Method for manufacturing decorative sheets, decorative sheets, decorative materials, and resin compositions

Abstract

To provide a method for manufacturing decorative sheets that can reduce the environmental impact when forming a surface protective layer and produce decorative sheets with good visibility. [Solution] The surface protective layer formation process comprises a coating process in which a resin composition is applied to a substrate to form a coating layer, a first irradiation process in which the coating layer is irradiated with a first wavelength light of 100 nm to less than 200 nm, and a second irradiation process in which a second wavelength light or electron beam of 200 nm to 450 nm is irradiated to obtain a surface protective layer. The resin composition contains an ionizing radiation-curable compound and particles containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is added at a rate of 3 moles or more per mole of molecule, and has a viscosity of 500 mPa·s or less at 25°C. The maximum value of the reflectance intensity at a reflection angle of 30° to 60° when light is incident at an incident angle of 45° on the surface of the surface protective layer opposite to the substrate is I max / Minimum value I min A method for manufacturing decorative sheets, wherein the ratio is between 1.0 and 1.8.

Description

[Technical Field]

[0001] This disclosure relates to a method for manufacturing decorative sheets, decorative sheets, decorative materials, and resin compositions. [Background technology]

[0002] For decorative sheets used in cosmetic materials, low gloss is sometimes required, for example, to improve aesthetic appeal. A method has been proposed for manufacturing a decorative sheet having a base material and a surface protective layer, wherein a decorative sheet exhibiting low gloss is obtained by forming an uneven shape on the surface of the surface protective layer opposite to the base material. For example, Patent Documents 1 and 2 disclose a decorative sheet including a base material layer and a surface protective layer, wherein the surface protective layer has low gloss. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 7243755 [Patent Document 2] Japanese Patent Publication No. 2022-25623 [Overview of the project] [Problems that the invention aims to solve]

[0004] In recent years, there has been a growing demand for manufacturing methods of decorative sheets that have a low environmental impact. Resin compositions for surface protective layers often involve mixing ionizing radiation-curable compounds, primarily composed of oligomers, with solvents to reduce viscosity and improve applicability. However, such solvent-containing resin compositions can volatilize during the formation of the surface protective layer, potentially posing adverse effects on the environment and operator safety.

[0005] To reduce environmental impact, it is effective to make the resin composition for the surface protective layer of decorative sheets solvent-free. By including an ionizing radiation-curable compound mainly composed of monomers in the resin composition for the surface protective layer, the viscosity of the resin composition is reduced, and the coatability is improved even without solvents. However, the inventors of this invention have found that in the case of an ionizing radiation-curable compound mainly composed of monomers, the flexibility of the coated layer decreases due to the large number of crosslinking points, making it difficult to control the surface shape to achieve low gloss. Furthermore, when the ionizing radiation-curable compound is mainly composed of monomers, the strength of the coated layer decreases, so it is necessary to reinforce it with particles. The inventors of this invention have found that when particles are used, specular reflection is strong, and the surface may appear whitish depending on the viewing angle, which can reduce visibility. As described above, the inventors of this application have newly discovered that it is difficult to achieve both a reduction in environmental impact when forming a surface protective layer and good visibility.

[0006] This disclosure has been made in view of the above-mentioned problems, and its main purpose is to provide a method for manufacturing a decorative sheet having a base material and a surface protective layer, which can reduce the environmental burden when forming the surface protective layer and can produce a decorative sheet with good visibility. [Means for solving the problem]

[0007] This disclosure provides a method for manufacturing a decorative sheet, comprising: a substrate preparation step of preparing a substrate having a first surface and a second surface facing the first surface; and a surface protection layer formation step of forming a surface protection layer on the first surface of the substrate, wherein the surface protection layer formation step includes: a coating process of applying a resin composition to the first surface of the substrate to form a coating layer; a first irradiation process of irradiating the coating layer with a first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate; and a process of applying a surface protection layer to the coating layer after the first irradiation process. The method comprises a second irradiation treatment to obtain the above surface protective layer by irradiating with a second wavelength light or electron beam of 200 nm to 450 nm, wherein the resin composition contains an ionizing radiation-curable compound containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is imparted at a viscosity of 500 mPa·s or less at 25°C, and the maximum value of the reflectance intensity at a reflection angle of 30° to 60° when light is incident at an incident angle of 45° on the surface of the above surface protective layer opposite to the substrate, is I max and minimum value I min Ratio I max / I min The present invention provides a method for manufacturing decorative sheets, wherein the ratio is between 1.0 and 1.8.

[0008] This disclosure provides a decorative sheet manufactured by the method for manufacturing a decorative sheet described above.

[0009] This disclosure provides a decorative material comprising an adherend and a decorative sheet disposed on the surface of the adherend, wherein the decorative sheet is the decorative sheet described above.

[0010] This disclosure provides a resin composition for forming the surface protective layer of a decorative sheet having a substrate and a surface protective layer, comprising an ionizing radiation-curable compound containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, and particles, wherein the resin composition has a viscosity of 500 mPa·s or less at 25°C. [Effects of the Invention]

[0011] The method for manufacturing decorative sheets described in this disclosure has the advantage of reducing environmental impact and producing decorative sheets with good visibility, since the resin composition for the surface protective layer has good coating properties even without solvents. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic cross-sectional view illustrating the method for manufacturing the decorative sheet in this disclosure. [Figure 2] This flowchart illustrates the surface protective layer formation process in this disclosure. [Figure 3] These are the measurement results of the reflectance intensity when light is incident at an incident angle of 45° on the surface protective layer in this disclosure and on a conventional surface protective layer. [Figure 4] This is an example of a microscopic image of the surface protective layer of the decorative sheet in this disclosure. [Figure 5] This is a schematic cross-sectional view illustrating the method for manufacturing the decorative sheet in this disclosure. [Figure 6] This is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. [Figure 7] This is a schematic cross-sectional view illustrating an example of a cosmetic material in this disclosure. [Modes for carrying out the invention]

[0013] The embodiments will be described below with reference to the drawings and other figures. However, this disclosure can be implemented in many different ways and should not be limited to the embodiments described below. In addition, the drawings may schematically represent the width, thickness, and shape of each part compared to the actual form in order to make the explanation clearer, but this is merely an example and should not be interpreted as limiting.

[0014] In this specification, when describing a configuration in which one member is placed on top of another member, the terms "on top" or "below" include, unless otherwise specified, both cases: when the other member is placed directly above or below the member in contact with it, and when the other member is placed above or below the member via yet another member. Similarly, when describing a configuration in this specification in which one member is placed on the surface of another member, the terms "on the surface" or "on the side of the surface" include, unless otherwise specified, both cases: when the other member is placed directly above or below the member in contact with it, and when the other member is placed above or below the member via yet another member.

[0015] Furthermore, in this specification, the terms “board,” “sheet,” and “film” are not distinguished from each other solely on the basis of their names. For example, “sheet” includes components that are also called “board” or “film.”

[0016] The manufacturing method of the decorative sheet, the decorative sheet, the decorative material, and the resin composition described herein will be explained in detail below.

[0017] A. Manufacturing method of decorative sheets The present disclosure is a method for manufacturing a decorative sheet, comprising: a substrate preparation step of preparing a substrate having a first surface and a second surface facing the first surface; and a surface protection layer formation step of forming a surface protection layer on the first surface of the substrate, wherein the surface protection layer formation step comprises: a coating process of applying a resin composition to the first surface of the substrate to form a coating layer; a first irradiation process of irradiating the coating layer with a first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate; and the surface protection layer formation step after the first irradiation process The present invention comprises a second irradiation treatment to obtain the surface protective layer by irradiating the coated layer with a second wavelength light or electron beam of 200 nm to 450 nm, wherein the resin composition contains an ionizing radiation-curable compound containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, and particles, the viscosity at 25°C is 500 mPa·s or less, and the maximum value of the reflectance intensity at a reflection angle of 30° to 60° when light is incident at an incident angle of 45° on the surface of the surface protective layer opposite to the substrate is I max and minimum value I min Ratio I max / I min However, it is between 1.0 and 1.8.

[0018] Figure 1 is a schematic cross-sectional view illustrating a method for manufacturing a decorative sheet according to this disclosure. First, as shown in Figure 1(a), a substrate 1 having a first surface 1a and a second surface 1b facing the first surface 1a is prepared (substrate preparation step). Next, as shown in Figure 1(b), a surface protection layer 2 is formed on the first surface 1a of the substrate 1 to obtain a decorative sheet 10 (surface protection layer formation step). Figure 2 is a flowchart illustrating the surface protection layer formation step according to this disclosure. The surface protection layer formation step according to this disclosure includes a coating process P1 in which a resin composition is applied to the first surface of the substrate to form a coating layer, a first irradiation process P2 in which the coating layer is irradiated with first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate, and a second irradiation process P3 in which the coating layer after the first irradiation process is irradiated with second wavelength light of 200 nm or more and 450 nm or less or an electron beam to obtain a surface protection layer.

[0019] In the present disclosure, the resin composition used in the coating process contains an ionizing radiation curable compound containing a bifunctional or higher functional modified (meth)acrylate monomer having 3 moles or more of modified species per mole of molecule, and particles, and has a viscosity at 25°C of 500 mPa·s or less. Further, as shown in FIG. 1(b), when light is incident at an incident angle of 45° with respect to the surface S1 on the opposite side of the substrate 1 of the surface protective layer 2 obtained by the second irradiation treatment, the maximum value I of the reflection intensity at a reflection angle of 30° or more and 60° or less max and the minimum value I min of the ratio I max / I min is 1.0 or more and 1.8 or less.

[0020] According to the present disclosure, since the resin composition applied in the coating process in the surface protective layer forming step contains a modified (meth)acrylate monomer as an ionizing radiation curable compound, the viscosity of the resin composition can be controlled within a predetermined range, and it can be applied well even without a solvent. Generally, a composition mainly containing a polymerizable monomer tends to have many crosslinking points and insufficient flexibility, and tends to volatilize due to its low molecular weight. In the present disclosure, by using a modified (meth)acrylate monomer having 3 moles or more of modified species per mole of molecule, the flexibility of the polymer becomes high, and a fine uneven shape is likely to be formed. Generally, when mainly containing a polymerizable monomer, the strength of the coating layer is lower than when mainly containing an oligomer. In the present disclosure, since the resin composition contains particles, the strength of the surface protective layer can be improved. On the other hand, when the resin composition contains particles, the specularly reflected light becomes stronger, the pattern changes depending on the observation angle, and the visibility may decrease. The inventors of the present invention performed the first irradiation treatment and the second irradiation treatment on the coating layer formed using the above resin composition, and formed a desired wrinkle structure on the surface opposite to the substrate of the surface protective layer, and found that a decorative sheet with good visibility in which irregular reflection of light by particles on the surface is suppressed can be manufactured. Specifically, when light is incident at an incident angle of 45 degrees with respect to the surface opposite to the substrate side of the surface protective layer, the ratio I of the maximum value to the minimum value of the reflection intensity at a reflection angle of 30° or more and 60° or less max / I minTo manufacture decorative sheets with a value of 1.8 or less. max / I min A value of 1.8 or less means that sufficiently uniform and fine wrinkles are formed by excimer irradiation, diffuse reflection due to wrinkles is dominant rather than diffuse reflection due to particles protruding from the surface, and the change in reflectivity with respect to the reflection angle is small; in other words, the design has a uniform low gloss depending on the viewing angle. Therefore, according to the method for manufacturing decorative sheets in this disclosure, the resin composition for the surface protective layer has good coating properties even without solvents, thus reducing the environmental impact, and it is possible to manufacture decorative sheets with good visibility.

[0021] The following describes each step in the manufacturing method of the decorative sheet as described in this disclosure.

[0022] 1. Base material preparation process This process involves preparing a substrate having a first surface and a second surface facing the first surface. The substrate is a component that supports the surface protective layer. By having a substrate in the decorative sheet, the surface protective layer can be easily formed, and various properties such as mechanical strength, suitability for post-processing, and design are improved, thus improving the usability of the sheet.

[0023] The substrate is not particularly limited and includes, for example, resin substrates, glass substrates, metal substrates, and fiber substrates. The type of substrate is appropriately selected depending on the application of the decorative sheet.

[0024] Examples of resins used in resin substrates include various synthetic resins and various natural resins. Examples of synthetic resins include thermoplastic resins and curable resins. Considering the suitability for manufacturing, handling, and post-processing of decorative sheets, thermoplastic resins are preferred.

[0025] Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate-(meth)acrylate copolymers; polyamide resins represented by nylon 6 and nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin.

[0026] Examples of natural resins include natural rubber, pine resin, and amber.

[0027] Examples of curable resins include ionizing radiation-curable resins and thermosetting resins.

[0028] Examples of metals used as the metal substrate include aluminum or aluminum alloys such as duralumin; iron or iron alloys such as carbon steel and stainless steel; copper or copper alloys such as brass and bronze; gold, silver, chromium, nickel, cobalt, tin, and titanium. The metal substrate may have a plating film or an anodic oxide film on its surface.

[0029] Examples of fibrous materials used in fibrous substrates include paper such as tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, sulfuric acid paper, paraffin paper, parchment paper, glassine paper, wallpaper backing paper, cardboard, and gypsum board base paper; and woven or nonwoven fabrics made of fibers such as polyester resin fibers, acrylic resin fibers, natural protein or cellulose fibers such as silk, cotton, and hemp, glass fibers, and carbon fibers. Various resins such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin may be added to the fibrous substrate. When the fibrous substrate is a paper substrate, the strength between the fibers of the paper substrate, or the interlayer strength between the paper substrate and other substrates can be improved. Also, fuzzing can be suppressed. As for the method of adding resin, the resin may be impregnated after papermaking, or the resin may be filled in during papermaking. Examples of paper substrates to which resin has been added include inter-paper reinforced paper and resin-impregnated paper.

[0030] In the case of a fiber substrate, it is preferable to have a permeation-preventing resin layer on the surface of the fiber substrate that is on the side of the protective surface layer. Examples of resins used for the permeation-preventing resin layer include two-component curing urethane resins. The permeation-preventing resin layer can be formed by methods such as coating.

[0031] The substrate may contain additives as needed. In the case of a resin substrate, examples of additives include inorganic fillers, flame retardants, lubricants, foaming agents, antioxidants, UV absorbers, light stabilizers, and colorants. Various additives can be used individually or in combination. There are no particular restrictions on the amount of additives, as long as they do not impair the surface properties or processing properties, and they can be set appropriately according to the required properties.

[0032] To improve weather resistance, it is preferable to use weather-resistant agents such as ultraviolet absorbers and light stabilizers among the above-mentioned additives. The ultraviolet absorbers and light stabilizers can be the same as those used in the surface protective layer described above.

[0033] The substrate may be a single layer or a laminate of two or more layers. In the case of a laminate, the substrate may consist of two or more layers of the same type of substrate or two or more layers of different types of substrates.

[0034] In this disclosure, the substrate may also serve as the decorative layer described later.

[0035] The substrate may be transparent or opaque. If the substrate is opaque, it can serve as a decorative layer.

[0036] Furthermore, the substrate may be colored. If the substrate is colored, it can serve as a decorative layer. The manner of coloring is not particularly limited; it may be transparent coloring or opaque coloring (concealing coloring), and these can be chosen arbitrarily.

[0037] If the substrate is colored, a coloring agent may be included. Examples of coloring agents include white pigments such as titanium white, inorganic pigments such as iron black, lead yellow, titanium yellow, reddish-brown, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo black pigments, and perylene black pigments; metallic pigments consisting of flaky foil pieces such as aluminum and brass; and pearlescent pigments consisting of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate. For example, if the surface hue of the substrate on which the decorative sheet is laminated varies, and it is desired to conceal the surface hue and improve the stability of the color tone of the decorative layer, an inorganic pigment such as a white pigment may be used.

[0038] The substrate may be surface-treated to improve adhesion to the layer in contact with it, such as adhesion to the decorative layer or adhesive layer. Examples of surface treatments include physical surface treatments such as oxidation and embossing, and chemical surface treatments. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of embossing methods include sandblasting and solvent treatment. These surface treatments are appropriately selected depending on the type of substrate, but corona discharge treatment is generally preferred considering the effectiveness and ease of operation of the surface treatment.

[0039] Furthermore, if the substrate is a laminate, an adhesive layer or primer layer may be placed between each layer to improve the adhesion between adjacent layers.

[0040] The thickness of the substrate is not particularly limited and is appropriately selected depending on the material of the substrate. In the case of a substrate containing resin, the thickness of the substrate may be, for example, 10 μm to 500 μm, 20 μm to 300 μm, or 40 μm to 200 μm. Also, if the substrate is a paper substrate, the basis weight may be, for example, 20 g / m². 2 More than 150g / m 2 The following applies: 30g / m 2 More than 100g / m 2 The following is also acceptable.

[0041] 2. Surface protective layer formation process This process involves forming a surface protection layer on the first surface of the substrate. As shown in Figure 5, when forming a decorative layer 3 on the substrate 1, the surface protection layer 2 is formed on the surface 3a of the decorative layer 3 opposite to the substrate 1.

[0042] As shown in Figure 2, this process involves performing a coating treatment P1, a first irradiation treatment P2, and a second irradiation treatment P3 in that order. Alternatively, a pre-curing treatment P4, described later, may be included after the coating treatment P1 and before the first irradiation treatment P2. Furthermore, an embossing treatment P5, described later, may be included after the second irradiation treatment P3.

[0043] (1) Coating treatment In the coating process, a resin composition is applied to the first surface of the substrate to form a coating layer. The coating layer may be formed directly on the first surface of the substrate, or it may be formed via other layers such as a decorative layer or a transparent resin layer.

[0044] The resin composition may be applied to at least a portion of the first surface of the substrate, but it is preferable to apply it so as to cover 50% or more of the area of ​​the first surface of the substrate, more preferably so as to cover 90% or more, and more preferably so as to cover 100%.

[0045] Examples of known methods for applying the resin composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating.

[0046] The resin composition in this disclosure comprises an ionizing radiation-curable compound containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, and particles, and having a viscosity of 500 mPa·s or less at 25°C.

[0047] (a) Composition of the resin composition (i) Modified (meth)acrylate monomer The resin composition in this disclosure has a modified (meth)acrylate monomer with two or more functionalities, to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, as an ionizing radiation-curable compound. (Meth)acrylate refers to either acrylate or methacrylate. An ionizing radiation-curable compound is a compound having an ionizing radiation-curable functional group. An ionizing radiation-curable functional group is a functional group that crosslinks and hardens upon irradiation with ionizing radiation.

[0048] The modified (meth)acrylate monomer in this disclosure has at least a (meth)acryloyl group as an ionizing radiation-curable functional group. The (meth)acryloyl group refers to either an acryloyl group or a methacloyl group. The number of functional groups ((meth)acryloyl groups) in the modified (meth)acrylate monomer in this disclosure is usually 2 or more, but may be 3 or more. On the other hand, the number of functional groups in the modified (meth)acrylate monomer is, for example, 8 or less, but may be 6 or less, or 4 or less. By having the number of functional groups within the above range, the number of crosslinking points does not become excessive, making it easier to obtain a sufficiently uniform and fine wrinkle structure. max / I min It is easy to adjust this to 1.8 or less. In particular, the number of functional groups of the modified (meth)acrylate monomer in this disclosure is preferably 4 or less. max / I min This is because it is easy to adjust it to 1.6 or less.

[0049] Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing and / or bridging molecules. While ultraviolet (UV) or electron beams (EB) are commonly used, the term also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0050] The modified (meth)acrylate monomer in this disclosure is a monomer to which a modified species is added at least 3 moles per mole of molecule. The modified species is preferably at least one of ethylene oxide (EO), propylene oxide (PO), and ε-caprolactone (Cl). That is, the modified (meth)acrylate monomer contains one or more of the structures of ethylene oxide, propylene oxide, and ε-caprolactone as a repeating structure. Examples of such repeating structures include the ring-opening structures of oxyethylene (-CH2CH2O-), oxypropylene (-CH2CH2CH2O-) or (-CH2CH(CH3)O-), and ε-caprolactone. The ratio of the modified species per mole of the modified (meth)acrylate monomer molecule is 3 moles or more, may be 5 moles or more, or may be 9 moles or more. When the ratio of the modified species is within the above range, the modified (meth)acrylate monomer molecule can rotate freely and becomes highly flexible, the flexibility of the polymer becomes high, and fine uneven shapes are easily formed. Unmodified (meth)acrylate monomers, or (meth)acrylate monomers with a low proportion of modified species, have more crosslinking points and fewer freely moving resin chains. Therefore, a sufficiently uniform and fine wrinkle structure cannot be formed. max / I min It becomes difficult to keep this within a predetermined range. On the other hand, the proportion of the modified species may be, for example, 50 moles or less, 40 moles or less, 35 moles or less, 30 moles or less, or 15 moles or less. If the proportion of the modified species is too high, the crosslinking density decreases and scratch resistance deteriorates.

[0051] In particular, the modified (meth)acrylate monomer in this disclosure is preferably a monomer with 3 to 15 moles of modified species per mole of molecule, and which is bifunctional to tetrafunctional. The viscosity of the resin composition is 200 mPa·s or less at 25°C, and I max / I min This allows the ratio to be set to 1.6 or less, resulting in better coating properties for the resin composition and further improved visibility.

[0052] The modified (meth)acrylate monomers in this disclosure can be used alone or in combination of multiple types. The content of the modified (meth)acrylate monomer in the resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass, based on the mass of the ionizing radiation-curable compound in the resin composition. By having the content of the modified (meth)acrylate monomer in the resin composition within the above range, the viscosity of the resin composition can be set within the range described later, and the coatability is improved.

[0053] The resin composition in this disclosure may contain a monofunctional (meth)acrylate monomer as an ionizing radiation-curable compound.

[0054] In this disclosure, it is preferable that the resin composition does not contain polymerizable polymers (prepolymers) and polymerizable oligomers as ionizing radiation-curable compounds. The viscosity of the resin composition is lowered by not containing polymerizable polymers and polymerizable oligomers. In this specification, "not containing polymerizable polymers and polymerizable oligomers" means that the resin composition is substantially free of polymerizable polymers and polymerizable oligomers, and specifically, the total amount of polymerizable polymers and polymerizable oligomers relative to the mass of the ionizing radiation-curable compound in the resin composition is 5% by mass or less.

[0055] On the other hand, the resin composition in this disclosure may contain at least one of a polymerizable polymer and a polymerizable oligomer as an ionizing radiation-curable compound. That is, the ionizing radiation-curable compound may be a combination of the above-mentioned modified (meth)acrylate monomer and at least one of a polymerizable polymer and a polymerizable oligomer.

[0056] The content of polymerizable polymers and polymerizable oligomers in the resin composition is limited to an amount such that the viscosity of the resin composition falls within the range described later. The total amount of polymerizable polymers and polymerizable oligomers relative to the mass of the ionizing radiation-curable compound in the resin composition may be, for example, 10% by mass or more and 60% by mass or less, or 20% by mass or more and 50% by mass or less.

[0057] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as one of the ionizing radiation-curable functional groups. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.

[0058] Furthermore, examples of polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins that have many reactive groups in a small molecule, and oligomers having cationic polymerizable functional groups in molecules such as novolac-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0059] Polymerizable oligomers can be used individually or in combination of multiple types. The number of functional groups in a polymerizable oligomer is, for example, 2 to 8, but may also be 2 to 6, or 2 to 4.

[0060] The weight-average molecular weight of the polymerizable oligomer is, for example, 2,500 to 7,500, but may also be 3,000 to 7,000, or 3,500 to 6,000.

[0061] Here, the weight-average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

[0062] The polymerizable polymer is not particularly limited, as long as it is a polymer having two or more ionizing radiation-curable functional groups in its molecule. Examples of polymerizable polymers include (meth)acrylate polymers having at least (meth)acryloyl groups as ionizing radiation-curable functional groups.

[0063] (ii) particles The resin composition in this disclosure contains particles. The inclusion of particles in the resin composition allows for the stable formation of wrinkles on the surface of the surface protective layer. max / I min This can be set to a predetermined range. In other words, the particles function as a wrinkle-forming stabilizer. Although it is possible to form a wrinkle structure in the surface protective layer without using particles as a wrinkle-forming stabilizer, using particles as a wrinkle-forming stabilizer stabilizes the formed wrinkle structure, providing a stable matte effect and uniformity of the surface condition due to the stable formation of wrinkles across the entire surface protective layer. In addition, the inclusion of particles improves the strength of the surface protective layer.

[0064] Furthermore, "wrinkle formation stabilization" means that the in-plane distribution (dispersion σ) of wrinkle shape, geometric characteristics (length, width, and length-to-width ratio of individual protrusions), and surface properties of wrinkles (Ra, RSm, Spc, etc.) converges more effectively with the addition of a wrinkle formation stabilizer compared to the case without the stabilizer. As a result, the in-plane distribution (dispersion σ) of the 60° gloss values ​​of the surface shape, which will be discussed later, also converges. The wrinkle formation stabilizer is added not to diffuse light and suppress light reflection or to create a matte finish, but to stabilize the wrinkle structure.

[0065] Conventionally, there is a method of adjusting gloss by adding a matting agent to create irregularities on the surface of the coating film. Even if the constituent materials and average particle size of the "matting agent" in the prior art and the "wrinkle-forming stabilizer" in this disclosure are the same or similar, they differ in their mechanisms (actions) of suppressing light reflection and matting, the structure for producing light reflection suppression and matting, and the relationship between the amount used and the degree of gloss (gloss value) of the surface.

[0066] In conventional technology, matting agents used to suppress light reflection and reduce gloss exert their own matting effect due to the light diffusion effect caused by their physical shape. Specifically, particles generally referred to as matting agents have a refractive index difference between the particle and the surrounding resin and air, and the matting effect is exerted by the reflection of light rays corresponding to the contour shape of the particle and the light diffusion effect due to the refractive interface. Therefore, if a matting agent is used in the surface protective layer, the ambient light (incident light) is diffused by the matting agent, resulting in a decrease in contrast.

[0067] On the other hand, wrinkle-forming stabilizers do not produce a matting effect through light diffusion caused by the reflection and refraction of light rays by the particles themselves, but rather by stabilizing the formation of wrinkles on the surface of the surface protective layer due to the wrinkle-forming stabilizer. This stabilizes the matting effect on the decorative sheet through the light diffusion effect at the refractive index difference interface between the surface and the air. Therefore, the wrinkle-forming stabilizers used in this disclosure differ from matting agents that produce a matting effect on their own (even if the constituent materials and average particle size of both are the same or similar), in terms of the mechanism (operation) of light reflection suppression and matting, and the structure for producing light reflection suppression and matting.

[0068] Furthermore, "wrinkle-forming stabilizers" and "matting agents" differ in their relationship to the amount contained and the surface gloss value. When the same substance A is used as a wrinkle-forming initiator AW (W: wrinkle), and this is included in a specific amount C to form wrinkles on the surface, the 60° gloss value G of the surface is... 60° AW(C) is the 60° gloss value G of the surface when substance A is used simply as a matting agent AM and is included in a specific amount C, but no wrinkles are formed on the surface. 60° AM This is clearly lower than (C). In other words, the following relationship holds: G 60° AW (C) <G 60° AM (C)

[0069] The average particle size in this disclosure is, for example, 1.3 μm or more, but may also be 1.5 μm or more, or 1.8 μm or more. By having the average particle size within the above range, the matting effect can be stably improved. On the other hand, the average particle size is, for example, 20 μm or less, but may also be 10 μm or less, 8 μm or less, or 7 μm or less. By having the average particle size within the above range, wrinkle formation is stable.

[0070] Here, the average particle size is the median diameter (D50) measured with a laser diffraction / scattering particle size distribution analyzer for the resin composition. Note that the average value obtained by observing the cross-section of the surface protective layer obtained from the resin composition and measuring the particle sizes of multiple particles will be substantially the same as the median diameter (D50) measured with a laser diffraction / scattering particle size distribution analyzer. Therefore, the average particle size may also be determined by observing the cross-section of the surface protective layer.

[0071] When determining the average particle size by cross-sectional observation of the surface protective layer, the cross-section in the thickness direction of the surface protective layer is observed using a scanning electron microscope (SEM) under conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000x. The average particle size (arithmetic mean diameter) is measured for 100 randomly selected non-aggregated particles. The particle size is the value measured by the distance between two parallel lines that maximize the distance between the two lines when the cross-section of the particle is sandwiched between them.

[0072] As particles, for example, inorganic particles and organic particles can be used. Examples of inorganic materials that make up inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate. Among these, silica is preferred because of its excellent transparency. In order to improve the strength of the surface protective layer, it is preferable to use inorganic particles. Examples of organic materials that make up organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, and polyester resin.

[0073] The particle shape is not particularly limited, but examples include spheres, polyhedra, flakes, and amorphous shapes. The surface of the particles may be coated with an organic compound to suppress light diffusion.

[0074] When silica is used as the particle, a smaller specific surface area is preferable when using the BET method by nitrogen adsorption. This is because light diffusion is suppressed. For example, a specific surface area of ​​50 m² is preferable. 2 / g or more 800m 2 It is less than / g and 100m 2 / g or more 500m 2 It may be less than / g.

[0075] To stabilize the formation of wrinkles by particles, the particle content in the resin composition is, for example, 0.10 parts by mass or more, and may be 0.50 parts by mass or more, or 0.75 parts by mass or more, per 100 parts by mass of the ionizing radiation-curable compound. By having a particle content within the above range, wrinkle formation is stabilized, and I max / I min This can be set to a predetermined range. On the other hand, the particle content in the resin composition is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of the ionizing radiation-curable compound. Also, if there are many particles, light scattering by the particles occurs, and I max / I minIt becomes difficult to keep the range within the specified limits. Furthermore, the applicability of the resin composition may decrease.

[0076] Conventional matting agents require a large amount to exhibit a matting effect due to the light diffusion effect caused by their physical shape. However, in this disclosure, as described above, even with a small amount, that is, a smaller amount than the amount required to exhibit a matting effect due to the light diffusion effect caused by the physical shape, an extremely superior matting effect is obtained compared to the effect obtained with conventional matting agents.

[0077] (iii) Additives In addition to the modified (meth)acrylate monomers and particles described above, the resin composition may also contain additives. Examples of additives include weather-resistant agents such as UV absorbers and light stabilizers.

[0078] The ultraviolet absorber is not particularly limited, and examples include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. The ultraviolet absorber is preferably a triazine-based ultraviolet absorber, and more preferably a hydroxyphenyltriazine-based ultraviolet absorber.

[0079] Furthermore, the ultraviolet absorber may have reactive functional groups in its molecule that have ethylenically double bonds, such as (meth)acryloyl groups, vinyl groups, and allyl groups.

[0080] The amount of ultraviolet absorber in the resin composition is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, per 100 parts by mass of the ionizing radiation-curable compound. Furthermore, the amount of ultraviolet absorber is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and particularly preferably 6.0 parts by mass or less, per 100 parts by mass of the ionizing radiation-curable compound. When the amount of ultraviolet absorber is within the above range, the effect of efficiently using the ultraviolet absorber can be obtained.

[0081] The resin composition may contain a light stabilizer. This improves the weather resistance of the surface protective layer. The light stabilizer is not particularly limited and examples include hindered amine light stabilizers such as piperidinyl sebacate-based light stabilizers. The light stabilizer may also have reactive functional groups with ethylenic double bonds in its molecule, such as (meth)acryloyl groups, vinyl groups, and allyl groups. The light stabilizer can be used alone or in combination of several types.

[0082] The content of the light stabilizer in the resin composition is preferably 0.1 parts by mass or more, more preferably 1.0 part by mass or more, per 100 parts by mass of the ionizing radiation-curable compound. Furthermore, the content of the light stabilizer is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and particularly preferably 6.0 parts by mass or less, per 100 parts by mass of the ionizing radiation-curable compound. When the content of the light stabilizer is within the above range, the effect of efficiently using the light stabilizer can be obtained.

[0083] If the ionizing radiation-curable compound is an ultraviolet-curable compound, the resin composition may contain a photopolymerization initiator, a photopolymerization accelerator, and the like.

[0084] Examples of photopolymerization initiators include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.

[0085] The content of the photopolymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the ionizing radiation-curable compound. When the content of the photopolymerization initiator is within the above range, sufficient pre-curing occurs, the viscosity of the surface protective layer composition (ink) increases sufficiently, and uniform wrinkles can be formed. Alternatively, the content of the photopolymerization initiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2.5 parts by mass or less, per 100 parts by mass of the ionizing radiation-curable compound. When the content of the photopolymerization initiator is within the above range, coloring and deterioration of the physical properties of the coated layer due to the photopolymerization initiator can be suppressed.

[0086] Furthermore, photopolymerization accelerators can reduce polymerization inhibition by air during curing and accelerate the curing speed. Examples of photopolymerization accelerators include one or more selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc. The content of the photopolymerization accelerator is the same as that of the photopolymerization initiator described above.

[0087] (iv) Others The resin compositions in this disclosure are preferably substantially solvent-free. That is, the resin compositions are preferably solvent-free. By being substantially solvent-free, the environmental burden caused by the volatilization of solvents during the formation of the surface protective layer can be reduced. In this specification, "substantially solvent-free resin composition" means that the amount of solvent contained in the resin composition is 10% by mass or less of the total mass of the resin composition. The solvent content is preferably 5% by mass or less of the total mass of the resin composition.

[0088] (b) Viscosity of the resin composition The viscosity of the resin composition in this disclosure is typically 500 mPa·s or less at 25°C. Having a viscosity within this range suppresses thickness variations and allows for uniform application. The viscosity of the resin composition is more preferably 450 mPa·s or less, even more preferably 400 mPa·s or less, and particularly preferably 200 mPa·s or less. On the other hand, the viscosity of the resin composition may be, for example, 10 mPa·s or more, and may also be 20 mPa·s or more.

[0089] The viscosity of a resin composition can be controlled by its composition. Specifically, the higher the content of modified (meth)acrylate monomers in the resin composition, the lower the viscosity tends to be. The lower the content of polymerizable oligomers and polymerizable polymers, the lower the viscosity tends to be. Also, the fewer the number of functional groups of the modified (meth)acrylate monomers, the lower the viscosity tends to be. Furthermore, in the case of modified (meth)acrylate monomers of the same type and number of functional groups, the higher the proportion of the modified species, the higher the viscosity tends to be.

[0090] The viscosity of the resin composition was measured using a method compliant with JIS Z8803:2011, which specifies the viscosity measurement method using a cone-plate rotational viscometer. For example, it can be measured using an ICI cone-plate viscometer and a thermocell for warming the sample. The cone plate diameter is 25 mm, and the shear rate is 10 s. -1 The following conditions shall be met. Specifically, the sample shall be placed in the apparatus with the temperature set to 40°C, cooled to 25°C at a cooling rate of 10°C / min, and the viscosity shall be measured. As an ICI cone plate viscometer, for example, the "MCR301" manufactured by Anton Paar can be used.

[0091] (c) Refractive index of the resin composition The refractive index of the resin composition in this disclosure is, for example, 1.5 or less. Having the refractive index of the resin composition within this range improves the visibility of the lower hilt. On the other hand, the refractive index of the resin composition may be, for example, 1.40 or more, or 1.45 or more. Having the refractive index of the resin composition within this range improves the light diffusion effect at the refractive index difference interface between the surface protective layer and the air.

[0092] The refractive index of the resin composition was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.) at a temperature of 23°C and with a sodium light source at a measurement wavelength of 589 nm, in accordance with the refractive index measurement method specified in JIS K 7142.

[0093] (2) First irradiation treatment and second irradiation treatment In the first irradiation treatment, the coated layer is irradiated with light of a first wavelength between 100 nm and less than 200 nm to form a wrinkled structure on the surface opposite to the substrate. In the subsequent second irradiation treatment, the coated layer is irradiated with light of a second wavelength between 200 nm and 450 nm or an electron beam to obtain a surface protective layer. The obtained surface protective layer has a surface shape with a wrinkled structure on the surface opposite to the substrate, and the maximum value of the reflectance intensity at a reflection angle between 30° and 60° when light is incident at an incident angle of 45° is I max and minimum value I min The ratio is I max / I min It is within the specified range.

[0094] Figure 3(a) is a graph showing the reflection intensity I at various reflection angles measured with a variable-angle photometer when light (visible light) is incident on the surface S1 of the surface protective layer 2 at an incident angle of 45°, as shown in Figure 3(b). In Figure 3(a), the solid line shows the reflection intensity I of the surface protective layer in this disclosure, and the dotted line shows the reflection intensity I′ of the conventional surface protective layer. As shown in Figure 3(a), the conventional surface protective layer has strong specular reflection (light reflected at a reflection angle of 45°), and the maximum reflection intensity I is between a reflection angle of 30° and 60°. max and minimum value I min The ratio is I max / I min It is greater than 1.8. max / Imin If the reflection intensity is too high, the design will appear white depending on the viewing angle, resulting in poor visibility. In contrast, as shown in Figure 3(a), the surface protective layer in this disclosure has a maximum reflection intensity of I at a reflection angle of 30° to 60°. max and minimum value I min The difference is small, specifically, I max / I min It is between 1.0 and 1.8. max / I min It is preferable that it is between 1.0 and 1.6. max / I min Because the above range is maintained, excimer irradiation creates sufficiently uniform and fine wrinkles, and diffuse reflection due to wrinkles is dominant rather than diffuse reflection due to particles protruding from the surface. As a result, the change in reflection intensity with respect to the reflection angle is small, meaning that the decorative sheet has a uniform low gloss depending on the viewing angle.

[0095] Here, when light (visible light) is incident at an incident angle of 45° on the surface opposite to the substrate of the surface protective layer, the reflection intensity for each reflection angle between 30° and 60° is measured using a variable-angle photometer. For example, a variable-angle photometer GP-200 manufactured by Murakami Color Technology Laboratory Co., Ltd. can be used. Details are described in the Examples section.

[0096] I max / I min This can be controlled by adjusting the proportion of modified species in the modified (meth)acrylate monomer in the resin composition, the particle content, the viscosity of the resin composition, the cumulative light intensity during the first irradiation, the temperature of the coated layer immediately before the first irradiation treatment, and the thickness of the surface protective layer.

[0097] In this disclosure, by performing the irradiation treatments of the first irradiation treatment and the second irradiation treatment, a wrinkled structure is obtained. max / I min A surface protective layer is obtained that has a specific surface shape that satisfies a predetermined range. The details of the mechanism by which the specific surface shape is obtained by irradiating with at least the first and second irradiation treatments described above are unknown, but it is presumed to be due to the following mechanism.

[0098] First, when the first irradiation treatment described above is performed using low-wavelength (short-wavelength) ultraviolet light, the energy of the ultraviolet light penetrates only to the surface, and the energy does not reach the layers below. As a result, only the surface of the coated layer begins to harden, and it is thought that this hardening shrinkage occurs only on the surface, forming a wrinkled structure. Thus, it is thought that the formation of the wrinkled structure occurs when the coated layer hardens only in a certain thickness direction from the surface due to irradiation with low-wavelength (short-wavelength) ultraviolet light.

[0099] Next, in the second irradiation treatment described above, by irradiating with at least one of either an electron beam or ultraviolet light with a high wavelength (long wavelength) of 200 nm to 400 nm, the curing process can be promoted from the near-surface portion where curing progresses slowly to the deeper portions in the depth direction, while maintaining the wrinkle structure formed on the surface of the coated layer. In other words, by further combining the above second irradiation treatment, the curing state is improved, the coated layer is completely cured, and a surface protective layer is obtained. As a result, it is thought that a wrinkle structure is more likely to appear on the surface of the surface protective layer. Furthermore, it is thought that scratch resistance is also improved as the entire thickness becomes cured and the curing state is improved.

[0100] In the first irradiation process described above, the first wavelength light with a wavelength of 100 nm or more and less than 200 nm is preferably "excimer light" which includes light in the ultraviolet wavelength range from gases such as noble gases like Ar, Kr, Xe, and Ne, halides of noble gases such as F, Cl, I, and Br, or dimers of excited states formed by the discharge of mixed gases thereon, i.e., excimers. Preferably, the wavelength of the excimer light and the excimer light source include, for example, light with a wavelength of 126 nm (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), and 193 nm (ArF) emitted from an Ar2 excimer. Both spontaneous emission light and highly coherent laser light produced by stimulated emission can be used as excimer light, but spontaneous emission light is usually sufficient. These discharge lamps that emit light (ultraviolet light) are also called "excimer lamps."

[0101] Excimer light is characterized by a single wavelength peak and a narrower full width at half maximum compared to ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). Using such excimer light makes it easier to induce wrinkle structures.

[0102] For the same reasons as above, the wavelength of the first wavelength light is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more. Also, the wavelength of the first wavelength light is less than 200 nm, and particularly preferably 172 nm (Xe2). Thus, in order to facilitate the expression of wrinkle structures, it is preferable to use lower wavelength (short wavelength) light, and it can be said that low wavelength (short wavelength) ultraviolet light in the region of less than 200 nm among low wavelength (short wavelength) ultraviolet light (wavelength: 280 nm or less) is preferable.

[0103] The integrated light intensity of the above wavelength light is preferably 50 mJ / cm². 2 More preferably 100 mJ / cm² 2That's all. If the cumulative light intensity is low, wrinkle formation will not be stable, I max / I min It becomes difficult to keep it within a predetermined range. Furthermore, the upper limit of the integrated light quantity of the above wavelength light is not particularly limited. Considering the reduction in the number of lamps required for irradiation with the above wavelength light and the improvement of productivity such as production efficiency, the integrated light quantity of the above wavelength light is preferably 1,000 mJ / cm 2 More preferably 300 mJ / cm² 2 The following applies:

[0104] The ultraviolet irradiance is preferably 1 mW / cm². 2 More preferably 5 mW / cm² 2 More preferably 10 mW / cm² 2 That concludes the explanation. Furthermore, the ultraviolet irradiance is preferably 10 W / cm². 2 More preferably 3 W / cm 2 More preferably, 1 W / cm 2 The following applies, especially considering productivity: UV irradiance should be 500 mW / cm². 2 The following is preferable: 300 mW / cm² 2 The following is more preferable: 150 mW / cm² 2 The following are even more preferable.

[0105] Furthermore, the oxygen concentration when irradiating with the above wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and particularly preferably 300 ppm or less.

[0106] The first wavelength light, between 100 nm and less than 200 nm, used in the first irradiation process described above can also be irradiated using an ultraviolet irradiation device that uses a low-pressure mercury lamp or the like as a light source.

[0107] In this disclosure, in the first irradiation treatment, it is preferable to set the temperature of the coated layer immediately before irradiation with ultraviolet light to 25°C or higher, and more preferably to 30°C or higher. The method for controlling the temperature of the coated layer is not particularly limited, but it can be controlled by methods such as heating the sheet during transport. When the temperature of the coated layer immediately before irradiation with ultraviolet light is within the above range, the temperature of the resin composition on the substrate rises and the viscosity decreases. Furthermore, the reactivity of the resin composition is also improved, so that sufficiently uniform and fine wrinkles can be formed. Therefore, the surface protective layer I max / I min This tends to fall within a predetermined range. The temperature of the coated layer immediately before irradiation with ultraviolet light is, for example, 50°C or less, and may also be 40°C or less. If the temperature of the coated layer immediately before irradiation with ultraviolet light is too high, the resin composition will volatilize easily, and the substrate will deform easily. The temperature of the coated layer immediately before irradiation with ultraviolet light is the temperature at the center of the side of the coated layer opposite to the substrate side.

[0108] After the first irradiation treatment using light of a first wavelength between 100 nm and less than 200 nm as described above, the second irradiation treatment is performed.

[0109] The electron beam irradiation conditions used in the second irradiation treatment described above are not particularly limited as long as the resin composition hardens. The electron beam acceleration voltage is preferably 10kV or higher, more preferably 30kV or higher, even more preferably 50kV, and even more preferably 75kV or higher. The electron beam acceleration voltage is also preferably 300kV or lower, more preferably 250kV or lower, and even more preferably 200kV or lower. When the electron beam acceleration voltage is within the above range, the cured product is more likely to retain the shape of the wrinkle structure. Scratch resistance is also improved. For the same reasons as above, the electron beam irradiation dose is preferably 5kGy or higher, more preferably 10kGy or higher, and even more preferably 15kGy or higher. The electron beam irradiation dose is also preferably 150kGy or lower, more preferably 125kGy or lower, and even more preferably 100kGy or lower.

[0110] The electron source is not particularly limited as long as it can achieve the above irradiation conditions. For example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonant transformer type, insulated core transformer type, and linear type, dynamitron type, and high-frequency type can be used.

[0111] The second wavelength light between 200 nm and 450 nm used in the second irradiation process described above can be irradiated using an ultraviolet irradiation device that uses, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp as a light source. Alternatively, excimer light between 200 nm and 400 nm, such as 222 nm (KrCl), 247 nm (KrF), or 308 nm (XeCl), may be used.

[0112] The wavelength of the second wavelength light is preferably 330 nm or more and 390 nm or less. When the wavelength of the second wavelength light is within this range, it is easier to maintain the shape of the wrinkle structure. For the same reasons as above, the output of the ultraviolet irradiation device is preferably 50 W / cm or more, more preferably 100 W / cm or more. The output of the ultraviolet irradiation device is preferably 300 W / cm or less, more preferably 200 W / cm or less. The irradiation speed is preferably 1 r / min or more, more preferably 3 r / min or more. The irradiation speed is preferably 50 r / min or less, more preferably 10 r / min or less.

[0113] (3) Pre-curing In this disclosure, it is preferable to perform a pre-curing treatment on the coated layer after the coating treatment and before the first irradiation treatment by irradiating the coated layer with ultraviolet light with a wavelength of 320 nm to 405 nm to pre-cur the resin composition. Pre-curing the coated layer as a whole by the ultraviolet irradiation treatment for pre-curing imparts appropriate viscosity to the resin composition (pre-gelling). As a result, sagging of the wrinkle structure formed by the first irradiation treatment is suppressed, and a wrinkle structure capable of exhibiting low gloss is obtained. That is, it is preferable to perform the irradiation treatment with ionizing radiation in the following order: ultraviolet irradiation treatment for pre-curing, first irradiation treatment, and second irradiation treatment.

[0114] In the ultraviolet irradiation treatment for the preliminary curing, the wavelength of the ultraviolet rays adopted is, for example, 350 nm or more, preferably 375 nm or more, more preferably 385 nm or more. On the other hand, the above wavelength may be, for example, 400 nm or less. By using the light of the above wavelength in the ultraviolet irradiation treatment for the preliminary curing, the overall preliminary curing of the coating layer can be efficiently performed.

[0115] The ultraviolet illuminance in the ultraviolet irradiation treatment for the preliminary curing is preferably 0.01 W / cm 2 or more, more preferably 0.1 W / cm 2 or more, still more preferably 0.3 W / cm 2 or more. Also, the ultraviolet illuminance is preferably 5 W / cm 2 or less, more preferably 3 W / cm 2 or less, still more preferably 2 W / cm 2 or less. When the ultraviolet illuminance is within the above range, the overall preliminary curing of the coating layer can be efficiently performed without the coating layer being completely cured.

[0116] The light with the wavelength adopted in the ultraviolet irradiation treatment for the preliminary curing can be irradiated, for example, using an ultraviolet irradiation device having a light source such as an LED light, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, etc. Among them, it is preferable to use an ultraviolet irradiation device having an LED light as the light source. This is because light with a single wavelength can be irradiated, and the effect of this treatment is less likely to be inhibited by an ultraviolet absorber.

[0117] (4) Embossing In the present disclosure, after the second irradiation treatment, an embossing may be provided. By performing the embossing, a surface protection layer having a surface shape with a wrinkle structure and an embossed portion on the surface opposite to the base material can be obtained. The embossed portion is a portion recessed toward the base material side more than the bottom of the recess of the wrinkle structure in the thickness direction. By having the embossed portion in the surface protection layer, a three-dimensional expression becomes possible and the design property is improved.

[0118] In embossing, for example, the sheet after the second irradiation treatment is heated and softened on a heating drum, then further heated with an infrared radiation heater, pressed and shaped with an embossing plate that has the desired shape of raised and recessed pattern, and then cooled and fixed. The heating temperature of the sheet during embossing is, for example, 80°C to 260°C, or 100°C to 200°C.

[0119] The raised and recessed patterns of the embossed plate are preferably patterns that correspond to the decorative layers (especially the patterns of the design layers) mentioned above. Examples include wood grain grooves, raised patterns (raised patterns of annual rings), hairline finishes, sand textures, and pear-skin finishes.

[0120] (5) Surface protective layer The surface protective layer obtained by the above method contains a cured resin which is a cured product of the above resin composition, and the surface of the surface protective layer opposite to the substrate has a wrinkled structure, max / I min This is within a predetermined range. By having a surface protective layer with such a specific surface shape, light reflection can be suppressed by the light diffusion effect at the refractive index difference interface between the surface protective layer and air. Furthermore, the change in reflection intensity with respect to the reflection angle is small, resulting in a decorative sheet with a uniform low gloss depending on the viewing angle.

[0121] The wrinkle structure preferably has an uneven shape due to irregular wrinkles. The irregular wrinkles preferably have multiple protrusions formed by multiple projections and recesses formed by being surrounded by multiple projections. Furthermore, the projections preferably have linear projections.

[0122] In this specification, "linear projection" means a projection whose length-to-width ratio (length / width) is 3 or greater, preferably 5 or greater, and more preferably 10 or greater. The method for determining the length and width of the projection is described below. Hereinafter, linear projections may be referred to as linear projections.

[0123] Figure 4 is a microscopic image of the surface of the surface protection layer 2 of the decorative sheet in this disclosure. As shown in Figure 4, the surface S1 of the surface protection layer 2 opposite to the substrate has a surface shape having a wrinkled structure. Figure 4 also shows that the surface shape of the surface protection layer has irregular wrinkles in a plan view; the irregular wrinkles have a plurality of convex parts 9 formed by a plurality of curved linear protrusions and a recess 8 formed by being surrounded by the plurality of protrusions (plural convex parts 9); at least a portion of the plurality of curved convex parts 9 are each formed by a meandering linear protrusion, and the meandering recess 8 is formed surrounded by the meandering linear protrusions. The surface shape of the surface protection layer has a wrinkled structure composed of irregular wrinkles as shown in Figure 4, which improves the matte effect.

[0124] Here, "curvature" means that, in a plan view, the convex portion 9 of a continuous line has one or more points where its extension direction reverses from one side to the other. Hereafter, the points where the extension direction of the convex portion 9 of a continuous line reverses from one side to the other may be referred to as reversed portions. An example of a reversed portion is a form that has an inflection point when the width of the plan view shape of the convex portion 9 of the line is ignored (when the width is considered to be 0) and it is approximated by a continuous curve. Another example of a reversed portion is a form that has a portion that is approximated by a V-shaped polyline or two sides enclosing one vertex of a triangle when the width of the plan view shape of the convex portion 9 of the line is ignored and it is approximated by a straight line.

[0125] Furthermore, "serpentine" means that, in a plan view, there are two or more inversion sections, and when the convex portion 9 of the line is moved in its direction of extension, there are sections where the direction of extension of the convex portion 9 alternately reverses in two adjacent inversion sections. For example, when the width of the plan view shape of the convex portion 9 of the line is ignored and it is approximated by a continuous curve, there is a form that has a section approximated by the Roman letter "S". Another example is when the width of the plan view shape of the convex portion 9 of the line is ignored and it is approximated by a straight line, there is a form that has a section approximated by the Roman letter "W".

[0126] In this specification, "irregular" means that the shape does not follow a certain rule, nor is it arranged according to a certain rule, and is not so-called patterned. Typical examples of non-irregular shapes (regular shapes) include, for example, a so-called lenticular lens in which multiple cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to their longitudinal direction, and other shapes that are arranged with a certain periodicity in a specific direction. Therefore, in this disclosure, the irregular wrinkles that may be present in the wrinkle structure that forms the surface shape of the surface protective layer include: the shape of a single protrusion itself is not a shape formed according to a certain rule such as periodicity, but is irregular; the shapes of multiple convex parts formed by multiple protrusions are not formed and arranged according to a certain rule, but are irregular; and the shape of the concave part surrounded by such multiple protrusions is also irregular.

[0127] In the wrinkle structure that forms the surface shape, if the shape of a single protrusion (single convex part), the shape and arrangement of multiple protrusions (multiple convex parts), or the shape of the recesses surrounded by multiple protrusions is irregular, the surface of the protective layer is likely to take on a specific surface shape. For the same reason, it is more preferable that all of these are irregular.

[0128] As described above, the surface of the protective layer has a wrinkled structure and is essentially an uneven shape. The convex and concave parts of the uneven shape are defined based on the midpoint of the height distribution in the uneven shape. Areas with heights exceeding this midpoint are defined as convex parts, and areas with heights below this midpoint are defined as concave parts. For example, by using the density difference (i.e., brightness difference) of an image with a density that corresponds 1:1 to the height of the protective layer surface, the darkest part of the density distribution image can be set to 255, and the lightest part of the density distribution image can be set to 0. Then, for gradations 0 to 255, gradations 0 to 127 can be defined as concave parts, and gradations 128 to 255 can be defined as convex parts by binarization. In this case, the midpoint of density relative to the midpoint of height is 127.

[0129] Furthermore, as shown in Figure 4, for example, it is preferable that the wrinkle structure has multiple protrusions formed by multiple projections that are irregular but have a certain degree of homogeneity, and recesses surrounded by the protrusions. Therefore, in the protrusions (projections) shown in Figure 4, shapes in which the width of the protrusions changes drastically or shapes in which the height of the protrusions changes drastically are not desirable for obtaining a matte finish. The following describes specific embodiments of the shape of the wrinkles constituting the wrinkle structure, that is, the shapes of the protrusions (projections) and recesses, which may be effective in improving the matte finish.

[0130] The shape of the recess may be acute, semicircular, or semielliptical in cross-sectional view, or a combination thereof. Furthermore, the shape of the recess may be such that a single convex portion has a recess in part in cross-sectional view.

[0131] On the other hand, the shape of the convex portion can be semicircular or semielliptical in cross-sectional view, although its width may vary.

[0132] The height of the protrusion (the height of the projection) is, for example, 0.5 μm or more, and may be 1 μm or more. Also, the height of the protrusion is, for example, 10 μm or less.

[0133] The depth of the recess is, for example, 0.5 μm or more, and may be 1 μm or more. Alternatively, the depth of the recess may be, for example, 10 μm or less.

[0134] The distance from the top of the convex portion to the bottom of the concave portion (the height difference between the convex and concave portions) is, for example, 1 μm or more, and may be 2 μm or more. Furthermore, the above distance is, for example, 20 μm or less, and may be 18 μm or less, or 16 μm or less. When the above distance falls within the above range, the matte effect is improved.

[0135] Here, the dimensions of the protrusions are the average value of 10 arbitrary protrusions (projections) in any 10 locations (100 μm square areas × 10 locations) on the surface of the protective layer, i.e., a total of 100 protrusions. The height of one protrusion (projection) is the average value of the heights of any 5 locations on that protrusion (projection).

[0136] Furthermore, the dimensions of the recessed portion are determined in the same way as the dimensions of the convex portion described above.

[0137] The proportion of the protrusions is, for example, 15% or more, may be 20% or more, or 30% or more. Also, the proportion of the protrusions is, for example, 80% or less, may be 70% or less, or 60% or less. When the proportion of the protrusions is within the above range, the surface of the protective layer tends to take on a specific surface shape in relation to the proportion of the recesses surrounded by the protrusions, and the matte effect is improved.

[0138] Here, the occupancy rate of the protrusions is the average value of the occupancy rate of the protrusions in any 10 locations (100 μm square area × 10 locations) of the surface protective layer.

[0139] The convex and concave portions may have areas that are substantially in the same direction and substantially the same width, but it is preferable that the length of such areas be short. When the length is short, the surface of the surface protective layer is more likely to take on a specific surface shape, and the matting effect is improved. Specifically, the length of continuous convex and concave portions that are substantially in the same direction and substantially the same width is, for example, 95 μm or less, but may also be 80 μm or less, or 70 μm or less. In addition, the length is, for example, 5 μm or more, but may also be 10 μm or more, or 15 μm or more. When the length is within the above range, the wrinkles become more irregular, and the matting effect is improved.

[0140] Here, it is preferable that 80% or more of any 10 protrusions and recesses (i.e., a total of 100 protrusions and recesses) in any 10 locations (100 μm square areas × 10 locations) of the surface protective layer satisfy the above condition. The above percentage may be 85% or more, 90% or more, or 95% or more.

[0141] In this specification, "approximately identical" means roughly the same, without branching, with approximately identical direction being within ±3° and approximately identical width being within ±5%.

[0142] Furthermore, the number of protrusions (projections) in a 100 μm square area may be, for example, 10 or more, 20 or more, or 30 or more. The number of protrusions may be, for example, 200 or less, 100 or less, or 70 or less. When the number of protrusions falls within the above range, the surface of the protective layer tends to take on a specific surface shape, improving the matte effect.

[0143] Here, the number of protrusions in a 100 μm square area is the average number of protrusions in 10 locations (100 μm square area × 10 locations) of the surface protective layer.

[0144] The surface of the protective layer preferably has a wrinkled structure on at least a portion of it, and more preferably has a wrinkled structure over its entire surface.

[0145] (a) Surface texture In the surface shape of the surface protective layer in this disclosure, the wrinkle structure preferably has the following surface properties. The surface properties of the wrinkle structure are controlled by adjusting the type of material used for the surface protective layer, the thickness of the surface protective layer, and the irradiation treatment conditions described later.

[0146] (i) RSm (average length of the curve element) The RSm (average length of curved elements) of the wrinkled structure, as specified in JIS B0601:2013, is, for example, 150 μm or less, but may also be 130 μm or less, or 120 μm or less. On the other hand, the above RSm (average length of curved elements) is, for example, 2 μm or more, but may also be 4 μm or more, or 8 μm or more.

[0147] RSm (Average Length of Curve Elements) is a lateral parameter of the contour curve, representing the average length of the contour curve elements within a given reference length. A smaller RSm indicates a greater number of protrusions within the reference length. Therefore, surface shapes with a small RSm have a denser distribution of protrusion vertices, resulting in a greater matte finish.

[0148] In this specification, the cutoff value for measuring RSm (average length of the curved element) is 0.8 mm. Furthermore, in this specification, RSm (average length of the curved element) is the average of measurements taken at any 10 locations.

[0149] (ii) Ra (arithmetic mean roughness) The arithmetic mean roughness (Ra) of the wrinkle structure, as specified in JIS B0601:2013, is, for example, 2.5 μm or less, may be 2.3 μm or less, or 2.0 μm or less. On the other hand, the above Ra (arithmetic mean roughness) is, for example, 0.1 μm or more, may be 0.2 μm or more, or 0.3 μm or more.

[0150] Ra (arithmetic mean roughness) is one of the parameters in the height direction of the contour curve, and is the average value of the height difference from the average surface in the contour curve over a reference length. A smaller Ra value indicates that the height difference between the convex parts and the corresponding concave parts in the wrinkle structure is smaller, and that the shape tends to be smoother and more uniform.

[0151] In this specification, the cutoff value for measuring Ra (arithmetic mean roughness) is 0.8 mm. Furthermore, in this specification, the above Ra (arithmetic mean roughness) is the average value of measurements taken at any 10 locations.

[0152] (iii) Rz (maximum height) The Rz (maximum height) of the wrinkle structure specified in JIS B0601:2013 is, for example, 12.5 μm or less, may be 12.0 μm or less, or may be 11.0 μm or less. On the other hand, the above Rz (maximum height) is, for example, 2.0 μm or more, may be 2.2 μm or more, or may be 2.5 μm or more.

[0153] Rz (maximum height) is one of the peak and height parameters of the contour curve, and is the sum of the height of the highest peak and the depth of the deepest valley in the contour curve at the reference length. The larger the numerical value of Rz (maximum height), the more it indicates that there are large (high) convex portions in terms of the valleys (concave portions), and there tends to be a large number of such convex portions.

[0154] In the measurement of Rz (maximum height) in this specification, the cut-off value is 0.8 mm. Also, in this specification, Rz (maximum height) is the average value of the measured values at any 10 locations.

[0155] (iv) Spc (arithmetic mean curvature of the apex of the protrusion) The Spc (arithmetic mean curvature of the apex of the protrusion) of the wrinkle structure specified in ISO 25178-2:2021 is, for example, 27000 mm -1 or less, may be 26000 mm -1 or less, or may be 25000 mm -1 or less. On the other hand, the above Spc (arithmetic mean curvature of the apex of the protrusion) is, for example, 1000 mm -1 or more, may be 1200 mm -1 or more, or may be 1400 mm -1 or more.

[0156] Spc (arithmetic mean curvature of the apex of the protrusion) is one of the three-dimensional surface texture parameters specified in ISO 25178-2:2021, and is the average curvature (average sharpness) of the tip of the peak, which is obtained from the arithmetic mean value of the radii of curvature of the peaks (apexes of the protrusions) of the portions classified as peaks (convex portions) in the solid image included in the reference area. Therefore, Spc (arithmetic mean curvature of the apex of the protrusion) is the reciprocal of the radius (mm) (mm -1)

[0157] The larger the value of Spc (arithmetic mean curvature of the projection vertex), the greater the curvature of the tip of the peak (convex part) (its reciprocal radius of curvature is smaller, and the shape of the tip becomes sharper). On the other hand, the smaller the value of Spc (arithmetic mean curvature of the projection vertex), the smaller the curvature of the projection vertex (its reciprocal radius of curvature is larger, and the shape of the tip becomes blunter). In other words, the smaller Spc (arithmetic mean curvature of the projection vertex), the more rounded the projection becomes and the closer it is to a plane, so the matte effect of the surface protective layer of the decorative sheet decreases.

[0158] In this specification, the cutoff value for measuring Spc (arithmetic mean curvature of the projection vertex) is 0.8 mm. Furthermore, in this specification, Spc (arithmetic mean curvature of the projection vertex) is the average value of measurements taken at any 10 locations.

[0159] (b) Physical properties of the surface protective layer The decorative sheet in this disclosure has a surface protective layer with a specific surface shape, thereby achieving a good matte finish. The matte finish makes the gloss less visible, resulting in a low-gloss appearance.

[0160] The 60° gloss value of the surface having the surface shape of the surface protective layer is, for example, 10.0 or less, but may also be 7.5 or less, 5.0 or less, 4.0 or less, or 3.6 or less.

[0161] Here, the 60° gloss value of the surface shape of the protective layer refers to the 60° specular gloss measured in accordance with JIS K5600-4-7:1999, and can be measured, for example, using a gloss meter. The 60° gloss value of the surface shape of the protective layer is the average value of measurements taken at any 10 locations.

[0162] (c) Thickness of the surface protective layer The thickness of the surface protective layer is not particularly limited as long as it is thick enough to form a specific surface shape, but for example, it may be 3 μm or more, 4 μm or more, or 5 μm or more. Alternatively, the thickness of the surface protective layer may be 300 μm or less, 200 μm or less, 150 μm or less, or 100 μm or less. When the thickness of the surface protective layer is within the above range, the surface shape is more likely to become a specific surface shape.

[0163] Here, the thickness of the surface protective layer is determined by measuring the thickness at 20 points on a cross-section of the decorative sheet using a scanning electron microscope (SEM), and taking the average of the 20 values. The SEM acceleration voltage is set to 3kV, and the magnification is set according to the thickness. The same procedure is followed for the thickness of the other layers.

[0164] 3. Decorative layer formation process The method for manufacturing a decorative sheet in this disclosure may include a decorative layer formation step, after the substrate preparation step and before the surface protection layer formation step, in which a decorative layer is formed on the first surface of the substrate. Figure 5 is a schematic cross-sectional view illustrating the method for manufacturing a decorative sheet in this disclosure. The method for manufacturing a decorative sheet shown in Figure 5 includes a substrate preparation step (Figure 5(a)) for preparing a substrate 1, a decorative layer formation step (Figure 5(b)) for forming a decorative layer 3 on the first surface 1a of the substrate 1, and a surface protection layer formation step (Figure 5(c)) for forming a surface protection layer 2 on the surface 3a of the decorative layer 3 opposite to the substrate 1.

[0165] In this process, a decorative layer is formed on the first surface of the substrate. The decorative layer allows for the addition of a design to the decorative sheet. Furthermore, as will be described later, if the decorative sheet has a transparent resin layer, the decorative layer may be placed between the substrate and the transparent resin layer.

[0166] The decorative layer may be, for example, a colored layer, a patterned layer, or a metallic layer. Furthermore, the decorative layer may have both a colored layer and a patterned layer.

[0167] The colored layer may be a so-called solid colored layer that is applied to the entire surface of the decorative sheet. The colored layer may contain a binder resin and a coloring agent. The colored layer can be formed by a coating method.

[0168] The patterns (designs) of the design layer are not particularly limited and include, for example, wood grain patterns such as annual rings and vessel grooves on the surface of wooden boards; stone patterns on the surface of stone slabs such as marble and granite; fabric patterns on the surface of cloth; leather grain patterns on the surface of leather; geometric patterns; letters; figures; and combinations thereof.

[0169] The pattern layer contains, for example, a binder resin and a coloring agent. The pattern layer can be formed by a printing method.

[0170] The binder resin used for the colored layer and the patterned layer is not particularly limited and includes, for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. In addition, various resins can be used, such as one-component curing resins and two-component curing resins accompanied by curing agents such as isocyanate compounds.

[0171] Examples of colorants used in the colored layer and patterned layer include pigments and dyes. Among these, the colorant is preferably a pigment with excellent opacity and weather resistance. The pigment can be the same as the pigment used in the substrate described above. The content of the colorant is, for example, 5 parts by mass or more and 90 parts by mass or less per 100 parts by mass of binder resin, and may be 15 parts by mass or more and 80 parts by mass or 30 parts by mass or more and 70 parts by mass or less.

[0172] The colored layer and the patterned layer may contain, as necessary, weather-resistant agents such as UV absorbers and light stabilizers, extender pigments, stabilizers, plasticizers, curing agents, catalysts, and other additives.

[0173] Examples of metal materials used for the metal layer include aluminum, chromium, tin, and indium. The metal layer can be formed by vapor deposition.

[0174] The thickness of the decorative layer is appropriately selected according to the desired design and type of decorative layer. If the decorative layer has at least one of a colored layer and a patterned layer, considering the need to conceal the base color of the substrate and improve the aesthetic appeal, the thickness of the decorative layer is, for example, 0.5 μm to 20 μm, may be 1 μm to 10 μm, or 2 μm to 5 μm.

[0175] The method for forming the decorative layer varies depending on the type of decorative layer, but one example is a coating method using a decorative layer-forming ink containing a colorant, a binder resin, and a solvent (or dispersion medium). For example, the decorative layer can be obtained by coating one side of the substrate with the decorative layer-forming ink and drying it.

[0176] Examples of the above-mentioned solvents (or dispersion media) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water.

[0177] Examples of the above coating methods include printing. Examples of printing methods include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Examples of coating methods for forming a solid layer include roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating.

[0178] 4.Transparent resin layer formation process The method for manufacturing a decorative sheet in this disclosure may include a transparent resin layer formation step, after the substrate preparation step and before the surface protective layer formation step, in which a transparent resin layer is formed on the first surface of the substrate. By forming a transparent resin layer, the strength of the decorative sheet can be increased.

[0179] The transparent resin layer only needs to be transparent enough that layers present on the substrate side (e.g., substrate, decorative layer, etc.) are visible, and may be colorless, colored, or semi-transparent.

[0180] Examples of resins that make up the transparent resin layer include polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter also referred to as "ABS resin"), acrylic resin, and vinyl chloride resin. Considering processability, polyolefin resins and vinyl chloride resins are preferred among these. The resin may be used alone or in combination of two or more types.

[0181] The transparent resin layer may contain additives as needed. Examples of additives include weather-resistant agents such as UV absorbers and light stabilizers. The weather-resistant agents can be appropriately selected from those described above.

[0182] The thickness of the transparent resin layer, considering processability, is, for example, 20 μm to 150 μm, but may also be 40 μm to 120 μm, or 60 μm to 100 μm.

[0183] Methods for forming a transparent resin layer include, for example, applying a resin composition or laminating a resin film by dry lamination.

[0184] 5. Other processes (1) Adhesive layer formation process The method for manufacturing a decorative sheet in this disclosure may include an adhesive layer forming step in which an adhesive layer is formed on the surface of the substrate opposite to the surface protective layer.

[0185] The adhesive layer may be transparent or opaque.

[0186] Examples of adhesives used in the bonding layer include curing adhesives and pressure-sensitive adhesives. Specific examples include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, silicone-based adhesives, and rubber-based adhesives. Furthermore, OCA (Optically Clear Adhesive) or OCR (Optically Clear Resin) can also be used as the bonding layer.

[0187] From the viewpoint of efficiently obtaining the desired adhesive strength, the thickness of the adhesive layer is, for example, 5 μm to 100 μm, may be 10 μm to 75 μm, or 20 μm to 50 μm.

[0188] Methods for forming the adhesive layer include, for example, applying an adhesive composition or laminating adhesive films by dry lamination.

[0189] After the adhesive layer is formed, a separator layer may be placed on the side of the adhesive layer opposite to the substrate. The separator layer is a protective component for the adhesive layer and is peeled off when the decorative sheet is attached to the substrate. Conventional known materials can be used as the separator layer.

[0190] Furthermore, when manufacturing a decorative sheet having a transparent resin layer, the adhesive layer may be formed between the transparent resin layer and the decorative layer.

[0191] (2) Primer layer formation process The method for manufacturing a decorative sheet in this disclosure may include a primer layer formation step to form a primer layer in order to improve the interlayer adhesion between the multiple layers constituting the decorative sheet. The primer layer may be placed between any layers between the surface protective layer and the substrate. Furthermore, if the decorative sheet has a transparent resin layer, the primer layer may be placed between the transparent resin layer and the surface protective layer. In addition, the primer layer may be placed on the side of the substrate opposite to the decorative layer (backside primer layer).

[0192] The primer layer is mainly composed of a binder resin and may contain additives such as UV absorbers and light stabilizers as needed.

[0193] Examples of binder resins include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and two or more hydroxyl groups in the terminal and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrified cotton), and cellulose acetate resin. These can be used individually or in combination.

[0194] Furthermore, the binder resin may be a resin to which a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent is added and crosslinked. For example, a resin in which a polyol-based resin such as an acrylic polyol resin is crosslinked and cured with an isocyanate-based curing agent is preferred, and a resin in which an acrylic polyol resin is crosslinked and cured with an isocyanate-based curing agent is more preferred.

[0195] The thickness of the primer layer is, for example, 0.5 μm or more, may be 1 μm or more, or 2 μm or more. Alternatively, the thickness of the primer layer may be, for example, 10 μm or less, may be 8 μm or less, or 6 μm or less.

[0196] Methods for forming the primer layer include applying a resin composition and, if necessary, drying and curing it.

[0197] B. Decorative sheet This disclosure provides a decorative sheet manufactured by the method for manufacturing a decorative sheet described above. Figures 6(a) and 6(b) are schematic cross-sectional views illustrating the decorative sheet in this disclosure. As shown in Figure 6(a), the decorative sheet 10 in this disclosure has a base material 1 and a surface protective layer 2. The surface protective layer 2 also contains a cured product of the resin composition described above, and the surface S1 opposite to the base material 1 has a wrinkled structure, and the maximum value of the reflectance intensity at a reflection angle of 30° to 60° when light is incident on the surface S1 at an incident angle of 45° is I max and minimum value I min The ratio is I max / I min This is within a specified range. Therefore, for the reasons mentioned above, it is possible to reduce the environmental burden during the manufacturing process, and the resulting decorative sheet has good visibility.

[0198] The base material and surface protective layer are the same as described above, so their explanation is omitted here.

[0199] The decorative sheet in this disclosure may have other layers in addition to the base material and surface protection layer. Examples of other layers include a decorative layer, a transparent resin layer, an adhesive layer, a separator layer, and a primer layer. As shown in Figure 6(b), the decorative sheet 10 of this disclosure may have a decorative layer 3 placed between the base material 1 and the surface protection layer 2. A transparent resin layer 4 may also be placed between the decorative layer 3 and the surface protection layer 2. A primer layer 7 may also be placed between the surface protection layer 2 and the transparent resin layer 4. An adhesive layer 5 and a separator layer 6 may also be placed on the second surface 1b side of the base material 1. The decorative sheet 10 shown in Figure 6(b) has the decorative layer 3, transparent resin layer 4, primer layer 7, and surface protection layer 2 on the first surface 1a side of the base material 1, in this order from the base material 1 side, and the adhesive layer 5 and separator layer 6 on the second surface 1b side of the base material 1, in this order from the base material 1 side.

[0200] The decorative layer, transparent resin layer, adhesive layer, separator layer, and primer layer are the same as described above, so their explanation is omitted here.

[0201] C. Decorative materials The decorative material in this disclosure is a decorative material comprising an adherend and a decorative sheet disposed on the surface of the adherend, wherein the decorative sheet is the decorative sheet described above.

[0202] Figure 7 is a schematic cross-sectional view illustrating a decorative material in this disclosure. The decorative material 100 shown in Figure 7 comprises an adherend 20 and a decorative sheet 10 placed on the surface of the adherend 20. The adherend 20 is placed on the second surface 1b side of the base material 1. In Figure 7, the decorative sheet 10 and the adherend 20 are bonded together via the adhesive layer 5 of the decorative sheet 10.

[0203] According to this disclosure, using the decorative sheet described above results in a decorative material that is highly visible and reduces environmental impact.

[0204] 1.Adherend The shape of the adherend is not particularly limited, but examples include flat plates, curved plates, and other plate-like shapes; three-dimensional shapes such as cylinders and polygonal prisms; and sheet-like shapes. The adherend may also be a wood-based material. Examples of wood-based materials include wood fiberboard. Examples of wood fiberboard include wood veneer, wood plywood, laminated wood, particleboard, and MDF (medium-density fiberboard). Examples of wood materials for wood-based materials include cedar, cypress, pine, and lauan.

[0205] The adherend may be a metal component. Examples of metals used for the metal component include iron, aluminum, copper, and alloys containing one or more of these metals. The adherend may also be a ceramic component such as glass or porcelain, or a non-ceramic component such as gypsum, cement, ALC (autoclaved lightweight concrete), or calcium silicate.

[0206] The adherend may be a resin component. Examples of resins used for resin components include acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulose resin, and rubber.

[0207] 2. Decorative sheet The decorative sheets described in this disclosure are the same as those described in "B. Decorative Sheets" above, so no further explanation is provided here.

[0208] 3. Decorative materials The decorative material in this disclosure may be a component used outdoors (exterior component) or a component used indoors (interior component), but it is preferable that it be an exterior component. This is because the decorative components in this disclosure have good weather resistance.

[0209] Exterior components are typically used outdoors. Examples of exterior applications include building materials. Building materials are used in buildings such as houses, offices, shops, hospitals, and clinics. Examples of exterior component applications include exterior walls, roofs, eaves, louvers, door pockets, window frames, doors, door frames, handrails, fences, and clotheslines.

[0210] D. Resin composition This disclosure provides a resin composition for forming the surface protective layer of a decorative sheet having a substrate and a surface protective layer, comprising an ionizing radiation-curable compound containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, and particles, wherein the resin composition has a viscosity of 500 mPa·s or less at 25°C.

[0211] The resin composition in this disclosure can be applied evenly even without a solvent. Furthermore, the surface has a wrinkled structure, max / I min A surface protective layer can be obtained in which the properties are within a predetermined range. Therefore, for the reasons described above, it is possible to manufacture decorative sheets that have good visibility and can reduce environmental impact.

[0212] The resin composition is the same as described in "A. Method for Manufacturing Decorative Sheets" above, so its explanation is omitted here.

[0213] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0214] [Example 1] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. On the transparent resin layer, a resin composition 1 having the composition described later and a viscosity of 25 mPa·s at 25°C was coated to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of resin composition 1 was 1.46. This coated layer was irradiated with ultraviolet light at a wavelength of 172 nm from an excimer lamp at an integrated light intensity of 100 mJ / cm². 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0215] (Composition of resin composition 1) 100 parts by mass of a difunctional acrylate monomer to which 4 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0216] [Example 2] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. On the transparent resin layer, a resin composition 2 having the composition described later and a viscosity of 60 mPa·s at 25°C was coated to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of resin composition 2 was 1.47. This coated layer was irradiated with ultraviolet light at a wavelength of 172 nm from an excimer lamp at an integrated light intensity of 100 mJ / cm². 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0217] (Composition of resin composition 2) 100 parts by mass of a difunctional acrylate monomer to which 9 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0218] [Example 3] A pattern layer was printed on a polypropylene film substrate with a thickness of 60 μm, and a transparent polypropylene film with a thickness of 80 μm was laminated thereon to form a transparent resin layer. On the transparent resin layer, Resin Composition 3 having the composition described below and a viscosity of 12 mPa·s at 25°C was applied with a thickness of 5 μm by a gravure printing method to obtain a coating layer (coating process). The refractive index of Resin Composition 3 was 1.45. With respect to this coating layer, ultraviolet rays with a wavelength of 172 nm irradiated from an excimer lamp were irradiated with an integrated light amount of 100 mJ / cm 2 (First irradiation treatment). The temperature of the coating layer immediately before irradiation with ultraviolet rays having a wavelength of 172 nm was 25°C. Subsequently, this coating layer was irradiated with an electron beam at a dose of 50 kGy (Second irradiation treatment). Thereby, a decorative sheet was obtained.

[0219] (Composition of Resin Composition 3) · 100 parts by mass of a bifunctional acrylate monomer having 3 mol of propylene oxide added per 1 mol · 0.5 parts by mass of silica particles having an average particle diameter of 8 μm

[0220] [Example 4] A pattern layer was printed on a polypropylene film substrate with a thickness of 60 μm, and a transparent polypropylene film with a thickness of 80 μm was laminated thereon to form a transparent resin layer. On the transparent resin layer, Resin Composition 4 having the composition described below and a viscosity of 70 mPa·s at 25°C was applied with a thickness of 5 μm by a gravure printing method to obtain a coating layer (coating process). The refractive index of Resin Composition 4 was 1.45. With respect to this coating layer, ultraviolet rays with a wavelength of 172 nm irradiated from an excimer lamp were irradiated with an integrated light amount of 100 mJ / cm 2 (First irradiation treatment). The temperature of the coating layer immediately before irradiation with ultraviolet rays having a wavelength of 172 nm was 25°C. Subsequently, this coating layer was irradiated with an electron beam at a dose of 50 kGy (Second irradiation treatment). Thereby, a decorative sheet was obtained.

[0221] (Composition of Resin Composition 4) ·100 parts by mass of a bifunctional acrylate monomer to which 12 mol of propylene oxide is added per 1 mol ·0.5 parts by mass of silica particles having an average particle diameter of 8 μm

[0222] [Example 5] A pattern layer was printed on a polypropylene film substrate with a thickness of 60 μm, and a transparent polypropylene film with a thickness of 80 μm was laminated thereon to form a transparent resin layer. On the transparent resin layer, a resin composition 5 having a viscosity of 61 mPa·s at 25°C and the composition described below was coated with a thickness of 5 μm by a gravure printing method to obtain a coating layer (coating process). The refractive index of the resin composition 5 was 1.47. For this coating layer, ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp was irradiated with an integrated light amount of 100 mJ / cm 2 (First irradiation treatment). The temperature of the coating layer immediately before irradiation with ultraviolet light having a wavelength of 172 nm was 25°C. Subsequently, this coating layer was irradiated with an electron beam at a dose of 50 kGy (Second irradiation treatment). Thereby, a decorative sheet was obtained.

[0223] (Composition of resin composition 5) ·100 parts by mass of a trifunctional acrylate monomer to which 3 mol of ethylene oxide is added per 1 mol ·0.5 parts by mass of silica particles having an average particle diameter of 8 μm

[0224] [Example 6] A pattern layer was printed on a polypropylene film substrate with a thickness of 60 μm, and a transparent polypropylene film with a thickness of 80 μm was laminated thereon to form a transparent resin layer. On the transparent resin layer, a resin composition 6 having a viscosity of 180 mPa·s at 25°C and the composition described below was coated with a thickness of 5 μm by a gravure printing method to obtain a coating layer (coating process). The refractive index of the resin composition 6 was 1.47. For this coating layer, ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp was irradiated with an integrated light amount of 100 mJ / cm 2 (First irradiation treatment). The temperature of the coating layer immediately before irradiation with ultraviolet light having a wavelength of 172 nm was 25°C. Subsequently, this coating layer was irradiated with an electron beam at a dose of 50 kGy (Second irradiation treatment). Thereby, a decorative sheet was obtained.

[0225] (Composition of resin composition 6) 100 parts by mass of a trifunctional acrylate monomer to which 15 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0226] [Example 7] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 7 having the composition described later and a viscosity of 84 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 7 was 1.46 or less. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0227] (Composition of resin composition 7) 100 parts by mass of a trifunctional acrylate monomer with 3 moles of propylene oxide per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0228] [Example 8] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 8 having the composition described later and a viscosity of 156 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of resin composition 8 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0229] (Composition of resin composition 8) 100 parts by mass of a tetrafunctional acrylate monomer to which 5 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0230] [Example 9] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 9 having the composition described later and a viscosity of 350 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of resin composition 9 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0231] (Composition of resin composition 9) 100 parts by mass of a tetrafunctional acrylate monomer to which 35 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0232] [Example 10] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 10 having the composition described later and a viscosity of 420 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 10 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0233] (Composition of resin composition 10) 100 parts by mass of a tetrafunctional acrylate monomer with 35 moles of propylene oxide per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0234] [Example 11] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 11 having the composition described later and a viscosity of 400 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 11 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0235] (Composition of resin composition 11) 100 parts by mass of a tetrafunctional acrylate monomer containing 35 moles of ε-caprolactone per mole. · 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0236] [Example 12] A pattern layer was printed on a polypropylene film substrate with a thickness of 60 μm, and a transparent polypropylene film with a thickness of 80 μm was laminated thereon to form a transparent resin layer. On the transparent resin layer, Resin Composition 12 having the composition described below and a viscosity of 320 mPa·s at 25°C was coated with a thickness of 5 μm by the gravure printing method to obtain a coating layer (coating process). The refractive index of Resin Composition 12 was 1.48. For this coating layer, ultraviolet rays with a wavelength of 172 nm irradiated from an excimer lamp were irradiated with an integrated light amount of 100 mJ / cm 2 (First irradiation treatment). The temperature of the coating layer immediately before irradiation with ultraviolet rays having a wavelength of 172 nm was 25°C. Subsequently, this coating layer was irradiated with an electron beam at a dose of 50 kGy (Second irradiation treatment). Thereby, a decorative sheet was obtained.

[0237] (Composition of Resin Composition 12) · 100 parts by mass of a hexafunctional acrylate monomer to which 12 moles of ethylene oxide are added per mole · 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0238] [Example 13] A pattern layer was printed on a polypropylene film substrate with a thickness of 60 μm, and a transparent polypropylene film with a thickness of 80 μm was laminated thereon to form a transparent resin layer. On the transparent resin layer, Resin Composition 13 having the composition described below and a viscosity of 381 mPa·s at 25°C was coated with a thickness of 5 μm by the gravure printing method to obtain a coating layer (coating process). The refractive index of Resin Composition 13 was 1.48. For this coating layer, ultraviolet rays with a wavelength of 172 nm irradiated from an excimer lamp were irradiated with an integrated light amount of 100 mJ / cm 2 (First irradiation treatment). The temperature of the coating layer immediately before irradiation with ultraviolet rays having a wavelength of 172 nm was 25°C. Subsequently, this coating layer was irradiated with an electron beam at a dose of 50 kGy (Second irradiation treatment). Thereby, a decorative sheet was obtained.

[0239] (Composition of Resin Composition 13) 100 parts by mass of a hexafunctional acrylate monomer to which 24 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0240] [Example 14] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 14 having the composition described later and a viscosity of 480 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 14 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0241] (Composition of resin composition 14) 100 parts by mass of a hexafunctional acrylate monomer with 12 moles of propylene oxide per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0242] [Example 15] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 15 having the composition described later and a viscosity of 440 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 15 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0243] (Composition of resin composition 15) 100 parts by mass of a hexafunctional acrylate monomer with 12 moles of ε-caprolactone per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0244] [Example 16] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 16 having the composition described later and a viscosity of 59 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 16 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0245] (Composition of resin composition 16) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 0.1 parts by mass of silica particles with an average particle size of 8 μm

[0246] [Example 17] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 17 having the composition described later and a viscosity of 120 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 17 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0247] (Composition of resin composition 17) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 10 parts by mass of silica particles with an average particle size of 8 μm

[0248] [Example 18] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 18 having the composition described later and a viscosity of 500 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 18 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0249] (Composition of resin composition 18) 50 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • Trifunctional urethane acrylate oligomer 50 parts by mass • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0250] [Example 19] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 19 having the composition described later and a viscosity of 61 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 19 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated onto this coated layer from an excimer lamp at an integrated light intensity of 50 mJ / cm². 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0251] (Composition of resin composition 19) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0252] [Example 20] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 20 having the composition described later and a viscosity of 61 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 20 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp was applied to this coated layer at an integrated light intensity of 100 mJ / cm². 2 The substrate was irradiated with ultraviolet light (first irradiation treatment). After heating the coated substrate, the temperature of the coated layer immediately before irradiation with ultraviolet light at a wavelength of 172 nm was 30°C. Subsequently, this coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0253] (Composition of resin composition 20) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0254] [Comparative Example 1] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 21 having the composition described later and a viscosity of 8 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 21 was 1.46. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0255] (Composition of resin composition 21) • 100 parts by mass of bifunctional acrylate monomer • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0256] [Comparative Example 2] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 22 having the composition described later and a viscosity of 105 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 22 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0257] (Composition of resin composition 22) • 100 parts by mass of trifunctional acrylate monomer • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0258] [Comparative Example 3] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 23 having the composition described later and a viscosity of 620 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 23 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0259] (Composition of resin composition 23) • 100 parts by mass of tetrafunctional acrylate monomer • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0260] [Comparative Example 4] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 24 having the composition described later and a viscosity of 5800 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 24 was 1.49. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0261] (Composition of resin composition 24) 100 parts by mass of 6-functional acrylate monomer • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0262] [Comparative Example 5] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 25 having the composition described later and a viscosity of 59 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 25 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0263] (Composition of resin composition 25) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • Silica particles with an average particle size of 8 μm: 0 parts by mass

[0264] [Comparative Example 6] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 26 having the composition described later and a viscosity of 71 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 26 was 1.48. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0265] (Composition of resin composition 26) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 15 parts by mass of silica particles with an average particle size of 8 μm

[0266] [Comparative Example 7] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 27 having the composition described later and a viscosity of 750 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 27 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0267] (Composition of resin composition 27) 25 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • Trifunctional urethane acrylate oligomer 75 parts by mass • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0268] [Comparative Example 8] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 28 having the composition described later and a viscosity of 61 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 28 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated onto this coated layer from an excimer lamp was applied at an integrated light intensity of 10 mJ / cm². 2 The coating layer was irradiated with ultraviolet light at a wavelength of 172 nm (first irradiation treatment). The temperature of the coated layer immediately before irradiation was 25°C. Subsequently, the coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0269] (Composition of resin composition 28) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0270] [Comparative Example 9] A pattern layer was printed on a 60 μm thick polypropylene film substrate, and an 80 μm thick transparent polypropylene film was laminated on top to form a transparent resin layer. A resin composition 29 having the composition described later and a viscosity of 61 mPa·s at 25°C was coated onto the transparent resin layer to a thickness of 5 μm by gravure printing to obtain a coated layer (coating treatment). The refractive index of the resin composition 29 was 1.47. Ultraviolet light with a wavelength of 172 nm irradiated from an excimer lamp at an integrated light intensity of 100 mJ / cm² was applied to this coated layer. 2The substrate was irradiated with UV light (first irradiation treatment). After coating, the substrate was cooled by blowing cold air onto it, and the temperature of the coated layer immediately before irradiation with UV light at a wavelength of 172 nm was 10°C. Subsequently, this coated layer was irradiated with an electron beam at a dose of 50 kGy (second irradiation treatment). This resulted in obtaining a decorative sheet.

[0271] (Composition of resin composition 29) 100 parts by mass of a trifunctional acrylate monomer to which 3 moles of ethylene oxide are attached per mole. • 0.5 parts by mass of silica particles with an average particle size of 8 μm

[0272] [Reflectance intensity measurement] The measurements were taken using a GP-200 variable-angle photometer manufactured by Murakami Color Technology Research Institute under the following conditions. <Measurement conditions> • Light source: 12V, 50W halogen lamp • Iris diaphragm: 10.5mm in diameter • Aperture diaphragm: 9.1mm in diameter ·Incidence angle: 45° <Measurement Procedure> Specifically, the measurements were performed according to the following procedure. (i) Sensitivity check A standard black glass plate BK-7 with a refractive index of 1.518 was installed. Hereafter, it will be referred to as standard black glass plate. Two light-reducing filters, 1.0% and 10.0%, were used. The sensitivity was set to 950. The high-voltage adjustment knob was adjusted so that the display, which monitors the output signal, showed 120. (ii) Measurement of standard plate When measuring a standard black glass plate at an incident angle of 45°, only specularly reflected light around a 45° receiving angle was detected. Therefore, the intensity of reflected light emitted from the surface of the standard black glass plate at angles from 30.0° to 60.0° was measured at 0.1° intervals. The intensity of reflected light from the standard black glass plate was measured before and after the measurement of the sample pieces. (iii) Preparation of sample A decorative sheet was cut into 5cm x 5cm squares to create test specimens. The test specimens were fixed to a suction sample stage. (iv) Measurement of the sample A suction sample stage with the test specimen fixed was fixed to the sample stage of a variable-angle photometer. Light from a light source was incident on the test specimen, and the light reflected by the surface of the test specimen was detected by a detector, and the intensity of the reflected light was measured. Hereafter, the reflected light will also be referred to as reflected light. A neutral density filter attached to the light source was selected so that the display, which is a monitor of the output signal, was approximately 20 to 180. Neutral density filters of 1.0%, 10.0%, and 50.0% were used individually or in combination. The light receiving angle was set to -90.0° to 90.0°. By changing the angle of the detector, the intensity of the reflected light emitted from the surface of the test specimen at the set light receiving angle was measured at 0.1° intervals. (v) Analysis: Receiving angle The maximum intensity of reflected light from a standard black glass plate at an incident angle of 45° is A. MAX A MAX The light-receiving angle at was set to 45.0°, and the light-receiving angle of the sample piece was corrected. For example, A MAX If the light-receiving angle was 46.0°, the sample measurement angle was shifted by 1.0°. Specifically, the sample measurement angle was corrected from 46.0° to 45.0°, and from 47.0° to 46.0°. (vi) Analysis: Light-reducing filter The intensity of reflected light from both the standard black glass plate and the sample piece was corrected using a neutral density filter. For example, when using a combination of 10.0% and 50.0% neutral density filters, the reflected light intensity was divided by 0.100 and then by 0.500 to obtain the corrected reflected light intensity. (Image A shows the correction applied using a neutral density filter.) MAX to A MAX-S That's what I decided. (vii) Analysis: Standardization In the measurement of a decorative sheet sample at an incident angle of 45°, the reflectance intensity at all light reception angles was A MAX-S Divided by and multiplied by 100, the normalized reflected light intensity I was obtained. The maximum value of I in the reflection angle range of 30° to 60° was determined. max and minimum value I min Ratio I max / I min The result was calculated.

[0273] [evaluation] • Visibility Twenty adult evaluators evaluated the decorative sheet by viewing it from a distance of 50 cm under a light source with an illuminance of 700 LUX, from the surface protective layer side. In the "Visibility" column of the "Evaluation," an "S" rating indicates that 18 or more of the 20 evaluators (90%) determined that the pattern did not appear white depending on the viewing angle and that the design was uniform. An "A" rating indicates that 16 or more of the 20 evaluators (80%) determined that the pattern did not appear white depending on the viewing angle and that the design was uniform. A "B" rating indicates that 15 or fewer of the 20 evaluators determined that the pattern did not appear white depending on the viewing angle and that the design was uniform.

[0274] • Coating suitability Twenty adult evaluators evaluated the decorative sheet by visually inspecting it from a distance of 50 cm under a light source with an illuminance of 700 LUX, viewing it from the surface protective layer side. An evaluation of "A" indicates that 16 or more of the 20 evaluators determined that the resin composition was uniformly transferred to the surface of the decorative sheet and that there was no deterioration in visibility due to uneven thickness within the surface. An evaluation of "B" indicates that 15 or fewer of the 20 evaluators determined that the resin composition was uniformly transferred to the surface of the decorative sheet and that there was no deterioration in visibility due to uneven thickness within the surface.

[0275] [Table 1]

[0276] [Table 2]

[0277] The decorative sheets obtained in Examples 1 to 20 were found to have good applicability and good visibility. On the other hand, Comparative Examples 1 to 6, Comparative Example 8 and Comparative Example 9 were... max / I minThe wrinkles were large and visibility was poor. This is presumed to be because, in Comparative Examples 1 to 4, the monomers did not contain modified species, resulting in too many crosslinking points and preventing the formation of uniform and fine wrinkles. Furthermore, Comparative Examples 3 and 4 had high viscosity and poor coatability of the resin composition. In Comparative Example 5, it is presumed that the low particle content in the resin composition prevented the formation of uniform and fine wrinkles. In Comparative Example 8, it is presumed that the low cumulative excimer light intensity prevented the formation of uniform and fine wrinkles. In Comparative Example 9, it is presumed that the low temperature of the coated layer immediately before excimer irradiation prevented the formation of uniform and fine wrinkles. In Comparative Example 6, it is presumed that the high particle content caused reflection by the particles. In Comparative Example 7, the high oligomer content in the resin composition resulted in high viscosity and poor coatability of the resin composition.

[0278] Thus, the present disclosure provides, for example, the following inventions.

[0279] [1] A substrate preparation step of preparing a substrate having a first surface and a second surface facing the first surface, A method for manufacturing a decorative sheet, comprising a surface protection layer forming step of forming a surface protection layer on the first surface of the substrate, The aforementioned surface protective layer formation step is, A coating process is performed to apply a resin composition to the first surface of the substrate to form a coating layer. A first irradiation treatment is performed in which the coated layer is irradiated with a first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate, The invention comprises a second irradiation treatment in which the coated layer after the first irradiation treatment is irradiated with a second wavelength light or electron beam of 200 nm to 450 nm to obtain the surface protective layer, The resin composition comprises an ionizing radiation-curable compound containing a bifunctional or more modified (meth)acrylate monomer to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, and particles, and has a viscosity of 500 mPa·s or less at 25°C. The maximum value of the reflected intensity at a reflection angle of 30° to 60° when light is incident at an incident angle of 45° on the surface of the surface protective layer opposite to the substrate. max and minimum value I min Ratio I max / I min A method for manufacturing decorative sheets, wherein the ratio is between 1.0 and 1.8. [2] The method for manufacturing a decorative sheet according to [1], wherein the surface protective layer formation step is a pre-curing treatment in which the coated layer is irradiated with light of a wavelength greater than 320 nm and less than or equal to 405 nm after the coating treatment and before the first irradiation treatment to pre-cure the resin composition. [3] The method for manufacturing a decorative sheet according to [1] or [2], wherein the surface protective layer formation step is an embossing step after the second irradiation treatment. [4] A method for manufacturing a decorative sheet according to any one of [1] to [3], comprising a decorative layer formation step of forming a decorative layer on the first surface of the substrate after the substrate preparation step and before the surface protective layer formation step. [5] A method for manufacturing a decorative sheet according to [4], comprising a transparent resin layer formation step, after the decorative layer formation step and before the surface protective layer formation step, in which a transparent resin layer is formed on the side of the decorative layer opposite to the substrate. [6] A method for producing a decorative sheet according to any one of [1] to [5], wherein the modified species is at least one of ethylene oxide, propylene oxide, and ε-caprolactone. [7] A method for manufacturing a decorative sheet according to any one of [1] to [6], wherein in the coating process in the surface protective layer formation step, the resin composition is applied so as to cover 90% or more of the area of ​​the first surface of the substrate. [8] A method for manufacturing a decorative sheet according to any one of [1] to [7], wherein, in the first irradiation treatment, the temperature of the coated layer immediately before irradiation with the first wavelength light is 25°C or higher. [9] A method for producing a decorative sheet according to any one of [1] to [8], wherein the solvent content in the resin composition is 10% by mass or less with respect to the total mass of the resin composition.

[10] A method for producing a decorative sheet according to any one of [1] to [9], wherein the content of the modified (meth)acrylate monomer in the resin composition is 50% by mass or more relative to the mass of the ionizing radiation-curable compound in the resin composition.

[11] The method for producing a decorative sheet according to any one of [1] to

[10] , wherein the resin composition does not contain polymerizable polymers and polymerizable oligomers.

[12] A method for producing a decorative sheet according to any one of [1] to

[11] , wherein the content of the particles in the resin composition is 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of the ionizing radiation-curable compound in the resin composition.

[13] A method for manufacturing a decorative sheet according to any one of [1] to

[12] , wherein the refractive index of the resin composition is 1.50 or less.

[14] The wrinkle structure has an uneven shape due to irregular wrinkles, The aforementioned irregular wrinkles have multiple protrusions formed by multiple projections and recesses formed by being surrounded by multiple projections. The method for manufacturing a decorative sheet according to any one of [1] to

[13] , wherein the projection has linear projections.

[15] A decorative sheet manufactured by the method for manufacturing decorative sheets described in any of [1] to

[14] .

[16] A decorative material comprising an adherend and a decorative sheet disposed on the surface of the adherend, A decorative material wherein the decorative sheet is the decorative sheet described in

[15] .

[17] A resin composition for forming the surface protective layer of a decorative sheet having a base material and a surface protective layer, A resin composition comprising an ionizing radiation-curable compound containing a modified (meth)acrylate monomer with two or more functionalities, to which a modified species is imparted at a rate of 3 moles or more per mole of molecule, and particles, wherein the viscosity at 25°C is 500 mPa·s or less. [Explanation of Symbols]

[0280] 1...Base material 2…Surface protective layer 3…Decorative layer 4…Transparent resin layer 5...adhesive layer 6…Separator layer 7…Primer layer 10… Decorative sheet 100… Decorative materials

Claims

1. A substrate preparation step of preparing a substrate having a first surface and a second surface facing the first surface, A method for manufacturing a decorative sheet, comprising a surface protection layer forming step of forming a surface protection layer on the first surface of the substrate, The aforementioned surface protective layer formation step is, A coating process is performed to apply a resin composition to the first surface of the substrate to form a coating layer. A first irradiation treatment is performed in which the coated layer is irradiated with a first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate, The invention comprises a second irradiation treatment in which the coated layer after the first irradiation treatment is irradiated with a second wavelength light or electron beam of 200 nm to 450 nm to obtain the surface protective layer, The resin composition comprises an ionizing radiation-curable compound containing a hexafunctional modified (meth)acrylate monomer to which a modified species is added at a rate of 3 moles or more per mole of molecule, and particles, and has a viscosity of 500 mPa·s or less at 25°C. The solvent content in the resin composition is 0% by mass or more and 10% by mass or less relative to the total mass of the resin composition. The maximum value I of the reflected intensity when light is incident at an incident angle of 45° on the surface of the surface protective layer opposite to the substrate, at a reflection angle of 30° to 60°. ｍａｘ and minimum value I ｍｉｎ Ratio I ｍａｘ / I ｍｉｎ However, it is between 1.0 and 1.8, The method for manufacturing a decorative sheet, wherein the surface protective layer formation step is performed after the second irradiation treatment, and includes an embossing treatment.

2. A substrate preparation step of preparing a substrate having a first surface and a second surface facing the first surface, A method for manufacturing a decorative sheet, comprising a surface protection layer forming step of forming a surface protection layer on the first surface of the substrate, The aforementioned surface protective layer formation step is, A coating process is performed to apply a resin composition to the first surface of the substrate to form a coating layer. A first irradiation treatment is performed in which the coated layer is irradiated with a first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate, The invention comprises a second irradiation treatment in which the coated layer after the first irradiation treatment is irradiated with a second wavelength light or electron beam of 200 nm to 450 nm to obtain the surface protective layer, The resin composition comprises an ionizing radiation-curable compound containing a hexafunctional modified (meth)acrylate monomer to which a modified species is added at a rate of 3 moles or more per mole of molecule, and particles, and has a viscosity of 500 mPa·s or less at 25°C. The solvent content in the resin composition is 0% by mass or more and 10% by mass or less relative to the total mass of the resin composition. The content of the modified (meth)acrylate monomer in the resin composition is 50% by mass or more relative to the mass of the ionizing radiation-curable compound in the resin composition. The maximum value I of the reflected intensity when light is incident at an incident angle of 45° on the surface of the surface protective layer opposite to the substrate, at a reflection angle of 30° to 60°. ｍａｘ and minimum value I ｍｉｎ Ratio I ｍａｘ / I ｍｉｎ A method for manufacturing decorative sheets, wherein the ratio is between 1.0 and 1.

8.

3. A substrate preparation step of preparing a substrate having a first surface and a second surface facing the first surface, A method for manufacturing a decorative sheet, comprising a surface protection layer forming step of forming a surface protection layer on the first surface of the substrate, The aforementioned surface protective layer formation step is, A coating process is performed to apply a resin composition to the first surface of the substrate to form a coating layer. A first irradiation treatment is performed in which the coated layer is irradiated with a first wavelength light of 100 nm or more and less than 200 nm to form a wrinkle structure on the surface opposite to the substrate, The invention comprises a second irradiation treatment in which the coated layer after the first irradiation treatment is irradiated with a second wavelength light or electron beam of 200 nm to 450 nm to obtain the surface protective layer, The resin composition comprises an ionizing radiation-curable compound containing a hexafunctional modified (meth)acrylate monomer to which a modified species is added at a rate of 3 moles or more per mole of molecule, and particles, and has a viscosity of 500 mPa·s or less at 25°C. The solvent content in the resin composition is 0% by mass or more and 10% by mass or less relative to the total mass of the resin composition. The aforementioned resin composition does not contain polymerizable polymers and polymerizable oligomers. The maximum value I of the reflection intensity at a reflection angle of 30° or more and 60° or less when light is incident at an incident angle of 45° with respect to the surface of the surface protection layer on the side opposite to the base material ｍａｘ and the minimum value I ｍｉｎ The ratio I ｍａｘ / I ｍｉｎ is 1.0 or more and 1.8 or less, a method for manufacturing a decorative sheet

4. The method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein the surface protective layer formation step comprises a pre-curing treatment in which the coated layer is irradiated with light of a wavelength greater than 320 nm and less than or equal to 405 nm after the coating treatment and before the first irradiation treatment to pre-cure the resin composition.

5. The method for manufacturing a decorative sheet according to claim 2 or 3, wherein the surface protective layer formation step comprises an embossing process after the second irradiation treatment.

6. A method for manufacturing a decorative sheet according to any one of claims 1 to 3, further comprising a decorative layer forming step of forming a decorative layer on the first surface of the substrate after the substrate preparation step and before the surface protective layer forming step.

7. A method for manufacturing a decorative sheet according to claim 6, comprising a transparent resin layer forming step, after the decorative layer forming step and before the surface protective layer forming step, in which a transparent resin layer is formed on the side of the decorative layer opposite to the substrate.

8. A method for producing a decorative sheet according to any one of claims 1 to 3, wherein the modified species is at least one of ethylene oxide, propylene oxide, and ε-caprolactone.

9. A method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein in the coating process in the surface protective layer formation step, the resin composition is applied so as to cover 90% or more of the area of ​​the first surface of the substrate.

10. A method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein, in the first irradiation treatment, the temperature of the coating layer immediately before irradiation with the first wavelength light is 25°C or higher.

11. A method for producing a decorative sheet according to claim 1 or 3, wherein the content of the modified (meth)acrylate monomer in the resin composition is 50% by mass or more relative to the mass of the ionizing radiation-curable compound in the resin composition.

12. The method for producing a decorative sheet according to claim 1 or claim 2, wherein the resin composition does not contain a polymerizable polymer and a polymerizable oligomer.

13. A method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein the content of the particles in the resin composition is 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of the ionizing radiation-curable compound in the resin composition.

14. A method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein the refractive index of the resin composition is 1.50 or less.

15. The wrinkle structure has an uneven shape due to irregular wrinkles, The aforementioned irregular wrinkles have multiple protrusions formed by multiple projections and recesses formed by being surrounded by multiple projections. The method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein the projection has linear projections.

16. A resin composition for forming the surface protective layer of a decorative sheet having a base material and a surface protective layer, An ionizing radiation-curable compound containing a hexafunctional modified (meth)acrylate monomer to which 3 moles or more of the modified species are attached per mole of molecule, and particles thereof, having a viscosity of 500 mPa·s or less at 25°C. The solvent content in the resin composition is 0% by mass or more and 10% by mass or less relative to the total mass of the resin composition. A resin composition in which the content of the modified (meth)acrylate monomer in the resin composition is 50% by mass or more relative to the mass of the ionizing radiation-curable compound in the resin composition.

17. A resin composition for forming the surface protective layer of a decorative sheet having a base material and a surface protective layer, An ionizing radiation-curable compound containing a hexafunctional modified (meth)acrylate monomer to which 3 moles or more of the modified species are attached per mole of molecule, and particles thereof, having a viscosity of 500 mPa·s or less at 25°C. The solvent content in the resin composition is 0% by mass or more and 10% by mass or less relative to the total mass of the resin composition. The resin composition is a resin composition that does not contain polymerizable polymers and polymerizable oligomers.

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