example, the resin and the particles described above. Using a conventional stirring method, the particles appear to be uniformly mixed at first glance, but particle aggregation and other factors can cause uneven particle dispersion in microscopic areas. In this case, wrinkles are less likely to form uniformly on the surface of the surface protective layer 5. That is, the surface protective layer 5 has more wrinkle-free areas. The above-mentioned unevenness can be eliminated by stirring the coating liquid for the surface protective layer more strongly or for a longer period of time than with a conventional stirring method.

[0086] 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 a sliding agent, 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 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 a low gloss can be formed without a gloss adjuster (matt additive).

[0087] 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.

[0088] Next, 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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).

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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 ２ More preferably, it is 100 mJ / cm or less. ２ More than 300mJ / cm ２ It is more preferable that:

[0101] <3> Effect The decorative sheet 1 described with reference to Figures 1 to 3 has the 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 over the surface, for example, when pressing the surface of the surface protective layer 5 with their finger and sliding their finger over the surface. That is, when touched by the above action, this decorative sheet 1 can gradually increase the contact area between the finger and the convex surface while keeping the pressure resistance due to contact between the finger and the surface small. This gives the user a tactile sensation as if the surface of the decorative sheet is sticking to the finger.

[0102] 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.

[0103] Furthermore, when the surface protective layer 5 contains the aforementioned sliding property imparting agent, the aforementioned pushing resistance can be further reduced. This allows the user to feel as if the surface of the decorative sheet is sticking to the user's fingers. Therefore, in the above case, it is possible to provide the user with an even more moisturized feel.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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 thickness of the cured film and the degree of in-plane expansion of the cured film will also be affected by the integrated light amount in the first irradiation step. The thickness of the cured film and the degree of in-plane expansion of the cured film will then affect the surface properties of the surface protective layer. Furthermore, the particle size and amount of particles in the coating film, as well as the thickness of the coating film, also affect the formation of wrinkles.

[0108] Therefore, for example, by appropriately setting the stirring method of the coating liquid for the surface protective layer, the composition of the ionizing radiation curable resin, the particle size and amount added, 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 protective layer having the desired surface properties.

[0109] In addition, the primary transfer product obtained by performing transfer using this decorative sheet 1 as a plate has wide convex portions on the top surface formed in a small area. When a primary transfer product with such convex portions formed is pressed with a finger, not only is there a large resistance to pressing, but even a slight increase in pressure significantly increases the contact area. As a result, the primary transfer product does not give the user a moist feel to the touch. On the other hand, a secondary transfer product obtained by performing transfer using the primary transfer product as a plate has a surface shape similar to that used for the primary transfer. Therefore, this secondary transfer product gives the user a moist feel to the touch.

[0110] The following describes examples of the present invention.

[0111] 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.

[0112] 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.).

[0113] Next, a coating liquid for the surface protective layer was prepared. The following ionizing radiation curable resin was used as the coating liquid for the surface protective layer. Ionizing radiation curable resin Type: Trimethylolpropane EO-modified triacrylate (15 moles of EO added) Product name: SR9035 (manufactured by Sartomer) Formulation: 100 parts by mass Next, the coating liquid for the surface protective layer was stirred. Stirring was performed as follows. First, the coating liquid for the surface protective layer was placed in a stirring vessel. A ZT-20 stirring vessel (manufactured by Satake Multinics Co., Ltd.) was used. A Satake Multi A Mixer AT14-VPR-0.09BI (manufactured by Satake Multinics Co., Ltd.) was used for stirring. Central stirring was used as the stirring method. The stirring time was 5 minutes.

[0114] Next, a coating liquid for a surface protective layer was applied onto the design layer 3. A coating film made of the coating liquid for a surface protective layer was formed to a thickness of 4.3 μm.

[0115] 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.

[0116] 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.

[0117] Example 2 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 5 μm Blending: 2 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.8 μm.

[0118] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 3 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 4.1 μm.

[0119] <Example 4> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 4 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 5.9 μm.

[0120] <Example 5> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 4.1 μm.

[0121] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 10 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 5.3 μm.

[0122] <Example 7> Decorative sheet 1 was produced in the same manner as in Example 1, except for the following points. That is, in this example, the same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the particle blending amount was 11 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5 μm.

[0123] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the particle blending amount was 12 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 5.3 μm.

[0124] <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, the same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 1.2 μm. The power for stirring the coating liquid for surface protective layer was 0.3 kW.

[0125] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 1.1 μm.

[0126] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 2.1 μm.

[0127] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 2.8 μm.

[0128] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 9.4 μm.

[0129] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the particle blending amount was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 17.2 μm.

[0130] <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 same particles as used in Example 2 were added to the coating liquid for surface protective layer, and the amount of particles was 5 parts by mass. Then, a coating film made of the coating liquid for surface protective layer was formed so as to have a thickness of 18.9 μm.

[0131] Example 15 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 310P (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 2 μm Blending: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.8 μm.

[0132] Example 16 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 420 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 3 μm Blending: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.6 μm.

[0133] Example 17 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 430 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 4 μm Blending: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.1 μm.

[0134] Example 18 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 450 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 8 μm Blend: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.9 μm.

[0135] Example 19 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 882 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 10 μm Blending: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 5.5 μm.

[0136] Example 20 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: Sylysia 780 (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 11 μm Blending: 5 parts by mass Then, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 4.8 μm.

[0137] <Example 21> Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions: In this example, the following particles were added to the coating liquid for surface protective layer: Particles Product name: sicastar 43-00-154 (manufactured by Corefront Co., Ltd.) Particle size: 14 μm Blend: 5 parts by mass Then, a coating film made from the coating liquid for surface protective layer was formed to a thickness of 5.3 μm.

[0138] Comparative Example 2 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.) The same particles as used in Example 2 were then added to the coating liquid for the surface protective layer, with the particle blend amount being 5 parts by mass. Furthermore, a coating film made from the coating liquid for the surface protective layer was formed to a thickness of 5 μm.

[0139] <Example 22> 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 (3 EO moles added) Product name: Miramer M3130 (manufactured by Miwon Co., Ltd.) Then, the same particles as used in Example 2 were added to the coating liquid for the surface protective layer, so that the particle blend amount was 5 parts by mass. In addition, a coating film made of the coating liquid for the surface protective layer was formed so as to have a thickness of 4.9 μm.

[0140] <Example 23> 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 (6 EO moles added) Product name: Miramer M3160 (manufactured by Miwon Co., Ltd.) Then, the same particles as used in Example 2 were added to the coating liquid for the surface protective layer, so that the particle blending amount was 5 parts by mass. In addition, a coating film made of the coating liquid for the surface protective layer was formed so as to have a thickness of 4.9 μm.

[0141] Example 24 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. Specifically, 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 same particles as used in Example 2 were then added to the coating liquid for the surface protective layer, with the particle blend amount being 5 parts by mass. A coating film made from the coating liquid for the surface protective layer was formed to a thickness of 5.3 μm.

[0142] <Example 25> 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.) Then, the same particles as used in Example 2 were added to the coating liquid for the surface protective layer, so that the particle blend amount was 5 parts by mass. Furthermore, a coating film made from the coating liquid for the surface protective layer was formed so that the thickness was 6.1 μm.

[0143] Example 26 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 (20 moles of EO added) Then, the same particles as used in Example 2 were added to the coating liquid for the surface protective layer, with the particle blend amount being 5 parts by mass. Furthermore, a coating film made of the coating liquid for the surface protective layer was formed to a thickness of 4.1 μm.

[0144] <Comparative Example 3> First, a shaping mold was prepared. The shaping mold was prepared by the same method as the manufacturing method of the decorative sheet according to Example 26, except for the following points. That is, in preparing the shaping mold, a coating film made of the surface protective layer coating liquid was formed to a thickness of 3.9 μm.

[0145] Next, using this mold, the surface shape of the mold was transferred as a template to the surface protective layer on the decorative sheet. The transfer was carried out by the following method.

[0146] A UV-curable polydimethylsiloxane liquid (agent A: X-34-4184A, agent B: X-34-4184B, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with decamethylcyclopentasiloxane (KF-995, manufactured by Shin-Etsu Chemical Co., Ltd.) and mixed so that the weight ratios of agent A, agent B, and diluent were 1:1:7 and 1:1:8, respectively, to prepare polydimethylsiloxane mixed liquids. Next, the polydimethylsiloxane liquid was applied to the above-mentioned mold for shaping at a coating amount of 10 g / m. ２After forming a coating film so that the thickness was 15 μm, a 15 μm thick PET film was pressed onto the coating film. After curing the polydimethylsiloxane mixture by UV irradiation, the shaping mold was peeled off from the UV-cured film of the polydimethylsiloxane mixture. This UV-cured film of the polydimethylsiloxane mixture is referred to as the primary transfer film. Furthermore, the uneven surface of the primary transfer film was subjected to UV ozone treatment, and then surface-modified with perfluorodecyltriethoxysilane by vapor deposition, and the reaction was completed in an oven at 100°C. The polydimethylsiloxane mixture was then coated onto the primary transfer film in the same amount as above, and a 15 μm thick PET film was pressed onto the coating film. The polydimethylsiloxane mixture was cured by UV irradiation and referred to as the secondary transfer film. By peeling this secondary transfer film from the primary transfer film, the mold used in Comparative Example 3 was obtained. The mold used in this Comparative Example 3 was pressed onto a coating of a surface protection layer formed in the same manner as in Example 26, except that curing was performed by excimer irradiation and electron beam irradiation.Then, electron beam irradiation similar to that in Example 26 was repeated twice from above the PET to harden the surface protection layer, and the secondary transfer film was peeled off, thereby forming the surface protection layer of Comparative Example 3.

[0147] In this manner, a decorative sheet was obtained.

[0148] <Example 27> 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.) Then, the same particles as used in Example 2 were added to the coating liquid for the surface protective layer, so that the particle blend amount was 5 parts by mass. Furthermore, a coating film made from the coating liquid for the surface protective layer was formed so that the thickness was 5.8 μm.

[0149] <Comparative Example 4> 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 (6 moles of EO added) Product name: Miramer M3160 (manufactured by Miwon Co., Ltd.) The same particles as used in Example 2 were then added to the coating liquid for the surface protective layer, with the particle blend amount being 15 parts by mass. Furthermore, a coating film made of the coating liquid for the surface protective layer was formed to a thickness of 5.2 μm.

[0150] <Example 28> 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: Ethylene glycol diacrylate (9 moles of EO added) Product name: Light Acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) Then, the same particles as used in Example 2 were added to the coating liquid for the surface protective layer, with the particle blend amount being 5 parts by mass. Furthermore, a coating film made from the coating liquid for the surface protective layer was formed so as to have a thickness of 5.7 μm.

[0151] Example 29 Decorative sheet 1 was produced in the same manner as in Example 5, with the following exceptions. In this example, the following sliding property imparting agent was further added to the coating liquid for surface protective layer. -Sliding property imparting agent Product name: Chaline R R-200 (manufactured by Shin-Etsu Chemical Co., Ltd.) Particle size: 2 μm Blend amount: 0.01 parts by mass Comparative Example 5 Decorative sheet 1 was produced in the same manner as in Example 1, with the following exceptions. In this example, the following ionizing radiation curable resin was used. -Ionizing radiation curable resin Type: Ethoxylated dipentaerythritol hexaacrylate (EO 12 moles added) Product name: NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) Then, the same particles as used in Example 2 were added to the coating liquid for surface protective layer, with the blend amount of particles being 5 parts by mass. In addition, a coating film made of the coating liquid for surface protective layer was formed to a thickness of 6.2 μm.

[0152] Comparative Example 6 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.) The same particles as used in Example 2 were then added to the coating liquid for the surface protective layer, with the particle blend amount being 5 parts by mass. Furthermore, a coating film made from the coating liquid for the surface protective layer was formed to a thickness of 6.8 μm.

[0153] <Evaluation> Each of the decorative sheets described above was subjected to the following evaluations.

[0154] (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.

[0155] (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 5 below represents this 60 degree glossiness.

[0156] (3) Skin Feel Skin feel was evaluated using the following method. First, advance preparation was performed to ensure consistency in evaluation criteria 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 two groups. Group 1: A feeling of resistance to pressure was felt, and a dry feeling was obtained. In other words, a smooth feeling was obtained. Group 2: Almost no resistance to pressure was felt, but the surface of the decorative sheet felt as if it was sticking to the finger. In other words, a moist feeling was obtained. Group 3: Almost no resistance to pressure was felt, but the finger felt as if it was sticking strongly to the surface of the decorative sheet. In other words, a strong, moist feeling was obtained. The above 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 consecutive evaluations.

[0157] Next, for each of the decorative sheets, each of the evaluators was blindfolded and asked to slide their fingers across the surface of the surface protective layer while pressing the surface with their fingers, and then to classify the tactile sensation into one of the two groups. This procedure was repeated until the evaluations by each evaluator were consistent for three or more consecutive evaluations, and the evaluation results were consistent between evaluators for three consecutive evaluations. Based on these results, the skin sensation was evaluated according to the following criteria: A (smooth): Group 1 B (moist): Group 2 BB (very moist): Group 3 (4) Fingerprint Resistance To evaluate fingerprint resistance, a fingerprint wiping evaluation was performed. Specifically, the 60-degree gloss of the surface of each decorative sheet was first measured, and this 60-degree gloss was used as the initial gloss. Next, a fingerprint resistance evaluation liquid was applied to the surface protective layer, and the fingerprint resistance evaluation liquid adhered 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 taken as the glossiness after wiping.

[0158] The fingerprint wiping rate was calculated using the following formula: Fingerprint wiping rate (%) = (glossiness after wiping / initial glossiness) × 100 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 (5) Stain Resistance To evaluate stain resistance, the Stain A test specified in the Japanese Agricultural Standards (JAS) was performed. 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.

[0159] 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.

[0160] (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.

[0161] 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.

[0162] (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 attached, so as not to scratch the decorative sheet.

[0163] Next, wood substrate B was bent 90 degrees along the V-shaped groove so that the surface of the decorative sheet facing the surface protective 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.

[0164] 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.

[0165] The evaluation results are shown in Tables 1 to 5. In Tables 1 to 5, 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 BB (very moist), this is indicated by entering the letter Y in the "BB (very moist)" column. If, in the manufacturing process of the decorative sheet 1, the same stirring method as the stirring method for the decorative sheet 1 of Example 1 was used, this is indicated by entering the letter A in the "Stirring method" column, and if the same stirring method as the stirring method for the decorative sheet 1 of Comparative Example 1 was used, this is indicated by entering the letter B in the "Stirring method" column.

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] As shown in Tables 1 to 5, the decorative sheets of Examples 1 to 29 provided the evaluators with a moist feel. Furthermore, the decorative sheets of Examples 1 to 6, 11, 12, 15 to 19, 23, 24, and 29 had low gloss and were excellent in fingerprint resistance, stain resistance, scratch resistance, and processability. On the other hand, as shown in Tables 2, 4, and 5, Comparative Examples 1 to 6 did not provide the evaluators with a moist feel, but rather provided a smooth feel.

[0172] 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. 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 having an uneven structure including a plurality of ridge-like portions each protruding in a ridge-like shape, and the wrinkle area rate on the surface of the surface protective layer being 0.45 or more and 1.0 or less.

2. The decorative sheet according to claim 1, wherein the surface protective layer comprises a cured resin and particles.

3. The decorative sheet according to claim 2, wherein said particles have an average particle size of 3 μm or more.

4. The decorative sheet according to claim 2, wherein said particles have an average particle size of 3 μm or more and 11 μm or less.

5. A decorative sheet according to any one of claims 2 to 4, wherein 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.

6. A decorative sheet according to any one of claims 2 to 5, wherein the resin is an ionizing radiation curable resin.

7. The decorative sheet according to any one of claims 2 to 6, wherein the resin is an acrylate.

8. The decorative sheet according to any one of claims 2 to 7, 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.

9. The decorative sheet according to any one of claims 2 to 7, 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.

10. A decorative sheet described in any one of claims 2 to 9, wherein the surface protective layer further contains a sliding property imparting agent, and the sliding property imparting agent is contained in the surface protective layer in an amount of 0.01 parts by mass or more and 0.03 parts by mass or less per 100 parts by mass of the resin.

11. The decorative sheet according to any one of claims 1 to 10, wherein the thickness t of said surface protective layer is 2 μm or more and 18 μm or less.

12. The decorative sheet according to any one of claims 1 to 11, further comprising a design layer between said base layer and said surface protective layer.

13. The decorative sheet according to any one of claims 1 to 12, wherein the surface protective layer has a glossiness of less than 10.

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

15. A method for manufacturing a decorative sheet comprising: stirring a coating liquid containing an ionizing radiation curable resin and particles; forming a coating film made of the coating liquid on an original fabric layer; carrying out a first irradiation step in which the coating film is irradiated with light having a wavelength of 200 nm or less; and then carrying out a second irradiation step in which the coating film is irradiated with ionizing radiation or ultraviolet light having a longer wavelength than the light irradiated in the first irradiation step, wherein the stirring of the coating liquid and the first irradiation step are carried out such that the surface of the coating film after the second irradiation step has a wrinkle area ratio of 0.45 to 1.0.

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