Decorative sheet

Abstract

A decorative sheet (1) is provided with a raw material layer (2) and a surface protection layer (5) provided on one surface of the raw material layer (2), the surface of the surface protection layer (5) is provided with an uneven structure including a plurality of ridge-shaped portions each protruding in a ridge shape, and the height (Rpk) of a protruding mountain portion of the uneven structure of the surface protection layer (5) is less than 3.5 [mu] m. The mass concentration C (mass%) of carbon atoms, the mass concentration O (mass%) of oxygen atoms, and the mass concentration Si (mass%) of silicon atoms in the surface protection layer (5) satisfy the following relational expression: 0.5 < = {Si / (C + O + Si)} * 100.

Description

Technical Field

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

[0002] Decorative sheets are used to decorate the surfaces of interior and exterior materials such as doors and windows, furniture, building materials, and flooring, imparting design and durability to these components. Decorative sheets are commonly used by attaching them to substrates such as wood, wood panels, metal sheets, non-combustible panels, paper substrates, and resin substrates using adhesives to create decorative panels.

[0003] Design can be achieved by, for example, using various printing methods to create patterns such as wood grain or stone grain. A plain, unpatterned decorative sheet is sometimes preferred. The presence or absence of a pattern and the type of pattern vary depending on the intended use and preference.

[0004] Surface gloss is also important for the design of decorative sheets. Decorative sheets can be selected from a variety of finishes, from high gloss like a mirror finish to low gloss that eliminates any reflection, depending on the application and preference.

[0005] As mentioned above, durability is another important function of decorative sheets, just as important as design. Durability is a comprehensive evaluation of scratch resistance, stain resistance, and whether these properties can be maintained over a long period of time. While requirements vary depending on the environment and conditions in which the decorative sheet is used, high-performance decorative sheets are always desired.

[0006] In order to impart durability, a surface protective layer is generally formed on the outermost surface of the decorative sheet. In addition, in order to adjust the glossiness, especially to achieve low gloss, a gloss modifier (matt additive) is generally added to the surface protective layer.

[0007] Furthermore, since the decorative sheet is generally subjected to processing such as cutting and bending in order to form a decorative material such as a decorative plate, it is desirable that the decorative sheet has processability that can withstand such processing.

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

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2019-119138 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] An object of the present invention is to provide a decorative sheet that imparts a smooth touch and has excellent uniformity of touch.

[0014] Means for solving problems

[0015] According to one aspect of the present invention, a decorative sheet is provided, comprising a raw material layer and a surface protective layer disposed on one surface of the raw material layer, wherein a concave-convex structure including a plurality of ridges, each protruding in a ridge-like manner, is disposed on the surface of the surface protective layer, wherein a height Rpk of the protruding peaks of the concave-convex structure of the surface protective layer is less than 3.5 μm, and a mass concentration C (mass %) of carbon atoms, a mass concentration O (mass %) of oxygen atoms, and a mass concentration Si (mass %) of silicon atoms in the surface protective layer satisfy the following relationship:

[0016] 0.5≤{Si / (C+O+Si)}×100.

[0017] According to another aspect of the present invention, there is provided the decorative sheet according to the above aspect, wherein the protruding peak height Rpk is 0.5 μm or greater.

[0018] According to another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the mass concentration C (mass %) of carbon atoms, the mass concentration O (mass %) of oxygen atoms, and the mass concentration Si (mass %) of silicon atoms in the surface protective layer satisfy

[0019] The following relationship:

[0020] 0.5≤{Si / (C+O+Si)}×100≤5.0.

[0021] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the average length RSm of the roughness curve elements of the concavo-convex structure of the surface protection layer is 800 μm or less. According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the average length RSm of the roughness curve elements of the concavo-convex structure of the surface protection layer is 350 μm or less.

[0022] According to yet another aspect of the present invention, there is provided the decorative sheet according to any one of the above aspects, wherein the average length RSm is 10 μm or greater.

[0023] According to yet another aspect of the present invention, there is provided the decorative sheet according to any one of the above aspects, wherein the thickness of the surface protection layer is not less than 2 μm and not more than 15 μm.

[0024] According to yet another aspect of the present invention, there is provided the decorative sheet according to any one of the above aspects, wherein the thickness of the surface protection layer is greater than or equal to 2 μm and less than 10 μm.

[0025] According to yet another aspect of the present invention, there is provided the decorative sheet according to any one of the above aspects, wherein the glossiness of the surface protection layer is 20.0 or less.

[0026] According to yet another aspect of the present invention, there is provided the decorative sheet according to any one of the above aspects, wherein the glossiness of the surface protection layer is 10.0 or less.

[0027] According to yet another aspect of the present invention, a decorative sheet according to any one of the above aspects is provided, wherein at least a portion of the plurality of ridge-shaped portions are adjacent in the width direction, and at a position where the at least a portion of the plurality of ridge-shaped portions are adjacent in the width direction, in a cross-section parallel to the width direction and the thickness direction of the surface protective layer, the portion where the concave-convex structure is provided has a sinusoidal wave shape.

[0028] According to yet another aspect of the present invention, there is provided the decorative sheet according to any one of the above aspects, wherein the surface protective layer comprises a cured product of an ionizing radiation-curable resin.

[0029] According to yet another aspect of the present invention, a decorative sheet according to the above aspect is provided, wherein the main component of the ionizing radiation curable resin is an acrylate containing a repeating structure, the repeating structure is any one of ethylene oxide, propylene oxide, and ε-caprolactone, and the number of repetitions of the repeating structure is 3 or more.

[0030] According to yet another aspect of the present invention, a decorative sheet according to the above aspect is provided, wherein the main component of the ionizing radiation curable resin is an acrylate, the acrylate is composed of a first acrylate having a repeating structure and a second acrylate having 1 to 6 functionalities, the repeating structure is any one of ethylene oxide, propylene oxide, and ε-caprolactone, and the number of repetitions of the repeating structure is 3 or more.

[0031] According to yet another aspect of the present invention, there is provided a decorative material comprising: the decorative sheet according to any one of the above aspects; and a base material to which the decorative sheet is attached.

[0032] Effects of the Invention

[0033] According to the present invention, a decorative sheet that imparts a smooth touch and has excellent uniformity of touch can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] [ Figure 1 ] Figure 1This is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention.

[0035] [ Figure 2 ] Figure 2 yes Figure 1 A cross-sectional view of a surface protective layer included in a decorative sheet.

[0036] [ Figure 3 ] Figure 3 This is a microscope image of a surface protection layer included in a decorative sheet according to an example of the present invention. DETAILED DESCRIPTION

[0037] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. The embodiments described below are embodiments that further specify any of the above aspects. The matters described below may be incorporated into the above aspects individually or in combination.

[0038] The embodiments described below are examples of configurations for embodying the technical concept of the present invention, and the technical concept of the present invention is not limited by the materials, shapes, and structures of the components described below. The technical concept of the present invention can be modified in various ways within the technical scope defined by the claims.

[0039] It should be noted that elements having the same or similar functions are denoted by the same reference numerals in the drawings referenced below, and repeated descriptions are omitted. In addition, the drawings are schematic, and the relationship between dimensions in a certain direction and dimensions in other directions, as well as the relationship between the dimensions of a certain component and the dimensions of other components, may differ from actual conditions.

[0040] <1> Decorative materials and decorative sheets

[0041] Figure 1 This is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. Figure 2 yes Figure 1 A cross-sectional view of a surface protective layer included in a decorative sheet. Figure 3 This is a micrograph of a surface protection layer included in a decorative sheet according to an example of the present invention.

[0042] It should be noted that Figure 2 The cross section shown is a cross section along the thickness direction of the surface protection layer. Figure 3 The micrographs are plane photographs obtained using a laser microscope (OLS-4000 manufactured by Olympus Corporation).

[0043] Figure 1The decorative material 11 shown includes a base material B and a decorative sheet 1 attached thereto. Here, the decorative material 11 is a decorative board. The decorative board can be flat, curved, or folded. The decorative material 11 can also have shapes other than boards.

[0044] Here, the substrate B is a plate. The plate is, for example, a wooden plate, an inorganic plate, a metal plate, or a composite plate made of multiple materials. The substrate B may also have a shape other than a plate.

[0045] The decorative sheet 1 includes a raw material layer 2, a pattern layer 3, a transparent resin layer 4, a surface protection layer 5, an adhesive layer 7, a primer layer 6, and a concealing layer 8. The pattern layer 3, the adhesive layer 7, the transparent resin layer 4, and the surface protection layer 5 are sequentially arranged on the surface of the raw material layer 2 opposite to the surface facing the substrate B. The concealing layer 8 and the primer layer 6 are sequentially arranged on the surface of the raw material layer 2 facing the substrate B. One or more of the pattern layer 3, the transparent resin layer 4, the primer layer 6, the adhesive layer 7, and the concealing layer 8 may be omitted. The following describes the elements included in the decorative sheet 1 in order.

[0046] <1.1> Raw material layer

[0047] As the raw material layer 2 or its material, for example, a material arbitrarily selected from paper, synthetic resin, synthetic resin foam, rubber, non-woven fabric, synthetic paper, metal foil, etc. can be used. Examples of paper include thin leaf paper, titanium paper, resin-impregnated paper, etc. Examples of synthetic resin include polyethylene, polypropylene, polybutene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic acid, etc. 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, polyurethane, etc. As non-woven fabric, organic or inorganic non-woven fabric can be used. Examples of metal as metal foil include aluminum, iron, gold, silver, etc.

[0048] Taking printing workability, cost, and the like into consideration, the thickness of the original material layer 2 is preferably within a range of 20 μm to 250 μm.

[0049] <1.2> Primer layer

[0050] When an olefin-based resin is used as the material for the raw material layer 2, the surface of the raw material layer 2 is often in an inert state. Therefore, in this case, it is preferable to provide a primer layer 6 between the raw material layer 2 and the substrate B. When the raw material layer 2 is composed of an olefin-based material, in order to omit the primer layer 6 and improve the adhesion between the raw material layer 2 and the substrate B, the raw material layer 2 may be subjected to a surface modification treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, or dichromic acid treatment.

[0051] As a material for the primer layer 6, for example, the material for the pattern layer 3 described later can be used. Since the primer layer 6 is applied to the back surface of the decorative sheet 1, an inorganic filler may be added to the primer layer 6 to prevent sticking and improve adhesion with the adhesive when the decorative sheet 1 is wound in a web shape. Examples of the inorganic filler include silica, alumina, magnesium oxide, titanium oxide, and barium sulfate.

[0052] <1.3> Hidden layer

[0053] To provide concealment to the decorative sheet 1 from the substrate B, for example, a colored sheet can be used as the base material layer 2, or an opaque concealing layer 8 can be provided. The concealing layer 8 can be composed of, for example, the same material as the pattern layer 3 described below. However, since the concealing layer 8 is intended for concealment, opaque pigments, such as titanium oxide and iron oxide, are preferably used as pigments. Furthermore, to enhance concealment, metals such as gold, silver, copper, and aluminum can be added to the material of the concealing layer 8. Thin aluminum flakes are often used.

[0054] <1.4> Pattern layer

[0055] The pattern layer 3 is formed by printing a pattern on the raw material layer 2 using ink. As a binder for the ink, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylics, polyesters, or modified forms thereof can be used alone or in combination. The binder can be any of aqueous, solvent-based, or emulsion-based, and can be a single-component or a two-component type using a curing agent. The pattern layer 3 can be formed by curing a layer formed from a curable ink using ultraviolet light or electron beam irradiation. The most common method is to use a urethane-based ink and cure it with an isocyanate. In addition to the binder, the ink used to form the pattern layer 3 may also contain, for example, colorants such as pigments and dyes found in conventional inks, extenders, solvents, and various additives. Examples of highly versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolones, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearlescent pigments such as mica.

[0056] In addition to ink application, the design layer 3 can also be designed by vapor deposition or sputtering of various metals. In particular, it is preferable to add a light stabilizer to the ink. This can suppress degradation of the decorative sheet 1 itself due to light degradation of the ink, thereby extending the life of the decorative sheet 1.

[0057] <1.5> Adhesive layer

[0058] The adhesive layer 7 is also called a heat-sensitive adhesive layer, an anchor coating layer, or a dry lamination adhesive layer.

[0059] The resin material of bonding layer 7 is not particularly limited, for example, can suitably select and use from resin materials such as acrylic acid series, polyester series, polyurethane series, epoxy series. In addition, as the resin material of bonding layer 7, for example, also can use ethylene-vinyl acetate copolymer resin system adhesive. The coating method can suitably select according to the viscosity etc. of adhesive. Usually use gravure coater, after utilizing gravure coater to form bonding layer 7 on the patterned layer 3, laminated transparent resin layer 4. It should be noted that, under the situation that obtains sufficient bonding strength between transparent resin layer 4 and the patterned layer 3, bonding layer 7 can be omitted.

[0060] <1.6> Transparent resin layer

[0061] As the resin material of the transparent resin layer 4, an olefin resin is preferably used. Examples of the olefin resin include polypropylene, polyethylene, and polybutene, and 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-di ... Polymers obtained by homopolymerization of ethylene-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc., or copolymerization of two or more thereof; copolymers obtained by copolymerizing ethylene or α-olefins with monomers other than these, such as ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-butyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-butyl acrylate copolymers.

[0062] Furthermore, to enhance the surface strength of the decorative sheet 1, highly crystalline polypropylene is preferably used as the resin for the transparent resin layer 4. It should be noted that various additives, such as heat stabilizers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents, and gloss modifiers, may be added to the transparent resin layer 4 as needed. Heat stabilizers generally include phenolic, sulfur, phosphorus, and hydrazine stabilizers in any combination, while light stabilizers generally include hindered amine stabilizers in any combination.

[0063] <1.7> Surface protective layer

[0064] 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 5 A. These ridge portions 5B form a concavo-convex structure.

[0065] Here, in the decorative sheet 1 according to this embodiment, "ridge" refers to a convex shape that is linear in plan view. The shape of the ridge portion 5B in plan view can be curved or linear, but from the perspective of the fingerprint resistance of the decorative sheet 1, a curved shape is preferred. Each ridge portion 5B can be branched or unbranched in plan view. In addition, in this disclosure, the ridge portion 5B is, for example, the portion extending from the lowest part to the top of the concave-convex shape provided on the surface of the surface protection layer 5, and the core portion 5A refers to the portion of the surface protection layer 5 excluding the ridge portion 5B.

[0066] For example, Figure 3 As shown, the ridges 5B are each curved, and at least a portion thereof is adjacent to each other in the width direction. At a position where at least a portion of the ridges 5B is adjacent to each other in the width direction, in a cross section of the surface protection layer 5 parallel to the width direction and the thickness direction of the surface protection layer 5, as shown in FIG. Figure 2 As shown, the portion provided with the concavo-convex structure has a wave shape such as a sine wave shape.

[0067] The peak height Rpk of the concavo-convex structure of the surface protection layer 5 is less than 3.5 μm. "Rpk" is a surface quality parameter defined in JIS B0671-2:2002. This peak height Rpk is more preferably 3.0 μm or less, and even more preferably 2.8 μm or less. A decorative sheet with increased peak height Rpk can give a rough feel to the user when the user slides their skin, for example, a finger, across the surface of the surface protection layer.

[0068] The height Rpk of the protruding peaks is preferably 0.5 μm or greater, more preferably 0.8 μm or greater, and even more preferably 1.0 μm or greater. A decorative sheet with a reduced height Rpk of the protruding peaks can generate greater friction when a user slides their skin, such as a finger, across the surface of the surface protection layer.

[0069] The average length RSm of the roughness curve elements of the concavo-convex structure of the surface protection layer 5 is preferably 800 μm or less, more preferably 550 μm or less, even more preferably 350 μm or less, even more preferably 320 μm or less, and even more preferably 300 μm or less. Here, "average length RSm of the roughness curve elements" is a surface property parameter specified in JIS B0601:2013. When a user slides their skin, for example, a finger, across the surface of the surface protection layer, the average length RSm of the roughness curve elements is preferably within the above range to provide the user with a smooth tactile feel.

[0070] The average length RSm is preferably 10 μm or more, more preferably 50 μm or more, and even more preferably 80 μm or more. A structure in which the average length RSm is small and the protruding peak height Rpk is somewhat large is difficult to manufacture.

[0071] The mass concentration C (mass %) of carbon atoms, the mass concentration O (mass %) of oxygen atoms, and the mass concentration Si (mass %) of silicon atoms in the surface protection layer 5 satisfy the following relational expression (1).

[0072] 0.5≤{Si / (C+O+Si)}×100 (1)

[0073] Here, surface protective layer 5 contains an ionizing radiation-curable resin and silica particles, described later. When surface protective layer 5 satisfies the above-mentioned relational expression (1), ridges 5B can be uniformly formed over a wide area, improving the uniformity of the tactile feel. From the same perspective, the value of {Si / (C+O+Si)}×100 is preferably 0.75 or greater, and more preferably 1.0 or greater.

[0074] The C (mass %), O (mass %), and Si (mass %) in the surface protection layer 5 preferably satisfy the following relational expression (2).

[0075] 0.5≤{Si / (C+O+Si)}×100≤5.0 (2)

[0076] From the viewpoints of scratch resistance, stain resistance, weather resistance, etc., the value of {Si / (C+O+Si)}×100 is preferably 5.0 or less. From the same viewpoint, the value of {Si / (C+O+Si)}×100 is more preferably 3.5 or less, and even more preferably 2.0 or less.

[0077] SEM-EDX analysis (scanning electron microscopy-energy dispersive X-ray analysis)

[0078] The C (mass %), O (mass %), and Si (mass %) contained in the surface protective layer 5 can be measured using scanning electron microscopy (SEM) observation and energy dispersive X-ray spectroscopy (EDX). EDX is a method of elemental analysis that detects characteristic X-rays generated by electron beam irradiation and separates them based on their energy. Here, a Regulus 8220 manufactured by Hitachi High-Tech Corporation was used as the SEM, and an AZtec Live / Ultim Max170 manufactured by Oxford, which was attached to the SEM, was used as the EDX instrument. Analysis was performed under the following conditions.

[0079] Analysis conditions

[0080] The surface of the surface protection layer 5 was subjected to a conductive treatment (Pt sputtering at 40 mA for 20 seconds), and the top coating surface was subjected to SEM-EDX analysis under the following conditions.

[0081] Accelerating voltage: 15 kV

[0082] Emission current: 10μA

[0083] Probe current: High

[0084] Condenser lens: 1

[0085] Measurement time: 60 seconds

[0086] Measurement magnification: 500 times

[0087] As will be described below, the decorative sheet 1 according to the present embodiment has excellent uniformity in smooth touch.

[0088] Figure 3 This is a microscopic photograph of a decorative sheet according to an example of the present invention, showing a small rectangular region with a side of several hundred micrometers.

[0089] exist Figure 3 In the microscopic region shown in the microscopic photograph of FIG, wrinkles corresponding to the ridge 5B are uniformly formed. The uniformity of the wrinkles contributes to the uniformity of the touch. Therefore, a decorative sheet having excellent uniformity of smooth touch (for example) Figure 3 As shown in the microscope photograph, the wrinkles need to be uniform.

[0090] However, even when wrinkles are uniformly present in such a specific micro region, other regions may also have wrinkles that are uniformly present in the same micro region. Figure 3 The wrinkles shown may be of different shapes or may include areas without wrinkles. Whether wrinkles are uniform across the entire surface of the surface protection layer 5 cannot always be confirmed by observing a microscopic image of a specific, small area of the size described above, or by visually inspecting the decorative sheet. Furthermore, if wrinkles are unevenly distributed across the surface of the surface protection layer 5, even if the unevenness cannot be confirmed by observing a microscopic image of a specific, small area or by visually inspecting the decorative sheet, the unevenness can be perceived as a different tactile sensation when the user slides their skin across the surface of the surface protection layer 5.

[0091] The decorative sheet 1 can be obtained by the method described below. Furthermore, the decorative sheet 1 has the aforementioned characteristics. When a user slides their skin over the surface of the surface protection layer 5, the decorative sheet 1 provides a smooth tactile feel, and this smooth tactile feel is excellent in uniformity.

[0092] The thickness of the surface protection layer 5 is preferably 2 μm to 15 μm, more preferably 2 μm to less than 10 μm, and even more preferably 2 μm to less than 8 μm. Reducing the thickness of the surface protection layer 5 makes it difficult to increase the height Rpk of the protruding peaks or the average length RSm. Increasing the thickness of the surface protection layer 5 tends to increase the height Rpk of the protruding peaks or the average length RSm.

[0093] Here, the thickness of the surface protection layer 5 is the thickness of a layer having a flat surface and an apparent area and volume equal to that of the surface protection layer 5. The thickness of the surface protection layer 5 can be calculated, for example, by the following method. First, a cross-section parallel to the thickness direction of the surface protection layer 5 and perpendicular to the longitudinal direction of the ridge 5B is imaged. Next, the dimensions of the surface protection layer 5 in the width direction of the ridge 5B and the area of the cross-section of the surface protection layer 5 are calculated from this cross-sectional image. The thickness of the surface protection layer 5 is obtained by dividing this area by the aforementioned dimensions.

[0094] In addition, when the surface protection layer coating liquid described later does not contain a solvent, the thickness of the coating film composed of the surface protection layer coating liquid is equal to the thickness of the surface protection layer 5 .

[0095] The glossiness of the surface protection layer 5 is preferably 20.0 or less, more preferably 10.0 or less, and even more preferably 8.0 or less. Here, the "glossiness" is a value measured at an incident angle of 60 degrees using a gloss meter according to JIS Z8741:1997.

[0096] <2> Method for manufacturing decorative sheet

[0097] The decorative sheet 1 is produced, for example, by the following method: For simplicity, descriptions of the design layer 3, the transparent resin layer 4, the primer layer 6, the adhesive layer 7, and the concealing layer 8 are omitted.

[0098] First, a coating film composed of a surface protective layer coating liquid is formed on one surface of the raw material 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, doctor blade coating, micro gravure coating, and die coating.

[0099] The surface protective layer coating liquid contains an ionizing radiation-curable resin. Here, "ionizing radiation" refers to a charged particle beam such as an electron beam. Ionizing radiation-curable resins are cured by irradiation with ionizing radiation. Alternatively, ionizing radiation-curable resins can be cured by irradiation with ultraviolet light. The ionizing radiation-curable resins used herein are cured by irradiation with light having a wavelength of 200 nm or less and have a high absorption coefficient for this light.

[0100] In the coating liquid for the surface protection layer, when the total solid content is set to 100 parts by mass, the amount of the ionizing radiation curable resin is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more. As the ionizing radiation curable resin, known resins such as various monomers or commercially available oligomers can be used, for example, (meth) acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins can be used. The ionizing radiation curable resin can be any one of an aqueous resin or a non-aqueous (organic solvent) resin.

[0101] The main component of the ionizing radiation curable resin is preferably an acrylate. Here, the main component of the ionizing radiation curable resin refers to a component that accounts for 60 parts by mass or more based on 100 parts by mass of the total solid content contained in the ionizing radiation curable resin. The ionizing radiation curable resin preferably contains 70 parts by mass or more of the acrylate, and more preferably contains 80 parts by mass or more of the acrylate.

[0102] The acrylate is preferably a difunctional or higher acrylate, more preferably a trifunctional or higher acrylate. To obtain a surface protective layer 5 having excellent scratch resistance, the acrylate is preferably trifunctional or higher. There is no upper limit on the number of functional groups of the acrylate, but according to one example, it is hexafunctional or lower.

[0103] The acrylate preferably contains a repeating structure. This repeating structure is, for example, any of an ethylene oxide (EO) structure, a propylene oxide (PO) structure, and an ε-caprolactone (CL) structure. The repeating structure is preferably ethylene oxide or propylene oxide. In trifunctional or higher-functional acrylates containing a repeating structure, the repeating structure may be positioned between an acryloyl group and a hydroxymethyl group in a ring-opened state.

[0104] The number of repetitions of the repeating structure is preferably 3 or more. When using an acrylate with a high number of repetitions, the cured film is more likely to expand in the in-plane direction during the second irradiation step described below, resulting in wrinkles corresponding to the ridges 5B on the coating surface. Furthermore, wrinkles can be uniformly generated over a wide area, contributing to a more uniform tactile feel. However, increasing the number of repetitions decreases the crosslinking density and the scratch resistance of the surface protective layer.

[0105] Examples of trifunctional acrylates containing a repeating structure include EO-modified, PO-modified, or CL-modified trimethylolpropane triacrylate, glycerol triacrylate, isocyanurate triacrylate, or pentaerythritol triacrylate. In trifunctional acrylates containing a repeating structure, the number of repetitions of the repeating structure is preferably 3 or more and 30 or less, more preferably 3 or more and 20 or less.

[0106] Examples of tetrafunctional acrylates containing a repeating structure include EO-modified, PO-modified, or CL-modified pentaerythritol tetraacrylates. In tetrafunctional acrylates containing a repeating structure, the number of repetitions of the repeating structure is preferably 12 or more, more preferably 12 or more and 50 or less, and even more preferably 20 or more and 50 or less.

[0107] The number of repetitions of the above-mentioned repeating structure can be analyzed using MALDI-TOF-MS. Ionizing radiation curable resins sometimes have a molecular weight distribution. In the case of a molecular weight distribution, the number of repetitions is set to the number of repetitions corresponding to the molecular weight having the strongest peak in the MALDI-TOF-MS mass spectrum.

[0108] As described above, the main component of the ionizing radiation-curable resin is preferably an acrylate. The acrylate can be composed of the acrylates described above. Alternatively, the acrylate can be composed of the acrylate described above (hereinafter referred to as the first acrylate) and a second acrylate different from the first acrylate. In this case, the mixing ratio of the first acrylate to the second acrylate is not particularly limited and can be, for example, a mass ratio within the range of 90:10 to 20:80. The second acrylate is, for example, a monofunctional to hexafunctional acrylate.

[0109] According to one example, the acrylate may be composed of a first acrylate having a repeating structure and a second acrylate having 1 to 6 functional groups. In this example, the repeating structure of the first acrylate is any one of ethylene oxide, propylene oxide, and ε-caprolactone, and the repeating structure is repeated three or more times.

[0110] The second acrylate preferably does not contain a repeating structure. That is, the second acrylate is preferably a mono- to hexa-functional acrylate that does not contain a repeating structure. Specifically, the second acrylate preferably does not contain any of the repeating structures of ethylene oxide, propylene oxide, and ε-caprolactone.

[0111] Examples of the second acrylate include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0112] When the second acrylate is used in addition to the first acrylate, the peak height Rpk tends to be smaller, and the average length RSm of the roughness curve element tends to be larger. As a result, the glossiness of the surface protection layer 5 can be increased, thereby increasing the glossiness variation, or the thickness of the surface protection layer 5 can be increased, thereby increasing the thickness variation.

[0113] As described above, the surface protective layer coating liquid contains silica particles. When the surface protective layer coating liquid contains silica particles, wrinkles can be generated more uniformly on the coating film surface in the second irradiation step described below, which contributes to improving the uniformity of the tactile feel.

[0114] The surface protective layer coating liquid may also contain particles other than silica particles. Examples of particles other than silica particles include particles made of organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads; or particles made of inorganic materials such as glass, aluminum oxide, titanium dioxide, zirconium oxide, calcium carbonate, and barium sulfate. Particles other than silica particles may be included in the surface protective layer coating liquid in an amount of, for example, 20% by mass or less of the total particles.

[0115] The average particle size (D50) of the particles containing silica particles is preferably 10 μm or less. The average particle size (D50) of the particles is more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less. When large particles are used, the particles may easily fall off the surface protection layer 5, making it difficult to achieve high scratch resistance. When the particles are small, the effect of uniformly generating wrinkles is small.

[0116] Here, the "average particle size (D50)" is the median particle size (D50) measured by a laser diffraction / scattering particle size distribution measuring device. It should be noted that, when the surface protective layer coating liquid contains particles, the surface protective layer 5 obtained by the coating liquid also contains particles. The average particle size of the particles contained in the surface protective layer 5 can be a value obtained by observing its cross section, measuring the particle size of multiple particles and averaging them. The value obtained in this way is substantially the same value as the median particle size (D50) measured by a laser diffraction / scattering particle size distribution measuring device. Therefore, the range of the above-mentioned average particle size can also be read as the range of the average particle size of the particles contained in the surface protective layer 5.

[0117] The amount of particles containing silica particles added per 100 parts by mass of the ionizing radiation-curable resin is preferably from 1.3 parts by mass to 22 parts by mass, more preferably from 1.3 parts by mass to 15 parts by mass, and even more preferably from 3 parts by mass to 10 parts by mass. If the surface protective layer coating liquid does not contain particles other than silica particles, the above amount refers to the amount of silica particles added. When the amount of particles is within the above range, the effect of uniform wrinkle formation is particularly significant.

[0118] The surface protective layer coating liquid may also contain a solvent or an additive (e.g., an antibacterial agent or mildewproofing agent) for improving the functionality of the final product. The surface protective layer coating liquid may also contain other additives such as ultraviolet absorbers and light stabilizers. As ultraviolet absorbers, for example, benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, etc. can be used. As light stabilizers, for example, hindered amine-based, etc. can be used. It should be noted that according to the method described herein, a surface protective layer 5 having a low gloss can be formed without a gloss modifier (matt additive).

[0119] When the first irradiation step described below is performed, or when the entire coating film composed of the surface protective layer coating liquid is cured by ultraviolet irradiation in the third irradiation step described below, the surface protective layer coating liquid preferably further contains a photoinitiator. The photoinitiator is not particularly limited, and examples thereof include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based photoinitiators.

[0120] The amount of photoinitiator added is preferably from 0.1 to 10 parts by mass, more preferably from 0.25 to 8 parts by mass, and even more preferably from 0.5 to 6 parts by mass, relative to 100 parts by mass of the ionizing radiation-curable resin. When the photoinitiator is less than 0.1 parts by mass, the effect of the first irradiation step, described below, is not readily apparent. When the photoinitiator is greater than 10 parts by mass, the coating film is completely cured, making it difficult to form wrinkles in the subsequent second irradiation step.

[0121] After forming a coating film composed of a coating liquid for a surface protective layer, it is preferably semi-cured by implementing a first irradiation process. In the first irradiation process, light with a wavelength of about 200 nm to 400 nm (hereinafter referred to as the first irradiation light) is irradiated to the coating film. By implementing the first irradiation process to semi-cure the coating film, the wrinkles generated by the second irradiation process described later can be formed more uniformly. In addition, the depth of the wrinkle shape can be designed according to the irradiation conditions of the first irradiation process to adjust the texture. The implementation of the first irradiation process is not necessary, and it can be implemented according to the properties of the required product.

[0122] In the first irradiation step, a high-pressure mercury lamp, a metal halide lamp, a single-wavelength LED lamp having a wavelength of 200 nm to 400 nm, etc. can be selected and used.

[0123] The cumulative light intensity of the first irradiation light is preferably set to 2 mJ / cm 2 Above 100mJ / cm 2 Below, more preferably 10 mJ / cm 2 Above 80mJ / cm 2 Below, more preferably set to 20mJ / cm 2 Above 60mJ / cm 2 When the integrated light intensity is reduced, the effect of the first irradiation step is less apparent. When the integrated light intensity is increased, the coating film is completely cured, and wrinkles are less likely to form in the subsequent second irradiation step.

[0124] After forming the coating film consisting of the surface protection layer coating liquid, or after implementing the first irradiation process, the second irradiation process is implemented. In the second irradiation process, the coating film is irradiated with light having a wavelength of 200nm or less (hereinafter referred to as the second irradiation light). The ionizing radiation curable resin contained in the surface protection layer coating liquid has a large absorption coefficient for the second irradiation light. Therefore, the second irradiation light incident on the coating film can only reach a position that is tens to hundreds of nm away from its outermost surface. Therefore, in the second irradiation process, a cross-linking reaction is carried out in the surface area of the coating film to form an extremely thin cured film. On the other hand, a cross-linking reaction is not carried out in other areas and remains uncured.

[0125] The coating film after the second irradiation step has wrinkles on the surface corresponding to the ridge portions 5B. The present inventors believe that the reason why wrinkles are generated on the coating film surface by the second irradiation step is as follows.

[0126] As mentioned above, the second irradiation light can only reach a position tens to hundreds of nm away from the outermost surface of the coating. That is, the cross-linking reaction of the ionizing radiation curable resin occurs only on the surface of the coating. Monomers present on the surface of the coating are cross-linked by the functional groups they have by the irradiation of the second irradiation light to form a cured film, but these functional groups are not all used for cross-linking between monomers present on the surface of the coating. That is, uncross-linked functional groups may remain in the cured film.

[0127] Since the second irradiation light does not reach monomers located far from the coating surface, a crosslinking reaction does not occur. However, some of the monomers located far from the coating surface migrate toward the cured film, causing a crosslinking reaction. This increases the number of molecules involved in the crosslinking reaction.

[0128] As the number of molecules participating in the cross-linking reaction on the coating film surface increases, the volume of the cured film increases. Since the cross-linking reaction occurs only on the coating film's surface, the cured film cannot increase in volume through the thickness direction and expands inward. As a result, wrinkles appear on the coating film's surface.

[0129] The second irradiation light can be extracted from excimer VUV (Vacuum Ultra Violet) light. Excimer VUV light can be generated by lamps using rare gases or rare gas halides. When high-energy electrons are applied from the outside to a lamp containing a gas enclosing a rare gas or rare gas halide, a large amount of discharge plasma (dielectric barrier discharge) is generated. This plasma discharge excites the atoms of the discharge gas (rare gas) and momentarily enters an excimer state. When the atoms return to the ground state from this excimer state, they emit light in a wavelength region unique to the excimer.

[0130] The gas used in the excimer lamp can be any gas that emits light below 200nm. Rare gases such as Xe, Ar, and Kr, or mixtures of rare gases such as ArBr and ArF with halogen gases, can be used. The wavelength (center wavelength) of the excimer lamp varies depending on the gas, with examples ranging from approximately 172nm for Xe, 126nm for Ar, 146nm for Kr, 165nm for ArBr, and 193nm for ArF.

[0131] Consider the difference of the size of photon energy, wavelength and organic binding energy, preferably use the xenon lamp that sends the excimer light of central wavelength being 172nm as light source.In addition, even consider that equipment maintains the acquisition etc. of the cost spent and material, also preferably use xenon lamp as light source.

[0132] The second irradiation step is performed in an atmosphere with a low oxygen concentration. Oxygen has a high absorption coefficient for light with a wavelength of 200 nm or less. Therefore, the second irradiation step is preferably performed in a nitrogen atmosphere, for example. The oxygen concentration in the gas phase during the second irradiation step, i.e., the residual oxygen concentration in the reaction atmosphere, is preferably set to 2000 ppm or less, and more preferably to 1000 ppm or less.

[0133] In addition, oxygen in the atmosphere inhibits free radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere affects the formation of wrinkles on the coating surface. Therefore, when the residual oxygen concentration in the reaction atmosphere changes, the surface properties of the surface protection layer 5 may also change.

[0134] The integrated light intensity of the second irradiation light is preferably set to 0.5 mJ / cm 2 Above 200mJ / cm 2 Below, more preferably 1 mJ / cm 2 Above 100mJ / cm 2 Below, more preferably set to 3mJ / cm 2 Above 50mJ / cm 2 When the accumulated light intensity is reduced, the in-plane expansion of the cured film decreases. When the accumulated light intensity is increased, the surface condition of the coating film deteriorates.

[0135] After the second irradiation step is completed, the third irradiation step is performed. In the third irradiation step, the coating film is irradiated with the third radiation or light to cure the entire coating film. In this way, the surface protection layer 5 is obtained.

[0136] The third radiation or irradiation light is ionizing radiation such as an electron beam, or ultraviolet light having a longer wavelength than the second irradiation light.

[0137] When the third radiation or irradiation light is ultraviolet light, the integrated light amount of the third irradiation light is preferably set to 10 mJ / cm 2 Above 500mJ / cm 2 Below, more preferably 50mJ / cm 2 Above 400mJ / cm 2 Below, more preferably set to 100mJ / cm 2 Above 300mJ / cm 2 the following.

[0138] The decorative sheet 1 can be manufactured, for example, by the above method. The decorative sheet 1 can also be manufactured by other methods. For example, the surface protection layer 5 can be formed by forming a plate using the above method and transferring the plate to form the surface protection layer 5 having a concavo-convex structure.

[0139] <3> Effect

[0140] Reference Figures 1 to 3The surface protection layer 5 of the decorative sheet 1 described above has the aforementioned surface properties. This decorative sheet 1 provides the user with a smooth and uniform tactile feel when sliding their skin, for example, their finger, across the surface of the surface protection layer 5. Specifically, the decorative sheet 1 allows the user to slide their finger, etc., with minimal friction, without the user feeling any large irregularities across the entire surface of the surface protection layer 5.

[0141] The decorative sheet 1 that provides a smooth touch to the user is suitable for applications that frequently or for long periods of time contact the user's skin, such as furniture. Articles using the decorative sheet 1 do not cause discomfort to the user when in contact with the user's skin.

[0142] Because the surface protection layer 5 of the decorative sheet 1 has the aforementioned surface properties, it can achieve low gloss even without a gloss modifier (matting additive). Gloss modifiers reduce the oleophobicity of the layer formed from the resin material, so surface protection layers containing gloss modifiers are susceptible to fingerprints. Surface protection layers 5 without gloss modifiers are less likely to absorb oil, making fingerprints less likely to adhere. Furthermore, surface protection layers 5 with excellent oleophobicity are less likely to absorb oil stains or contaminants. Furthermore, when the surface of a surface protection layer 5 without a gloss modifier is scratched, the gloss modifier particles do not fall off. Therefore, decorative sheets 1 including such surface protection layers 5 are less likely to suffer gloss changes or scratches.

[0143] The reason why the surface protection layer 5 having the above-mentioned surface properties is obtained by the above-mentioned method is as follows.

[0144] Oxygen in the gas phase not only absorbs short-wavelength ultraviolet light but also inhibits free radical polymerization. The effect of oxygen contained in the gas phase on free radical polymerization is greatest in the portion of a coating film composed of an ionizing radiation-curable resin adjacent to the gas phase, and decreases with increasing distance from the coating surface. Therefore, by varying the oxygen concentration in the gas phase during the second irradiation step, the relationship between the distance from the coating surface and the degree of crosslinking can be altered.

[0145] When this relationship changes, the thickness of the cured film produced on the surface of the coating during the second irradiation step and the degree of in-plane expansion of the cured film due to the crosslinking reaction also change. The cumulative amount of light during the second irradiation step also affects the thickness of the cured film and the degree of in-plane expansion of the cured film. Furthermore, the thickness of the cured film and the degree of in-plane expansion of the cured film affect the surface properties of the surface protective layer. Furthermore, the thickness of the coating also affects the formation of wrinkles.

[0146] Therefore, for example, by appropriately setting the composition of the ionizing radiation curable resin, the thickness of the coating film, the oxygen concentration in the gas phase in the second irradiation step, and the integrated light intensity in the second irradiation step, a surface protective layer having desired surface properties can be obtained.

[0147] Example

[0148] Hereinafter, examples of the present invention will be described.

[0149] <Example 1>

[0150] The reference was created by Figures 1 to 3 The decorative sheet 1 is described. It should be noted that, in this example, the transparent resin layer 4, the primer layer 6, the adhesive layer 7 and the concealing layer 8 are omitted.

[0151] First, prepare a unit area mass of 50g / m 2 Impregnated paper (GFR-506: manufactured by Kojin Co., Ltd.) was used as the base material layer 2. A pattern layer 3 was formed on one surface of the base material layer 2 using an oil-based nitrocellulose resin-based gravure printing ink (PCNT (PCRNT) various colors: manufactured by Toyo Ink Co., Ltd.).

[0152] Next, a surface protection layer coating liquid is applied onto the pattern layer 3. As the surface protection layer coating liquid, a coating liquid prepared by blending the following particles into the following ionizing radiation curable resin is used.

[0153] ·Ionizing radiation curable resin

[0154] Type: Ethylene glycol diacrylate (EO9 molar addition)

[0155] Product Name: Light Acrylate 9EG-A (Kyoeisha Chemical Co., Ltd.)

[0156] Mixing: 100 parts by mass

[0157] ·particle

[0158] Product name: Sylysia (registered trademark) 250N (manufactured by Fuji Silysia Chemical Ltd.)

[0159] Particle size: 5μm

[0160] Mixing: 2 parts by mass

[0161] Photoinitiator

[0162] Trade name: Irgacure 184 (BASF Japan Ltd.)

[0163] Mixing: 1 part by mass

[0164] A coating film composed of the surface protective layer coating liquid was formed to a thickness of 5 μm.

[0165] Then, the first irradiation step was performed. Specifically, a high-pressure mercury lamp with a main wavelength of ultraviolet light of 365 nm was used in the atmosphere so that the cumulative light intensity became 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating liquid is irradiated in a manner to semi-cure the coating film.

[0166] Next, the second irradiation step was performed. Specifically, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating liquid was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0167] Finally, the third irradiation step is performed. Specifically, the coating film is irradiated with ionizing radiation to cure the entire film, thereby forming the surface protection layer 5.

[0168] The decorative sheet 1 was obtained through the above-described process.

[0169] <Example 2>

[0170] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0171] ·Ionizing radiation curable resin

[0172] Type: Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0173] Product name: Miramer M3160 (made by Miwon)

[0174] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0175] <Example 3>

[0176] A decorative sheet 1 was produced by the same method as in Example 2 except for the following points. Specifically, in this example, the blending amount of the following particles was changed.

[0177] ·particle

[0178] Trade name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.)

[0179] Particle size: 5μm

[0180] Mixing: 1.3 parts by mass

[0181] <Example 4>

[0182] A decorative sheet 1 was produced by the same method as in Example 2 except for the following points. Specifically, in this example, the blending amount of the following particles was changed.

[0183] ·particle

[0184] Trade name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.)

[0185] Particle size: 5μm

[0186] Mixing: 15 parts by mass

[0187] <Example 5>

[0188] A decorative sheet 1 was produced by the same method as in Example 2 except for the following points. Specifically, in this example, the blending amount of the following particles was changed.

[0189] ·particle

[0190] Trade name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.)

[0191] Particle size: 5μm

[0192] Mixing: 22 parts by mass

[0193] <Example 6>

[0194] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0195] ·Ionizing radiation curable resin

[0196] Type: Trimethylolpropane EO modified triacrylate (EO15 molar addition)

[0197] Product name: SR9035 (manufactured by Sartomer)

[0198] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0199] <Example 7>

[0200] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0201] ·Ionizing radiation curable resin

[0202] Type: Trimethylolpropane EO modified triacrylate (EO3 molar addition)

[0203] Product name: Miramer M3130 (made by Miwon)

[0204] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity became 100 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0205] <Example 8>

[0206] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0207] ·Ionizing radiation curable resin

[0208] Type: Trimethylolpropane PO modified triacrylate (PO6 molar addition)

[0209] Product name: NK Ester A-TMPT-6PO (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0210] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0211] <Example 9>

[0212] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0213] ·Ionizing radiation curable resin

[0214] Type: Caprolactone-modified tris-(2-acryloyloxyethyl) isocyanurate (caprolactone (CL) 3 mol addition)

[0215] Product name: NK Ester A-9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0216] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity became 100 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0217] <Example 10>

[0218] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: Specifically, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 1 μm.

[0219] ·Ionizing radiation curable resin

[0220] Type: Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0221] Product name: Miramer M3160 (made by Miwon)

[0222] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 10 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0223] <Example 11>

[0224] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: Specifically, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 2 μm.

[0225] ·Ionizing radiation curable resin

[0226] Type: Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0227] Product name: Miramer M3160 (made by Miwon)

[0228] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 10 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0229] <Example 12>

[0230] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: That is, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 9 μm.

[0231] ·Ionizing radiation curable resin

[0232] Type: Trimethylolpropane EO modified triacrylate (EO3 molar addition)

[0233] Product name: Miramer M3130 (made by Miwon)

[0234] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 150 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0235] <Example 13>

[0236] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0237] ·Ionizing radiation curable resin

[0238] Type: Ethoxylated pentaerythritol tetraacrylate (EO35 molar addition)

[0239] Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0240] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0241] <Example 14>

[0242] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0243] ·Ionizing radiation curable resin

[0244] Type: Ethoxylated pentaerythritol tetraacrylate (EO50 molar addition)

[0245] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0246] <Example 15>

[0247] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0248] ·Ionizing radiation curable resin

[0249] Type: Ethoxylated pentaerythritol tetraacrylate (EO20 molar addition)

[0250] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 100 ppm at atmospheric pressure so that the accumulated light intensity was 100 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0251] <Example 16>

[0252] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0253] ·Ionizing radiation curable resin

[0254] Type: Propoxylated pentaerythritol tetraacrylate (PO35 molar addition)

[0255] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 50 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0256] <Example 17>

[0257] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0258] ·Ionizing radiation curable resin

[0259] Type: Caprolactone modified pentaerythritol tetraacrylate (CL20 molar addition)

[0260] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 100 ppm at atmospheric pressure so that the accumulated light intensity was 100 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0261] <Example 18>

[0262] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: Specifically, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 1 μm.

[0263] ·Ionizing radiation curable resin

[0264] Type: Ethoxylated pentaerythritol tetraacrylate (EO35 molar addition)

[0265] Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0266] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 10 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0267] <Example 19>

[0268] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: Specifically, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 2 μm.

[0269] ·Ionizing radiation curable resin

[0270] Type: Ethoxylated pentaerythritol tetraacrylate (EO35 molar addition)

[0271] Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0272] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 10 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0273] <Example 20>

[0274] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: That is, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 9 μm.

[0275] ·Ionizing radiation curable resin

[0276] Type: Ethoxylated pentaerythritol tetraacrylate (EO20 molar addition)

[0277] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 150 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0278] <Example 21>

[0279] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0280] ·Ionizing radiation curable resin

[0281] Type: Ethoxylated dipentaerythritol hexaacrylate (EO12 mole addition)

[0282] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 100 ppm at atmospheric pressure so that the accumulated light intensity was 150 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0283] <Example 22>

[0284] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0285] ·Ionizing radiation curable resin 1

[0286] Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0287] Product name: Miramer M3160 (made by Miwon)

[0288] Mixing: 60 parts by mass

[0289] ·Ionizing radiation curable resin 2

[0290] Type: Dipentaerythritol hexaacrylate

[0291] Product name: Miramer M600 (made by Miwon)

[0292] Mixing: 40 parts by mass

[0293] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 10 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0294] <Example 23>

[0295] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points. That is, in this example, the following ionizing radiation curable resin was used.

[0296] ·Ionizing radiation curable resin 1

[0297] Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0298] Product name: Miramer M3160 (made by Miwon)

[0299] Mixing: 40 parts by mass

[0300] ·Ionizing radiation curable resin 2

[0301] Type: Dipentaerythritol hexaacrylate

[0302] Product name: Miramer M600 (made by Miwon)

[0303] Mixing: 60 parts by mass

[0304] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 10 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0305] <Example 24>

[0306] A decorative sheet 1 was produced by the same method as in Example 1 except for the following points: That is, in this example, the following ionizing radiation curable resin was used, and a coating film composed of the surface protective layer coating liquid was formed to a thickness of 14 μm.

[0307] ·Ionizing radiation curable resin 1

[0308] Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0309] Product name: Miramer M3160 (made by Miwon)

[0310] Mixing: 40 parts by mass

[0311] ·Ionizing radiation curable resin 2

[0312] Type: Dipentaerythritol hexaacrylate

[0313] Product name: Miramer M600 (made by Miwon)

[0314] Mixing: 60 parts by mass

[0315] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 100 ppm at atmospheric pressure so that the accumulated light intensity was 100 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0316] <Comparative Example 1>

[0317] A decorative sheet was produced in the same manner as in Example 1 except for the following: That is, in this example, a coating liquid prepared by blending the following particles into the following ionizing radiation curable resin was used as the coating liquid for the surface protective layer.

[0318] ·Ionizing radiation curable resin

[0319] Type: Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0320] Product name: Miramer M3160 (made by Miwon)

[0321] Mixing: 100 parts by mass

[0322] ·particle

[0323] Trade name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.)

[0324] Particle size: 5μm

[0325] Mixing: 15 parts by mass

[0326] Furthermore, the coating film composed of the surface protection layer coating liquid is cured only by the third irradiation step without performing the first irradiation step and the second irradiation step.

[0327] <Comparative Example 2>

[0328] A decorative sheet was produced in the same manner as in Example 1 except for the following: That is, in this example, a coating liquid prepared by blending the following particles into the following ionizing radiation curable resin was used as the coating liquid for the surface protective layer.

[0329] ·Ionizing radiation curable resin

[0330] Type: Ethoxylated pentaerythritol tetraacrylate (EO35 molar addition)

[0331] Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0332] Mixing: 100 parts by mass

[0333] ·particle

[0334] Trade name: Sylysia 250N (manufactured by Fuji Silysia Chemical Ltd.)

[0335] Particle size: 5μm

[0336] Mixing: 15 parts by mass

[0337] Furthermore, the coating film composed of the surface protection layer coating liquid is cured only by the third irradiation step without performing the first irradiation step and the second irradiation step.

[0338] <Comparative Example 3>

[0339] A decorative sheet was produced in the same manner as in Example 1 except for the following: That is, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 10 μm.

[0340] ·Ionizing radiation curable resin

[0341] Type: Trimethylolpropane EO modified triacrylate (EO6 molar addition)

[0342] Product name: Miramer M3160 (made by Miwon)

[0343] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 500 ppm at atmospheric pressure so that the accumulated light intensity was 150 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0344] <Comparative Example 4>

[0345] A decorative sheet was produced in the same manner as in Example 1 except for the following: That is, in this example, the following ionizing radiation curable resin was used, and a coating film made of the surface protective layer coating liquid was formed to a thickness of 10 μm.

[0346] ·Ionizing radiation curable resin

[0347] Type: Ethoxylated pentaerythritol tetraacrylate (EO35 molar addition)

[0348] Product name: NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0349] In the second irradiation step, a Xe excimer lamp was used in a nitrogen atmosphere with an oxygen concentration of 200 ppm at atmospheric pressure so that the accumulated light intensity was 150 mJ / cm 2 The surface of the coating film composed of the surface protective layer coating solution was irradiated with ultraviolet rays having a wavelength of 172 nm.

[0350] <Comparative Example 5>

[0351] A decorative sheet was produced by the same method as in Example 1 except for the following points: In this example, particles (Sylysia 250N) were not blended.

[0352] <Evaluation>

[0353] The following evaluations were performed on each of the decorative sheets.

[0354] (1) Glossiness

[0355] Glossiness The 60-degree glossiness was measured using Rhopoint IQ (manufactured by Konica Minolta, Inc.) The “60-degree glossiness value” in Tables 1 to 3 below indicates the 60-degree glossiness.

[0356] (2) Skin touch

[0357] Skin feel was evaluated by the following method.

[0358] First, we conducted preliminary preparations to ensure consistent evaluation criteria across all evaluators. Specifically, we prepared 10 standard test pieces with varying surface properties. Next, we had 20 blindfolded evaluators swipe their fingers across the surfaces of the standard test pieces and categorize their tactile sensations into the following five groups.

[0359] Group 1: The bumps are barely noticeable and the friction is minimal.

[0360] Group 2: Feeling the presence of small bumps or slightly greater friction.

[0361] Group 3: The touch sensation is between the touch sensations of Group 1 and Group 2.

[0362] Group 4: Feel the presence of large bumps.

[0363] Group 5: No bumps or depressions can be felt, but strong friction is felt.

[0364] Repeat the above steps until the evaluation results of each evaluator are consistent for more than 3 times in a row, and the evaluation results of the evaluators are consistent for 3 times in a row.

[0365] Next, for each decorative sheet, the evaluators blindfolded themselves and slid their fingers across the surface of the surface protective layer. The touch was then classified into the five groups described above. This procedure was repeated until the evaluators' evaluations agreed three or more times, and until the evaluations between the evaluators agreed three times in a row. Based on these results, the skin feel was evaluated according to the following criteria.

[0366] AAA (smooth): Group 1

[0367] AA (Smooth): Group 3

[0368] A (Smooth): Group 2

[0369] B (rough or slippery): Group 4 or 5

[0370] (3) Uniformity of touch

[0371] The 20 evaluators who evaluated the skin feel evaluated the uniformity of the touch by the following method after the evaluation of the skin feel.

[0372] Test pieces measuring 10 cm long by 10 cm wide were cut from each decorative sheet. The 20 blindfolded evaluators were instructed to freely slide their fingers across the entire surface of the surface protective layer of each test piece. The uniformity of the tactile feel was then classified into the following three groups based on the presence or degree of change in the skin feel (smooth feel).

[0373] Group 1: Parts where no difference in skin touch was felt (smooth touch).

[0374] Group 2: Although some areas felt a difference in skin texture (smooth texture), the degree of change was slight.

[0375] Group 3: Areas where a noticeable difference in skin touch (smooth touch) was felt.

[0376] This step was then repeated until the evaluations by each evaluator were consistent for three or more consecutive times, and until the evaluations by the evaluators were consistent for three consecutive times. Based on these results, the uniformity of the tactile feel was evaluated according to the following criteria. Note that this evaluation was not performed for the decorative sheets of Comparative Examples 1 to 4, which received a rating of B for skin feel.

[0377] AA: Group 1

[0378] A: Group 2

[0379] B: Group 3.

[0380] (4) Fingerprint resistance

[0381] As an evaluation of anti-fingerprint properties, evaluation of fingerprint wiping properties was performed.

[0382] Specifically, the 60° glossiness of each decorative sheet surface was first measured, and this 60° glossiness was used as the initial glossiness. Next, an anti-fingerprint evaluation liquid was applied to the surface protective layer, and the anti-fingerprint evaluation liquid adhered to the decorative sheet surface was wiped off. Here, a higher fatty acid was used as the anti-fingerprint evaluation liquid. The 60° glossiness of the portion after wiping with the anti-fingerprint evaluation liquid was then measured, and this 60° glossiness was used as the post-wiping glossiness.

[0383] The fingerprint wipe rate is calculated according to the following formula.

[0384] Fingerprint wiping rate (%) = (glossiness after wiping / initial glossiness) × 100

[0385] The evaluation criteria are as follows.

[0386] AA: 70% or more and less than 250%

[0387] A: 50% or more and less than 70%, or 250% or more and less than 300%

[0388] B: less than 50%, or more than 300%

[0389] (5)Pollution resistance

[0390] To evaluate stain resistance, the Stain A test specified in the Japanese Agricultural Standards (JAS) was conducted. 10 mm wide lines were drawn on the surface protective layer of each decorative sheet using blue ink, black quick-drying ink, and a red crayon. The lines were then wiped clean with a cloth containing ethanol.

[0391] The evaluation criteria are as follows.

[0392] AA: Can easily wipe off all colored threads.

[0393] A: You can wipe part of each color thread, but dirt will remain on some parts.

[0394] B: The colored threads cannot be wiped.

[0395] (6) Injury resistance test

[0396] Each decorative sheet was attached to a wooden substrate B using a urethane adhesive. A stainless steel wool rubbing test was then performed to evaluate scratch resistance. Specifically, the decorative sheet was rubbed back and forth 20 times with stainless steel wool while applying a 100g load. Any scratches or gloss changes on the decorative sheet surface were visually observed.

[0397] The evaluation criteria are as follows.

[0398] AA: No surface damage or gloss changes.

[0399] A: The surface has slight damage or gloss changes.

[0400] B: The surface has obvious damage or gloss changes.

[0401] [Table 1]

[0402]

[0403] [Table 2]

[0404]

[0405] [Table 3]

[0406]

[0407] [Table 4]

[0408]

[0409] As shown in Tables 1 to 3, the decorative sheets involved in Examples 1 to 24 gave the evaluators a smooth touch and uniformity of touch. In addition, the decorative sheets involved in Examples 1 to 24 had low gloss and excellent fingerprint resistance, stain resistance and scratch resistance. In contrast, as shown in Table 4, the decorative sheets involved in Comparative Examples 1 and 2 did not give the evaluators a smooth touch, and their fingerprint resistance, stain resistance and scratch resistance were poor. In addition, the decorative sheets involved in Comparative Examples 3 and 4 had low gloss and excellent fingerprint resistance, stain resistance and scratch resistance, but did not give the evaluators a smooth touch. In addition, the decorative sheet involved in Comparative Example 5 had low gloss and excellent fingerprint resistance, stain resistance and scratch resistance, and gave the evaluators a smooth touch, but had poor uniformity of touch.

[0410] Explanation of symbols

[0411] 1…Decorative sheet, 2…Original material layer, 3…Design layer, 4…Transparent resin layer, 5…Surface protection layer, 5A…Core portion, 5B…Ridge portion, 6…Primer layer, 7…Adhesive layer, 8…Concealing layer, 11…Decorative material, B…Base material

Claims

1. A decorative sheet comprising a raw material layer and a surface protection layer provided on one surface of the raw material layer, The surface of the surface protection layer is provided with a concavo-convex structure including a plurality of ridge portions each protruding in a ridge shape. The height Rpk of the protruding peaks of the concavo-convex structure of the surface protection layer is less than 3.5 μm. The mass concentration C (mass %) of carbon atoms, the mass concentration O (mass %) of oxygen atoms, and the mass concentration Si (mass %) of silicon atoms in the surface protective layer satisfy the following relationship: 0.5≤{Si / (C+O+Si)}×100.

2. The decorative sheet according to claim 1, wherein: The protruding peak height Rpk is greater than or equal to 0.5 μm.

3. The decorative sheet according to claim 1 or 2, wherein: The mass concentration C (mass %) of carbon atoms, the mass concentration O (mass %) of oxygen atoms, and the mass concentration Si (mass %) of silicon atoms in the surface protective layer satisfy the following relationship: 0.5≤{Si / (C+O+Si)}×100≤5.

0.

4. The decorative sheet according to any one of claims 1 to 3, wherein: The surface protection layer has a roughness curve element having an average length RSm of 800 μm or less of the concavo-convex structure.

5. The decorative sheet according to any one of claims 1 to 3, wherein: The surface protection layer has an average length RSm of roughness curve elements of the concavo-convex structure of 350 μm or less.

6. The decorative sheet according to claim 4 or 5, wherein: The average length RSm is 10 μm or more.

7. The decorative sheet according to any one of claims 1 to 6, wherein: The surface protection layer has a thickness of 2 μm to 15 μm.

8. The decorative sheet according to any one of claims 1 to 6, wherein: The surface protection layer has a thickness of 2 μm or more and less than 10 μm.

9. The decorative sheet according to any one of claims 1 to 8, wherein: The surface protection layer has a glossiness of 20.0 or less.

10. The decorative sheet according to any one of claims 1 to 8, wherein: The surface protection layer has a glossiness of 10.0 or less.

11. The decorative sheet according to any one of claims 1 to 10, wherein: At least a portion of the multiple ridge-shaped portions are adjacent in the width direction, and at the position where the at least a portion of the multiple ridge-shaped portions are adjacent in the width direction, in a cross-section parallel to the width direction and the thickness direction of the surface protective layer, the portion where the concave-convex structure is provided has a sinusoidal wave shape.

12. The decorative sheet according to any one of claims 1 to 11, wherein: The surface protective layer comprises a cured product of an ionizing radiation curable resin, The main component of the ionizing radiation curable resin is an acrylate containing a repeating structure. The repeating structure is any one of ethylene oxide, propylene oxide, and ε-caprolactone, The repeating number of the repeating structure is 3 or more.

13. The decorative sheet according to any one of claims 1 to 11, wherein: The surface protective layer comprises a cured product of an ionizing radiation curable resin, The main component of the ionizing radiation curable resin is acrylate, which is composed of a first acrylate containing a repeating structure and a second acrylate with 1 to 6 functionalities. The repeating structure is any one of ethylene oxide, propylene oxide, and ε-caprolactone, and the number of repetitions of the repeating structure is 3 or more.

14. A decorative material comprising: The decorative sheet according to any one of claims 1 to 13, and A substrate for pasting the decorative sheet.

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