Decorative sheets and decorative resin molded products

Abstract

The present invention provides a decorative sheet having both excellent tactile feel and design. The decorative sheet comprises at least a base layer, a partially provided raised layer, and a first resin layer in this order, wherein the first resin layer contains a matting agent and the raised layer contains particles.

Description

Technical Field

[0001] The present invention relates to a decorative sheet and a decorative resin molded product. Background Art

[0002] Currently, decorative resin molded articles made by laminating decorative sheets onto the surface of resin molded articles are used in vehicle interior and exterior decorative parts, building interior decorative materials, and home appliance housings. In the manufacture of such decorative resin molded articles, molding methods such as injection molding are used, in which a pre-designed decorative sheet is integrated with the resin. Representative examples of such molding methods include: insert molding, in which a decorative sheet is pre-molded into a three-dimensional shape using a vacuum forming mold, then inserted into an injection molding mold, and a fluidized resin is injected into the mold, thereby integrating the resin and decorative sheet; and simultaneous decoration by injection molding, in which a decorative sheet inserted into the mold during injection molding is integrated with the molten resin injected into the mold cavity. In addition to molding methods using injection molding, decorative sheets are also used in decoration methods such as vacuum pressing, in which decorative sheets are attached to a pre-molded body while applying heat or pressure.

[0003] Known methods for imparting a high-quality texture to decorative resin molded articles include providing a resin layer containing a matting agent on a decorative sheet and providing a concave-convex surface on the surface of the decorative sheet. For example, Patent Document 1 describes a decorative sheet comprising, in this order, a first resin layer containing a matting agent, a second resin layer partially provided on the first resin layer, and a raised layer containing resin and organic particles provided on the second resin layer. In the decorative sheet described in Patent Document 1, the second resin layer is partially laminated on the first resin layer containing a matting agent, creating a gloss difference between the laminated area and the unlaminated area, resulting in a high degree of design quality (gloss / matt effect). Furthermore, by laminating a raised layer containing resin and organic particles on the second resin layer, an excellent tactile feel can be achieved without compromising the gloss / matt effect.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-65261 Summary of the Invention

[0007] Technical problem to be solved by the invention

[0008] The decorative sheet described in Patent Document 1 has high design properties and exhibits excellent tactile feel.

[0009] On the other hand, in order to provide tactile sensation by providing concavities and convexities on the surface of the decorative sheet, when providing a raised layer on the layer providing the gloss difference, the influence of the raised layer on the gloss also needs to be considered. In order to make the gloss of the layer providing the gloss difference similar to that of the raised layer, restrictions are imposed on the selection of materials (the freedom of material selection may decrease). Therefore, new technologies are required to provide decorative sheets with both excellent tactile sensation and design sense.

[0010] Under such circumstances, the main object of the present invention is to provide a decorative sheet having both excellent tactile feel and design. Another object of the present invention is to provide a decorative resin molded article.

[0011] Technical solutions to technical problems

[0012] The present invention provides the following aspects.

[0013] Item 1. A decorative sheet comprising at least a base layer, a partially provided raised layer, and a first resin layer in this order, wherein the first resin layer contains a matting agent, and the raised layer contains particles.

[0014] Item 2. The decorative sheet according to Item 1, wherein the first resin layer is formed on the entire surface of one side of the decorative sheet.

[0015] Item 3. The decorative sheet according to Item 1 or 2, wherein a second resin layer is provided on the side of the first resin layer opposite to the raised layer side.

[0016] Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the raised layer contains organic particles as the particles.

[0017] Item 5. The decorative sheet according to Item 4, wherein the organic particles are at least one of polyurethane beads and acrylic beads.

[0018] Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the first resin layer has a thickness of 2 μm to 10 μm.

[0019] Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the particles contained in the raised layer have a median particle size of 15 μm to 60 μm.

[0020] Item 8. The decorative sheet according to any one of Items 1 to 7, further comprising a pattern layer between the base layer and the raised layer.

[0021] Item 9. The decorative sheet according to any one of Items 1 to 8, wherein the average thickness of the raised layer is less than 50 μm.

[0022] Item 10. A decorative resin molded article comprising at least a molding resin layer, a base material layer, a partially provided raised layer, and a first resin layer in this order, wherein the first resin layer contains a matting agent, and the raised layer contains particles.

[0023] Effects of the Invention

[0024] The present invention can provide a decorative sheet having both excellent tactile feel and design, and can also provide a decorative resin molded article using the decorative sheet. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0026] Figure 2 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0027] Figure 3 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0028] Figure 4 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0029] Figure 5 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0030] Figure 6 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0031] Figure 7 This is a schematic cross-sectional view of an example of the decorative sheet of the present invention.

[0032] Figure 8 This is a schematic cross-sectional view of an example of a decorative resin molded article using the decorative sheet of the present invention. DETAILED DESCRIPTION

[0033] 1. Decorative sheet

[0034] The decorative sheet of the present invention is characterized by comprising, in this order, at least a base layer, a partially provided raised layer, and a first resin layer, wherein the first resin layer contains a matting agent and the raised layer contains particles. This configuration allows the decorative sheet of the present invention to achieve both excellent tactile feel and design. More specifically, the surface irregularities of the decorative sheet, created by the raised layer partially provided on the base layer, impart an excellent tactile feel. Furthermore, the first resin layer containing the matting agent is formed on the raised layer. This prevents the design based on the first resin layer from being impaired by the raised layer when the decorative sheet is viewed from above, allowing for the desired design to be realized.

[0035] The decorative sheet of the present invention is described in detail below. Throughout this specification, numerical ranges indicated by "to" refer to "above" or "below," except where "above" or "below" is explicitly stated. For example, a range of 2 to 15 mm refers to a range of 2 mm to 15 mm. Furthermore, throughout this specification, "(meth)acrylate" refers to "acrylate or methacrylate," and other similar terms have the same meaning.

[0036] Laminated structure of decorative sheets

[0037] like Figures 1 to 6 As shown, the decorative sheet 10 of the present invention has a laminated structure comprising at least a base layer 1, a raised layer 2, and a first resin layer 11 laminated in this order. The raised layer 2 is partially provided on the base layer 1. Furthermore, a plurality of raised layers 2 are provided on the base layer 1. In the decorative sheet 10 of the present invention, the plurality of raised layers 2 are partially provided on the base layer 1, thereby imparting a concavo-convex surface.

[0038] The first resin layer 11 is provided on at least a portion of the ridge layer 2. The first resin layer 11 is preferably provided on the entire surface of the ridge layer 2, and more preferably provided on the entire surface of one side of the decorative sheet 10. Figures 1 to 6 The figure shows a mode in which the first resin layer 11 is provided on the entire surface of one side of the decorative sheet 10 .

[0039] like Figures 2 to 7 As shown, in the decorative sheet 10 of the present invention, a second resin layer 12 may be provided on the side of the first resin layer 11 opposite to the ridge layer 2 side as needed. The second resin layer 12 may be provided on the entire surface of the first resin layer 11 opposite to the ridge layer 2 side (see Figure 4 ), or partially set (see Figure 2 、 Figure 3 、 Figure 5 、 Figure 6 and Figure 7 The second resin layer 12 is provided on at least a portion of the first resin layer 11 . Figure 2 、 Figure 3 、 Figure 5 、 Figure 6 and Figure 7 The diagram shows a method in which the second resin layer 12 is provided on a portion of the first resin layer 11. More specifically, Figure 2 、 Figure 3 and Figure 7 The diagram shows a mode in which the second resin layer 12 is provided on a portion of the first resin layer 11 and on the entire surface of the ridge layer 2. Figure 5 and Figure 6 The diagram shows a mode in which the second resin layer 12 is provided on a portion of the first resin layer 11 and on a portion of the ridge layer 2 .

[0040] like Figure 7 As shown, in the decorative sheet 10 of the present invention, a third resin layer 13 may be provided on the side of the ridge layer 2 opposite to the first resin layer 11 as needed. In the decorative sheet of the present invention, the third resin layer 13 may be provided on the entire surface of the ridge layer 2 opposite to the first resin layer 11 (see Figure 7 ), or partially set.

[0041] In the decorative sheet 10 of the present invention, a pattern layer 3 may be provided as needed between the base layer 1 and the raised layer 2. Furthermore, although not shown in the figure, the decorative sheet 10 may include a primer layer or the like between the raised layer 2 and the pattern layer 3, a concealing layer or the like between the base layer 1 and the pattern layer 3, a back adhesive layer or the like on the back surface of the base layer (the side opposite to the raised layer 2), and other layers may be provided at any desired locations.

[0042] As the laminated structure of the decorative sheet of the present invention, there can be listed: a laminated structure formed by laminating substrate layer 1 / raised layer 2 / first resin layer 11 in sequence; a laminated structure formed by laminating substrate layer 1 / raised layer 2 / first resin layer 11 / second resin layer 12 in sequence; a laminated structure formed by laminating substrate layer 1 / patterned layer 3 / raised layer 2 / first resin layer 11 in sequence; a laminated structure formed by laminating substrate layer 1 / patterned layer 3 / third resin layer 13 / raised layer 2 / first resin layer 11 / second resin layer 12 in sequence; and a laminated structure formed by laminating substrate layer 1 / patterned layer 3 / raised layer 2 / first resin layer 11 / second resin layer 12 in sequence, etc. Figure 1 , as one embodiment of the laminated structure of the decorative sheet of the present invention, a schematic cross-sectional view of an example of a decorative sheet in which a base material layer 1 / a ridge layer 2 / a first resin layer 11 are laminated in this order is shown. Figure 2 and Figure 4 , as one embodiment of the laminated structure of the decorative sheet of the present invention, a schematic cross-sectional view of an example of a decorative sheet in which a base material layer 1 / a raised layer 2 / a first resin layer 11 / a second resin layer 12 are laminated in this order is shown. Figure 3 、 Figure 5 and Figure 6 , as one embodiment of the laminated structure of the decorative sheet of the present invention, a schematic cross-sectional view of an example of a decorative sheet in which a base material layer 1 / a pattern layer 3 / a raised layer 2 / a first resin layer 11 / a second resin layer 12 are laminated in this order is shown. Figure 7 , as one embodiment of the laminated structure of the decorative sheet of the present invention, a cross-sectional schematic diagram of an example of a decorative sheet comprising a base material layer 1, a patterned layer 3, a third resin layer 13, a raised layer 2, a first resin layer 11, and a second resin layer 12 is shown in this order. Here, " / " indicates the separation between layers.

[0043] Composition of each layer forming the decorative sheet

[0044] [Base material layer 1]

[0045] The substrate layer 1 is a resin sheet (resin film) that plays the role of a support in the decorative sheet of the present invention. There is no particular limitation on the resin component used in the substrate layer 1. It can be appropriately selected based on the formability and compatibility with the molding resin. Preferably, a resin film formed from a thermoplastic resin can be cited. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter, sometimes also marked as "ABS resin"), acrylonitrile-styrene-acrylate resin (hereinafter, sometimes also marked as "ASA resin"), acrylic resin, polyolefin resins such as polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET), etc. Among these, ABS resin and acrylic resin are preferred from the perspective of formability. In addition, the substrate layer 1 can be formed by a single-layer sheet of these resins, or by a multi-layer sheet of the same or different resins.

[0046] There is no particular limitation on the flexural modulus of the substrate layer 1. For example, when the decorative sheet of the present invention is integrated with a molding resin by insert molding, the flexural modulus of the substrate layer 1 at 25°C in the decorative sheet of the present invention can be 500 to 4,000 MPa, preferably 750 to 3,000 MPa. The flexural modulus at 25°C is a value measured in accordance with JIS K7171:2016. When the flexural modulus at 25°C is 500 MPa or more, the decorative sheet has sufficient rigidity, and even when used in the insert molding method, the surface properties and moldability are better. In addition, when the flexural modulus at 25°C is 4,000 MPa or less, sufficient tension can be applied during roll-to-roll manufacturing, and relaxation is less likely to occur. Therefore, the pattern can be repeatedly printed without deviation, which is the so-called good pattern registration.

[0047] About substrate layer 1, in order to improve the adhesion with the layer arranged thereon, surface treatment can be implemented on one surface or both surfaces.As surface treatment, chemical surface treatments such as oxidation and physical surface treatments such as embossing can be listed.As oxidation, for example, corona discharge treatment, chromating, flame treatment, hot air treatment, ozone ultraviolet treatment, etc. can be listed.In addition, as embossing, for example, sandblasting, solvent treatment, etc. can be listed.These surface treatments can be appropriately selected according to the type of resin component constituting substrate layer 1. From the viewpoints of effect and operability, it is preferred to list corona discharge treatment.

[0048] Furthermore, the base material layer 1 may be subjected to treatment such as forming a known adhesive layer.

[0049] Furthermore, the substrate layer 1 may be colored with a colorant or may be uncolored. Furthermore, the substrate layer 1 may be opaque, colorless and transparent, colored and transparent, or translucent. The colorant used in the substrate layer 1 is not particularly limited, but preferably includes a colorant that does not change color at temperatures above 150°C. Specific examples include existing dry pigments, color pastes, and masterbatch resin compositions.

[0050] The thickness of the base layer 1 can be appropriately set depending on the application of the decorative sheet, the molding method for integration with the molding resin, and other factors, and is typically about 25 to 1000 μm, or about 50 to 700 μm. More specifically, when the decorative sheet of the present invention is subjected to insert molding, the thickness of the base layer 1 is typically about 50 to 1000 μm, preferably about 100 to 700 μm, and more preferably about 100 to 500 μm. Furthermore, when the decorative sheet of the present invention is subjected to injection molding and simultaneous decoration, the thickness of the base layer 1 is typically about 25 to 200 μm, preferably about 50 to 200 μm, and more preferably about 70 to 200 μm.

[0051] [Uplift layer 2]

[0052] In the decorative sheet of the present invention, a raised layer 2 containing particles is formed on a base layer 1. The raised layer 2 of the present invention is preferably formed by raised printing in such a manner as to give the surface of the decorative sheet a desired tactile feel based on the concave-convex shape. Figures 1 to 7 The form represented by the convex shape in the cross-sectional schematic diagram as shown includes not only a form in which conical or cylindrical protrusions are formed on the surface of the decorative sheet, but also a form in which protrusions such as duct patterns are extended linearly.

[0053] In the decorative sheet formed by laminating a first resin layer 11 and, as needed, a second resin layer 12 on a raised layer 2, from the viewpoint of exhibiting excellent tactile feel, the average thickness (height) of the raised layer 2 of the decorative sheet of the present invention is preferably 5 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and particularly preferably 20 μm or more. In addition, the preferred upper limit of the average thickness of the raised layer 2 is preferably 50 μm or less, more preferably less than 50 μm, and further preferably 40 μm or less. By setting the average thickness of the raised layer 2 to the above range, the tactile feel and designability of the decorative sheet can be more appropriately improved. In this specification, the average thickness of the raised layer 2 is a value calculated by observing the cross section of the decorative sheet using a scanning electron microscope (SEM) and taking the average value of 10 measured values. The observation using the scanning electron microscope (SEM) is carried out under the conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000 times.

[0054] From the perspective of suppressing deformation of the raised layer 2 and forming a desired shape, the resin forming the raised layer 2 is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (e.g., an electron beam curable resin). From the perspective of high surface hardness and productivity, an ionizing radiation curable resin is particularly preferred.

[0055] Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins, silicone resins, and polysiloxane resins.

[0056] Curing agents such as crosslinking agents and polymerization initiators, and polymerization accelerators may be added to the above resins. For example, curing agents such as isocyanates and organic sulfonates may be added to unsaturated polyester resins and polyurethane resins, and organic amines may be added to epoxy resins. Peroxides such as methyl ethyl ketone peroxide and free radical initiators such as azobisisobutyronitrile may be added to unsaturated polyester resins.

[0057] Examples of a method for forming the ridge layer 2 from a thermosetting resin include a method of applying a thermosetting resin solution by a coating method such as roll coating, gravure coating, gravure printing, or screen printing, followed by drying and curing.

[0058] Ionizing radiation-curable resins are resins that crosslink and cure by irradiation with ionizing radiation. Specifically, resins obtained by appropriately mixing at least one of prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule are mentioned. Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or crosslinking molecules. Ultraviolet rays (UV) or electron beams (EB) are commonly used, but also include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Among ionizing radiation-curable resins, electron beam-curable resins can be solvent-free and do not require a photopolymerization initiator to obtain stable curing properties. Therefore, they are suitable for forming the raised layer 2.

[0059] <Ionizing radiation curable resin>

[0060] Suitable monomers for use as ionizing radiation-curable resins include (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule, with polyfunctional (meth)acrylate monomers being preferred. Polyfunctional (meth)acrylate monomers may be any monomer having two or more (difunctional or higher), preferably three or more (trifunctional or higher), polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone-modified dicyclopentene di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate. Acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. These monomers may be used alone or in combination of two or more.

[0061] In addition, as the above-mentioned oligomer used as the ionizing radiation curable resin, a (meth)acrylate oligomer having a free radical polymerizable unsaturated group in the molecule is suitable, and among them, a multifunctional (meth)acrylate oligomer having two or more (difunctional or more) polymerizable unsaturated bonds in the molecule is preferred. Examples of the multifunctional (meth)acrylate oligomer include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, polyurethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, and oligomers having a cationic polymerizable functional group in the molecule (such as novolac-type epoxy resin, bisphenol-type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Among them, polycarbonate (meth) acrylate is not particularly limited as long as the polymer main chain has a carbonate bond and the end or side chain has a (meth) acrylate group. For example, it can be obtained by esterifying polycarbonate polyol with (meth) acrylic acid. Polycarbonate (meth) acrylate can be, for example, polyurethane (meth) acrylate having a polycarbonate skeleton. Polyurethane (meth) acrylate having a polycarbonate skeleton can be obtained by reacting polycarbonate polyol, a polyisocyanate compound and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by free radical copolymerization of silicone macromonomer and (meth) acrylate monomer. Polyurethane (meth) acrylate can be obtained by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained by reacting (meth) acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or a novolac-type epoxy resin and esterifying it. In addition, carboxyl-modified epoxy (meth) acrylates obtained by partially modifying the epoxy (meth) acrylate with a dicarboxylic acid anhydride can also be used. Polyester (meth) acrylates can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensing a polycarboxylic acid with a polyol with (meth) acrylic acid, or by esterifying the hydroxyl groups at the ends of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth) acrylic acid. Polyether (meth) acrylates can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylates can be obtained by adding (meth) acrylic acid to the side chains of polybutadiene oligomers. Silicone (meth) acrylates can be obtained by adding (meth) acrylic acid to the ends or side chains of silicone having a polysiloxane bond in the main chain. Among these, polycarbonate (meth) acrylates, polyurethane (meth) acrylates, and the like are particularly preferred as multifunctional (meth) acrylate oligomers.These oligomers may be used alone or in combination of two or more.

[0062] When three-dimensional moldability is required for decorative sheets, such as when used to manufacture decorative resin molded articles, among the aforementioned ionizing radiation-curable resins, multifunctional polycarbonate (meth)acrylates are preferred for achieving excellent three-dimensional moldability. Furthermore, from the perspective of achieving both three-dimensional moldability and damage resistance, a combination of a multifunctional polycarbonate (meth)acrylate and a multifunctional (meth)acrylate is more preferred. Furthermore, when using a multifunctional (meth)acrylate monomer as an ionizing radiation-curable resin, from the perspective of achieving excellent three-dimensional moldability, it is preferably used in combination with a thermoplastic resin such as an acrylic resin. From the perspective of achieving both three-dimensional moldability and damage resistance, the mass ratio of the multifunctional (meth)acrylate monomer to the thermoplastic resin in the ionizing radiation-curable resin composition is preferably 25:75 to 75:25. Multifunctional polycarbonate (meth)acrylates and multifunctional (meth)acrylates are described in detail below.

[0063] <Multifunctional polycarbonate (meth)acrylate>

[0064] There are no particular limitations on the polyfunctional polycarbonate (meth)acrylate as long as the polymer main chain has a carbonate bond and two or more (meth)acrylate groups are present at the end or in the side chain. Furthermore, from the perspective of achieving good crosslinking and curing, the number of functional groups per molecule of the (meth)acrylate is preferably 2 to 6. The polyfunctional polycarbonate (meth)acrylate may be used alone or in combination of two or more.

[0065] Multifunctional polycarbonate (meth)acrylates can be obtained, for example, by converting some or all of the hydroxyl groups of a polycarbonate polyol into (meth)acrylates (acrylates or methacrylates). This esterification reaction can be carried out using conventional esterification reactions. Examples include: 1) condensation of a polycarbonate polyol with an acrylic acid halide or a methacrylic acid halide in the presence of a base; 2) condensation of a polycarbonate polyol with acrylic anhydride or methacrylic anhydride in the presence of a catalyst; or 3) condensation of a polycarbonate polyol with acrylic acid or methacrylic acid in the presence of an acid catalyst.

[0066] Polycarbonate polyols are polymers having carbonate bonds in the polymer main chain and two or more, preferably 2 to 50, and more preferably 3 to 50, hydroxyl groups at the terminals or side chains. Typical methods for producing these polycarbonate polyols include methods utilizing a polycondensation reaction of a diol compound (A), a trivalent or higher polyol (B), and a compound (C) serving as a carbonyl component.

[0067] The diol compound (A) used as a raw material of polycarbonate polyol is represented by the general formula HO-R 1 -OH represents. Among them, R 1 It is a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain an ether bond. 1 For example, it is a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

[0068] Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, neopentyl glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These diols may be used alone or in combination of two or more.

[0069] Examples of trivalent or higher polyols (B) used as raw materials for polycarbonate polyols include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, di-trimethylolpropane, dipentaerythritol, glycerol, and sorbitol. Furthermore, the trivalent or higher polyols may be alcohols having hydroxyl groups obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl groups of the above-mentioned polyols. These polyols may be used alone or in combination of two or more.

[0070] The carbonyl component compound (C) used as a raw material for the polycarbonate polyol is any compound selected from carbonic acid diesters, phosgene, or their equivalents. Specific examples of such compounds include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; and halogenated formates such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. These compounds may be used alone or in combination of two or more.

[0071] Polycarbonate polyols can be synthesized by subjecting the aforementioned diol compound (A), a trivalent or higher polyol (B), and a carbonyl component compound (C) to a polycondensation reaction under conventional conditions. The molar ratio of the diol compound (A) to the polyol (B) can be, for example, in the range of 50:50 to 99:1. Furthermore, the molar ratio of the carbonyl component compound (C) to the diol compound (A) and the polyol (B) can be, for example, in the range of 0.2 to 2 equivalents relative to the hydroxyl groups of the diol compound and the polyol.

[0072] The equivalent number (eq. / mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the aforementioned addition ratio can be, for example, an average of 3 or more per molecule, preferably 3 to 50, and more preferably 3 to 20. When this equivalent number is met, the necessary amount of (meth)acrylate groups can be formed by the esterification reaction described below, and appropriate flexibility can be imparted to the polyfunctional polycarbonate (meth)acrylate resin. The terminal functional groups of the polycarbonate polyol are generally OH groups, but some of them may also be carbonate groups.

[0073] The method for producing the polycarbonate polyol described above is described in, for example, Japanese Patent Application Laid-Open No. 64-1726. Alternatively, the polycarbonate polyol can be produced by transesterification of a polycarbonate diol with a trivalent or higher polyol as described in Japanese Patent Application Laid-Open No. 3-181517.

[0074] The molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited. For example, the weight average molecular weight can be 5,000 or greater, preferably 10,000 or greater. The upper limit of the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is not particularly limited. From the perspective of controlling the viscosity to be not excessively high, for example, it can be 100,000 or less, preferably 500,000 or less. The weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is preferably 10,000 to 50,000, more preferably 10,000 to 20,000.

[0075] In this specification, the weight average molecular weight of the polyfunctional polycarbonate (meth)acrylate is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[0076] The content of the multifunctional polycarbonate (meth)acrylate in the ionizing radiation curable resin composition for forming the raised layer 2 is not particularly limited as long as the effects of the present invention can be achieved. From the viewpoint of being able to maintain the concave-convex shape formed by the raised layer 2 even due to heat and pressure during injection molding and more effectively suppressing the deterioration of the high texture exhibited by the decorative sheet, it is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more.

[0077] <Multifunctional (meth)acrylate>

[0078] There are no particular restrictions on the multifunctional (meth)acrylate, but multifunctional polyurethane (meth)acrylate is preferred. As long as the polymer main chain has a polyurethane bond and the terminal or side chain has two or more (meth)acrylates, there are no particular restrictions on the multifunctional polyurethane (meth)acrylate. Such a multifunctional polyurethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate using (meth)acrylic acid. In addition, with respect to the multifunctional polyurethane (meth)acrylate, from the viewpoint of making crosslinking and curing better, 2 to 12 functional groups per molecule can be preferably listed. In addition, the multifunctional (meth)acrylate can also be a compound obtained by silicone modification. The multifunctional (meth)acrylate can be used alone or in combination of two or more.

[0079] The molecular weight of the polyfunctional (meth)acrylate is not particularly limited. For example, the weight average molecular weight can be 2,000 or greater, preferably 5,000 or greater. The upper limit of the weight average molecular weight of the polyfunctional (meth)acrylate is not particularly limited. From the perspective of controlling the viscosity to be not excessively high, for example, it can be 30,000 or less, preferably 10,000 or less.

[0080] In this specification, the weight average molecular weight of the polyfunctional (meth)acrylate is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[0081] The content of the multifunctional (meth)acrylate in the ionizing radiation curable resin composition for forming the raised layer 2 is not particularly limited as long as the effects of the present invention can be achieved. From the viewpoint of being able to maintain the concave-convex shape formed by the raised layer 2 even due to heat and pressure during injection molding and more effectively suppressing the deterioration of the high texture exhibited by the decorative sheet, it is preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0082] When a polyfunctional polycarbonate (meth)acrylate and a polyfunctional (meth)acrylate are used together in the ionizing radiation curable resin composition for forming the raised layer 2, their mass ratio (polyfunctional polycarbonate (meth)acrylate:polyfunctional (meth)acrylate) is preferably about 50:50 to 99:1, more preferably about 80:20 to 99:1, and further preferably about 85:15 to 99:1.

[0083] The formation of the raised layer 2 can be carried out, for example, by coating and cross-linking the prepared ionizing radiation curable resin composition after preparing it. In addition, the viscosity of the ionizing radiation curable resin composition can be any viscosity that can form an uncured resin layer on the layer adjacent to the raised layer 2 by the coating method described later. In the present invention, the prepared coating liquid is coated on the layer adjacent to the raised layer 2 with the above-mentioned thickness by known methods such as gravure coating, rod coating, roller coating, reverse roller coating, and jolt coating, preferably gravure coating, to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the raised layer 2. Among them, when electron beams are used as ionizing radiation, the acceleration voltage thereof can be appropriately selected according to the resin used and the thickness of the layer, and generally, an acceleration voltage of about 70 to 300 kV can be cited.

[0084] During electron beam irradiation, the higher the acceleration voltage, the greater the transmittance. Therefore, when using a resin that is easily degraded by electron beam irradiation beneath the raised layer 2, the acceleration voltage should be selected so that the electron beam penetration depth is substantially equal to the thickness of the raised layer 2. This prevents excess electron beam irradiation of the layers beneath the raised layer 2 and minimizes degradation of the layers caused by excess electron beams. Furthermore, the irradiation dose is preferably a dose that saturates the crosslink density of the raised layer 2, typically within the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The electron beam source is not particularly limited; for example, various electron beam accelerators such as the Cockcroft-Walton type, the Van der Graaf type, the resonant transformer type, the insulating core transformer type, the linear type, the dynamite type, and the high-frequency type can be used. When ultraviolet light is used as the ionizing radiation, irradiation with light containing ultraviolet light having a wavelength of 190 to 380 nm is sufficient. The ultraviolet light source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

[0085] The raised layer 2 contains particles. By making the raised layer 2 contain particles, even if the raised layer 2 is not formed thickly, the raised layer 2 can also appropriately contribute to having both excellent touch and design. The average thickness of the raised layer 2 and the average particle size of the particles can be the same value. That is, in the decorative sheet of the present invention, from the perspective of showing excellent touch, the average particle size of the particles is preferably 5 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and further preferably 20 μm or more. In addition, the preferred upper limit of the average particle size is preferably 60 μm or less, more preferably 50 μm or less, further preferably less than 50 μm, further preferably 40 μm or less, and particularly preferably 35 μm or less. By setting the average particle size of the particles contained in the raised layer 2 to the above range, the touch and design of the decorative sheet can be more appropriately improved.

[0086] The particles contained in the raised layer 2 are not particularly limited and may be either organic particles or inorganic particles. However, organic particles are particularly preferred from the viewpoint of achieving both excellent tactile feel and design properties.

[0087] As organic particles, there are no particular limitations, and resin beads are generally used. Examples of resin beads include acrylic beads, polyurethane beads, nylon beads, and styrene beads. Among these, acrylic beads or polyurethane beads are preferably used from the perspective of suppressing the whitening of the raised layer 2, imparting an excellent sense of touch, and improving the scratch resistance of the decorative sheet. In particular, acrylic beads or polyurethane beads are preferably used from the perspective of suppressing the whitening of the raised layer 2, and polyurethane beads are preferably used from the perspective of improving scratch resistance. In addition, cross-linked resin beads are preferably used from the perspective of imparting an excellent sense of touch and improving the scratch resistance of the raised layer 2. As cross-linked resin beads, specifically cross-linked acrylic beads and cross-linked polyurethane beads can be mentioned.

[0088] The average particle size of the organic particles contained in the raised layer 2 is preferably 15 μm or larger, more preferably 20 μm or larger. The preferred upper limit of this average particle size is preferably 60 μm or smaller, more preferably 50 μm or smaller, more preferably less than 50 μm, even more preferably 40 μm or smaller, and particularly preferably 35 μm or smaller. Preferred ranges for the particle size of the organic particles include 5 to 60 μm, 4 to 50 μm, 5 μm or larger and less than 60 μm, 3 to 40 μm, and 10 to 80 μm. To achieve the effects of the present invention, it is preferred that at least 90% of the organic particles contained in the raised layer 2 meet these particle sizes, based on the number of particles. If the average particle size of the organic particles is less than 15 μm, an excellent tactile feel may not be achieved. Furthermore, if the average particle size of the organic particles exceeds 60 μm, production stability decreases, making it difficult to reproducibly form the raised layer 2 in the desired shape. In the present invention, the organic resin is uniformly distributed, so the average thickness of the raised layer 2 is approximately equal to the average particle size of the organic particles. Furthermore, regarding the raised layer 2, when the raised layer 2 is formed by raised printing, the average particle size of the organic particles is preferably no greater than half the plate depth from the perspective of ink transfer stability. In the present invention, the average particle size refers to the average particle size (arithmetic mean particle size) obtained by observing a cross-section of the layer in the thickness direction using a scanning electron microscope (SEM) at an accelerating voltage of 3.0 kV and a magnification of 50,000x and measuring the particle sizes of 100 randomly selected non-aggregates of particles.

[0089] In the decorative sheet of the present invention, the organic particles are preferably contained at a ratio of 50% by mass or less in the solid content of the resin composition forming the raised layer 2, and more preferably at a ratio of 40% by mass or less. When the content of the above-mentioned organic particles is 50% by mass or less, the organic particles are uniformly distributed in the coating film (raised layer 2), so the touch is stable. When the content of the above-mentioned organic particles exceeds 50% by mass, the organic particles agglomerate, and the average thickness of the raised layer may be unstable, which may damage the transparency of the raised layer 2, and thus the design properties may be reduced. The content of the above-mentioned organic particles is preferably 2% by mass, and more preferably 10% by mass or more. When the content of the above-mentioned organic particles is less than 2% by mass, in addition to the insufficient touch, the thixotropy of the resin composition forming the raised layer is also insufficient, and it may be difficult to form the raised layer 2 by raised printing.

[0090] As inorganic particles, there are no particular restrictions as long as they are particles formed from inorganic compounds, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, aluminum oxide particles, and glass ball particles, among which silica particles are preferably included. One type of inorganic particle can be used alone, or two or more types can be used in combination. As the average particle size of the inorganic particles, for example, about 0.5 to 20 μm, preferably about 1 to 10 μm can be included. As described above, the average particle size of the inorganic particles refers to the average value (arithmetic mean particle size) of the particle size obtained by observing a cross section in the thickness direction of the layer using a scanning electron microscope (SEM) under the conditions of an acceleration voltage of 3.0 kV and a magnification of 50,000 times and measuring the non-agglomerated mass of 100 randomly selected particles.

[0091] When the raised layer 2 contains inorganic particles, the content of the inorganic particles is not particularly limited, but is preferably about 1 to 60 parts by mass, more preferably about 1 to 40 parts by mass, relative to 100 parts by mass of the resin contained in the raised layer 2. The inorganic particles may be used alone or in combination of two or more.

[0092] In the raised layer 2, various additives can be added according to the desired physical properties of the raised layer 2. As such additives, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, defoaming agents, fillers, solvents, colorants, etc. can be listed. These additives can be appropriately selected from commonly used additives. In addition, as ultraviolet absorbers and light stabilizers, reactive ultraviolet absorbers and light stabilizers having polymerizable groups such as (meth)acryloyl groups in the molecules can be used.

[0093] In the decorative sheet 10 of the present invention, the ratio of the area of the raised layer 2 to the area of one side of the substrate layer 1 is preferably 3 to 80%, more preferably 3 to 50%, even more preferably 5 to 50%, even more preferably 5 to 40%, and even more preferably 6 to 30%. Providing the raised layer 2 within this range can provide a decorative sheet with a superior tactile feel. If the cross-section of the raised layer 2 is, for example, trapezoidal or conical, and the areas of the upper and lower surfaces of the raised layer 2 are different, the area of the raised layer 2 is the area of the surface of the substrate layer 1 side of the raised layer 2.

[0094] As described above, when the decorative sheet of the present invention is used for injection molding or vacuum forming, from the viewpoint of suppressing deformation of the raised layer 2, forming a desired shape, and improving three-dimensional moldability, it is preferred to use polycarbonate (meth)acrylate as the ionizing radiation curable resin constituting the raised layer 2.

[0095] When the decorative sheet of the present invention is used for injection molding or vacuum forming, it is also preferable to form the raised layer 2 from a mixture of an ionizing radiation curable resin and a thermoplastic resin from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional moldability. The type of thermoplastic resin and the preferred mixing ratio of the ionizing radiation curable resin and the thermoplastic resin can be the same as those described below for the first resin layer 11.

[0096] [First resin layer 11]

[0097] The first resin layer 11 contains a matting agent for purposes such as adjusting the gloss of the decorative sheet 10. In the decorative sheet 10 of the present invention, the first resin layer 11 is provided on at least a portion of the raised layer 2. The first resin layer 11 is preferably provided on the entire surface of the raised layer 2, and more preferably provided on the entire surface of one side of the decorative sheet 10 (i.e., a full-surface coating). Figures 1 to 7 The figure shows a mode in which the first resin layer 11 is provided on the entire surface of one side of the decorative sheet 10. The first resin layer 11 is preferably in contact with the ridge layer 2. When the decorative sheet 10 has the second resin layer 12, the first resin layer 11 is preferably in contact with the second resin layer 12.

[0098] Examples of the resin constituting the first resin layer 11 include phenolic resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensate, silicone resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ionomer, polymethylpentene, acrylate, methacrylate, polycarbonate, and cellulose triacetate.

[0099] Alternatively, an ionizing radiation curable resin may be used to form the first resin layer 11. The ionizing radiation curable resin may be exemplified by the same resins as those described in detail in the section [Rising Layer 2].

[0100] The first resin layer 11 contains a matting agent. There is no particular limitation on the matting agent, and a wide range of well-known matting agents can be used. Examples of matting agents include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, aluminosilicate, and barium sulfate; and resin (organic) particles such as acrylic beads, polyethylene, polyurethane resin, polycarbonate, and polyamide (nylon). The average particle size of the particles is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm. The amount of matting agent added is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, based on the resin composition (excluding the solvent) that forms the first resin layer 11. The shape of the particles is polyhedron, spherical, scaly, etc. Among the above-mentioned inorganic particles and organic particles, silica is preferred.

[0101] The thickness of the first resin layer 11 is preferably adjusted based on the tactile feel of the uneven shape, taking into account the average thickness of the raised layer 2 and other factors. From this perspective, the thickness of the first resin layer 11 is preferably approximately 2 to 10 μm, more preferably approximately 0.1 to 20 μm, even more preferably approximately 0.3 to 10 μm, and even more preferably approximately 0.5 to 5 μm. The thickness of the first resin layer 11 refers to the thickness of the first resin layer 11 not on the raised layer 2.

[0102] When the decorative sheet of the present invention is used for injection molding or vacuum molding, the aforementioned polycarbonate (meth)acrylate is preferably used as the ionizing radiation curable resin constituting the first resin layer 11 from the viewpoint of improving the scratch resistance of the decorative sheet and improving the three-dimensional moldability.

[0103] When the decorative sheet of the present invention is used in injection molding or vacuum forming applications, it is also preferable to form the first resin layer 11 from a mixture of an ionizing radiation-curable resin and a thermoplastic resin, in order to improve the scratch resistance of the decorative sheet and enhance its three-dimensional moldability. Examples of thermoplastic resins include acrylic resins, polyurethane resins, and olefin resins, with acrylic resins being particularly preferred. The mixing ratio of the ionizing radiation-curable resin to the thermoplastic resin, by mass, is preferably approximately 10:90 to 75:25, and more preferably approximately 25:75 to 50:50.

[0104] [Second resin layer 12]

[0105] The decorative sheet 10 of the present invention may have a second resin layer 12 on part or all of its surface, as needed, for purposes such as gloss adjustment. The second resin layer 12 is provided on the side of the first resin layer 11 opposite to the raised layer 2. The second resin layer 12 may be provided on a portion of the first resin layer 11, and is preferably provided on at least a portion of the raised layer. Figure 2 、 Figure 3 、 Figure 5 、 Figure 6 and Figure 7 The diagram shows a method in which the second resin layer 12 is provided on a portion of the first resin layer 11. More specifically, Figure 2 、 Figure 3 and Figure 7 The diagram shows a mode in which the second resin layer 12 is provided on a portion of the first resin layer 11 and on the entire surface of the ridge layer 2. Figure 5 and Figure 6 The figure shows a mode in which the second resin layer 12 is provided on a part of the first resin layer 11 and on a part of the ridge layer 2. Figure 4 The figure shows a mode in which the second resin layer 12 is provided on the entire surface of the first resin layer 11 on the side opposite to the ridge layer 2 side.

[0106] By providing the second resin layer 12 on the first resin layer 11, the first resin layer 11 containing the matting agent is exposed in areas and not exposed in areas, creating a gloss difference between the areas, thereby imparting a high degree of design to the decorative sheet of the present invention. To achieve a more superior design, the second resin layer 12 preferably has a higher gloss than the first resin layer 11. Specifically, the first resin layer 11 preferably has a relatively low gloss due to the inclusion of the matting agent, while the second resin layer 12 has a relatively high gloss, thereby creating a designed gloss difference between the first and second resin layers 11, 12.

[0107] In addition, in the decorative sheet 10 of the present invention, the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed are preferably formed in the same style. The same style means that the position where the raised layer 2 is formed and the position where the second resin layer 12 is formed are located at positions that are related to each other when viewed from above. Specifically, it includes: when viewed from above, (a) the second resin layer 12 is located at the same position as the raised layer 2; (b) the second resin layer 12 is located at a position different from the raised layer 2; (c) the second resin layer 12 is located at a certain distance and direction away from the raised layer 2, etc. More specifically, as Figure 3 As shown, the locations where the raised layers 2 are formed become the convex portions of the surface of the decorative sheet 10, and the second resin layer 12 is formed on the raised layers 2. The first resin layer 11 is exposed in the recessed portions between the raised layers 2. This allows the gloss difference between the first resin layer 11 (low gloss) and the second resin layer 12 (high gloss) to be utilized to further enhance the three-dimensional effect created by the combination of visual design and tactile feel. Although not shown, the locations where the raised layers 2 are formed can also be formed in the recessed portions between the raised layers 2. In this case, the first resin layer 11 is also exposed in the recessed portions between the raised layers 2.

[0108] The second resin layer 12 is preferably a transparent resin layer, wherein transparency includes any of colorless transparency, colored transparency, and translucent transparency.

[0109] Examples of the resin constituting the second resin layer 12 include phenolic resins, urea resins, diallyl phthalate, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, aminoalkyd resins, melamine-urea co-condensates, silicone resins, polysiloxanes, polyethylene terephthalate, polybutylene terephthalate, polyamides, polyethylene, polypropylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, ionomers, polymethylpentene, acrylic acid esters, methacrylic acid esters, polycarbonates, and cellulose triacetate. Furthermore, the aforementioned ionizing radiation-curable resins may also be used. These resins may be used alone or in combination of two or more.

[0110] Furthermore, the second resin layer 12 may contain a matting agent to adjust the gloss. When the second resin layer 12 contains a matting agent, the content of the matting agent in the second resin layer 12 is preferably less than that in the first resin layer 11. By making the content of the matting agent in the second resin layer 12 less than that in the first resin layer 11, the gloss of the second resin layer 12 can be easily increased compared to that of the first resin layer 11, thereby achieving excellent design properties.

[0111] Examples of the matting agent used in the second resin layer 12 include the same matting agents as those listed for the first resin layer 11. The amount of the matting agent added is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the resin composition (excluding the solvent) forming the second resin layer 12. The phrase "the content of the matting agent in the second resin layer 12 is less than the content of the matting agent in the first resin layer 11" means that the mass of the matting agent per unit mass of the solid content of the resin composition forming the second resin layer 12 is less than the mass of the matting agent per unit mass of the solid content of the resin composition forming the first resin layer 11.

[0112] When the decorative sheet 10 of the present invention contains the pattern layer 3 described later, it is preferred that the second resin layer 12 is configured to form the same style as the pattern of the pattern layer 3. By forming a structure in which the pattern of the pattern layer 3 and the pattern of the second resin layer 12 form the same style, a decorative sheet with better design can be made. Among them, in the present invention, the same style of the pattern of the pattern layer 3 and the second resin layer 12 can be listed as follows: when the decorative sheet is viewed from above, the position of the pattern of the pattern layer 3 corresponds to the position where the second resin layer 12 is formed (so-called positive); the position of the pattern of the pattern layer 3 corresponds to the position where the second resin layer 12 is not formed (so-called negative). As an example of the same style of the pattern of the pattern layer 3 and the second resin layer 12, in Figure 3The negative method is exemplified in . Figure 6 In the example, the pattern of the design layer 3 is formed in the same style as the second resin layer 12 , and the ridge layer 2 and the design layer 3 are not formed in the same style.

[0113] In the decorative sheet 10 of the present invention, the design layer 3 has a wood grain pattern. A second resin layer 12 having a higher gloss than the first resin layer 11 is preferably provided on portions of the wood grain other than at least one of the winter grain pattern and the duct pattern. This reduces the gloss of the winter grain pattern and / or the duct pattern, thereby achieving an excellent design similar to that of natural wood. When forming the second resin layer as described above, it is preferred to use a plate with the same wood grain pattern and / or the duct pattern as the design layer 3 reversed (i.e., in a negative state) and print using a known printing method. Preferred printing methods include gravure printing and screen printing.

[0114] The second resin layer 12 may be colored, but it is particularly desirable not to mix a colorant.

[0115] From the viewpoint of achieving both excellent tactile feel and design, the thickness of the second resin layer is preferably about 0.1 to 20 μm, more preferably about 0.5 to 10 μm, and even more preferably about 1 to 5 μm.

[0116] When the decorative sheet 10 of the present invention is used for injection molding or vacuum molding, polycarbonate (meth)acrylate is preferably used as the ionizing radiation-curable resin constituting the second resin layer 12 from the viewpoint of improving the scratch resistance of the decorative sheet 10 and improving the three-dimensional moldability. The polycarbonate (meth)acrylate can be the same compound as exemplified in the section [Elevated Layer 2].

[0117] Furthermore, when the decorative sheet 10 of the present invention is used for injection molding or vacuum molding, it is also preferable to form the second resin layer 12 from a mixture of an ionizing radiation curable resin and a thermoplastic resin from the viewpoint of improving the scratch resistance of the decorative sheet 10 and improving the three-dimensional moldability. The type of thermoplastic resin and the preferred mixing ratio of the ionizing radiation curable resin and the thermoplastic resin may be the same as described in the section [First Resin Layer 11].

[0118] [Third resin layer 13]

[0119] The third resin layer 13 is provided, as needed, on the side of the raised layer 2 opposite the first resin layer 11 (below the raised layer 2) for purposes such as improving the chemical resistance of the decorative sheet. Specifically, the presence of particles in the raised layer 2 can sometimes make it easier for chemicals to penetrate through the raised layer 2. For example, if a patterned layer 3 (described later) is provided below the raised layer 2, chemicals may penetrate the patterned layer 3, thereby reducing the chemical resistance of the decorative sheet. Providing the third resin layer 13 between the raised layer 2 and the patterned layer 3 can prevent chemicals from penetrating the patterned layer 3.

[0120] The third resin layer 13 is provided on the lower side of at least a portion of the raised layer 2. The third resin layer 13 is preferably provided on the lower side of the entire surface of the raised layer 2, and is preferably provided on the entire surface of one surface side of the decorative sheet (i.e., a full-surface coating layer). Figure 7 , the third resin layer 13 is shown as being provided on the entire surface of one surface side of the decorative sheet. The third resin layer 13 is preferably in contact with the raised layer 2. In addition, when the decorative sheet 10 includes the pattern layer 3, the third resin layer 13 is preferably in contact with both the raised layer 2 and the pattern layer 3.

[0121] Examples of the resin constituting the third resin layer 13 include phenolic resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensate, silicone resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ionomer, polymethylpentene, acrylate, methacrylate, polycarbonate, and cellulose triacetate.

[0122] Alternatively, an ionizing radiation curable resin may be used to form the third resin layer 13. The ionizing radiation curable resin may be exemplified by the same resins as those described in detail in the section [Rising Layer 2].

[0123] Considering chemical resistance and the like, the thickness of the third resin layer 13 is, for example, preferably about 2 to 10 μm, more preferably about 0.1 to 20 μm, further preferably about 0.3 to 10 μm, and even more preferably about 0.5 to 5 μm.

[0124] [Pattern layer 3]

[0125] The pattern layer 3 is a layer provided under the raised layer 2 as needed for the purpose of imparting decorative properties to the decorative sheet. The raised layer 2 and the pattern layer 3 may be in contact with each other or may be laminated via a primer layer or the like described later.

[0126] The pattern layer 3 may be formed with a desired pattern using, for example, an ink composition. The ink composition used to form the pattern layer 3 may be a composition obtained by appropriately mixing a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like with a binder.

[0127] The binder used in the ink composition is not particularly limited. Examples thereof include polyurethane resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic acid copolymers, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, cellulose nitrate resins, and cellulose acetate resins. These binders may be used alone or in combination of two or more.

[0128] There are no particular restrictions on the colorant used in the ink composition, and examples thereof include: inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, chrome yellow, titanium yellow, iron red, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metallic pigments containing flaky foils such as aluminum and brass; pearlescent (pearl) pigments containing flaky foils such as titanium dioxide-coated mica and basic lead carbonate, etc.

[0129] The pattern formed by the pattern layer 3 is not particularly limited. Examples include wood grain patterns, marble patterns (e.g., travertine marble patterns) and other stone patterns imitating rock surfaces, fabric patterns imitating cloth-like patterns, tile patterns, brickwork patterns, and the like. These patterns may be combined to form inlaid wood or patchwork patterns, or may be a single color with no pattern (so-called full-surface painting). These patterns may be formed by multicolor printing using conventional process colors of yellow, red, cyan, and black, or by unique multicolor printing using plates of various colors that form the pattern.

[0130] The thickness of the pattern layer 3 is not particularly limited, and is, for example, 1 to 30 μm, preferably 1 to 20 μm.

[0131] In addition, the pattern layer 3 can also be a metal film layer. As the metal forming the metal film layer, for example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc and alloys containing at least one of these can be listed. The method for forming the metal film layer is not particularly limited. For example, evaporation methods such as vacuum evaporation using the above-mentioned metals, sputtering, ion plating, etc. can be listed. The metal film layer can be provided on the entire surface or partially. In addition, in order to improve the adhesion with the adjacent layer, a primer layer using a known resin can also be provided on the surface or back of the metal film layer.

[0132] [Base coat]

[0133] For the purpose of improving the adhesiveness of the ridge layer 2 and the like, a primer layer is provided under the ridge layer 2 as needed.

[0134] From the viewpoint of improving the adhesion between the raised layer 2 and the layer located therebelow, it is preferable to provide a primer layer directly below the raised layer 2. The primer layer is provided between the raised layer 2 and the patterned layer 3, for example.

[0135] As the primer composition constituting the basecoat layer, a composition containing a binder resin such as a polyurethane resin, a (meth)acrylic resin, a (meth)acrylic acid-polyurethane copolymer, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a butyral resin, a chlorinated polypropylene, or a chlorinated polyethylene is preferably used. These resins may be used alone or in combination of two or more. Among these, polyurethane resins, (meth)acrylic acid resins, and (meth)acrylic acid-polyurethane copolymers are preferred.

[0136] As the polyurethane resin, a polyurethane having a polyol as the main agent and an isocyanate as the crosslinking agent (curing agent) can be used. As a polyol, a compound having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc. can be used. As the above-mentioned isocyanate, a polyisocyanate having two or more isocyanate groups in the molecule, an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, or an aliphatic (or alicyclic) isocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. can be used. In addition, a polyurethane resin and a butyraldehyde resin can also be mixed to form it.

[0137] From the perspectives of adhesion to the raised layer 2, difficulty of interaction after lamination of the raised layer 2, physical properties, and moldability, it is preferred to use an acrylic polyol or polyester polyol in combination as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking agent. It is particularly preferred to use an acrylic polyol and hexamethylene diisocyanate in combination.

[0138] Examples of the (meth)acrylic resin include homopolymers of (meth)acrylates, copolymers of two or more different (meth)acrylate monomers, and copolymers of (meth)acrylates and other monomers. Specifically, (meth)acrylic resins composed of homopolymers or copolymers containing (meth)acrylates, such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, and styrene-methyl (meth)acrylate copolymer, can be suitably used.

[0139] As the (meth)acrylic acid-polyurethane copolymer, for example, an acrylic acid-polyurethane (polyester polyurethane) block copolymer is preferred. As the curing agent, the various isocyanates described above can be used. Regarding the acrylic acid-polyurethane (polyester polyurethane) block copolymer, the acrylic acid / polyurethane ratio (mass ratio) is preferably adjusted within a range of preferably 9 / 1 to 1 / 9, and more preferably 8 / 2 to 2 / 8, as desired.

[0140] The thickness of the primer layer is not particularly limited, but is, for example, about 0.5 to 20 μm, preferably 1 to 5 μm.

[0141] The primer composition is used to form the undercoat layer by conventional coating methods such as gravure coating, reverse gravure coating, gravure offset coating, spin coating, roll coating, reverse roll coating, contact coating, roller coating, dip coating, screen coating, wire bar coating, flow coating, douche coating, pouring coating, brush coating, and spray coating, as well as transfer coating. Transfer coating involves forming a coating film of the undercoat layer or adhesive layer on a sheet (film substrate) and then coating the surface of the target layer in the decorative sheet.

[0142] [Hidden Layer]

[0143] The concealing layer is provided between the base layer 1 and the raised layer 2 , or between the base layer 1 and the pattern layer 3 when providing the pattern layer 3 , as needed, to suppress changes or variations in the color of the base layer 1 .

[0144] In order to prevent the base material layer 1 from adversely affecting the color tone and pattern of the decorative sheet, the concealing layer is usually formed as an opaque layer.

[0145] The concealing layer is formed using an ink composition obtained by appropriately mixing a binder with a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. The ink composition for forming the concealing layer can be appropriately selected from the composition used for the pattern layer 3 described above.

[0146] The concealing layer is generally set to a thickness of about 1 to 20 μm, and is preferably formed as a so-called full-coat printed layer.

[0147] The concealing layer can be formed by conventional printing methods such as gravure printing, offset printing, screen printing, printing from a transfer sheet, and inkjet printing; and conventional coating methods such as gravure coating, reverse gravure coating, gravure offset coating, spin coating, roller coating, and reverse roller coating.

[0148] [Back adhesive layer]

[0149] The back adhesive layer is a layer provided on the side opposite to the outer surface of the decorative sheet as needed for the purpose of improving adhesion with the molding resin when molding a decorative resin molded article.

[0150] Depending on the molding resin used for the decorative resin molded article, a thermoplastic resin or a curable resin can be used for the back adhesive layer.

[0151] Examples of the thermoplastic resin used to form the back adhesive layer include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic polyurethane resins, thermoplastic polyester resins, polyamide resins, and rubber-based resins. These thermoplastic resins may be used alone or in combination of two or more.

[0152] Examples of the thermosetting resin for forming the back adhesive layer include polyurethane resins and epoxy resins. These thermosetting resins may be used alone or in combination of two or more.

[0153] 2. Manufacturing method of decorative sheet

[0154] The decorative sheet 10 of the present invention can be manufactured using a method comprising laminating the layers to produce a laminate comprising at least the base layer 1, the raised layer 2, and the first resin layer 11 laminated in this order on one surface of the base layer 1. Specific conditions for the composition, thickness, and method of forming each layer are as described above in the section "Composition of Each Layer." As described above, the decorative sheet 10 may further include a second resin layer 12, a patterned layer 3, a primer layer, a concealing layer, a backside adhesive layer, and the like, as needed.

[0155] 3. Decorative resin molded products

[0156] The decorative resin molded article 20 of the present invention is obtained by integrating the molding resin with the decorative sheet of the present invention. That is, the decorative resin molded article 20 of the present invention is characterized in that: Figure 8 As shown in the schematic diagram of FIG, the decorative resin molded article 20 of the present invention comprises, in order, at least a molded resin layer 4, a base layer 1, a raised layer 2, and a first resin layer 11. The first resin layer 11 contains a matting agent, and the raised layer 2 contains particles. One surface of the decorative resin molded article 20 of the present invention has a concave-convex shape. The decorative resin molded article 20 of the present invention may further comprise, as necessary, at least one of the aforementioned second resin layer 12, the patterned layer 3, the primer layer, the concealing layer, and the backside adhesive layer.

[0157] The decorative resin molded article of the present invention can be produced, for example, using the decorative sheet of the present invention by various injection molding methods, such as insert molding, injection molding and decoration, blow molding, and gas injection molding. In the present invention, the decorative sheet of the present invention is subjected to various injection molding methods to produce a decorative resin molded article, thereby achieving excellent adhesion between the decorative sheet and the molded resin layer. Among these injection molding methods, insert molding and injection molding and decoration are preferred.

[0158] In the insert molding method, the decorative sheet of the present invention is first vacuum-formed into the surface shape of the molded article using a vacuum forming mold in a vacuum forming step (offline pre-molding). Subsequently, excess portions are trimmed as needed to produce a molded sheet. This molded sheet is then inserted into an injection molding mold. The mold is closed, and a fluidized resin is injected into the mold and solidified. Simultaneously with the injection molding, the decorative sheet is integrated with the outer surface of the resin molded article, thereby producing a decorative resin molded article.

[0159] More specifically, the decorative resin molded article of the present invention can be produced by an insert molding method including the following steps.

[0160] A vacuum forming step of preforming the decorative sheet of the present invention into a three-dimensional shape using a vacuum forming mold;

[0161] a trimming step of trimming excess portions of the vacuum-formed decorative sheet to obtain a formed sheet; and

[0162] The molding sheet is inserted into the injection molding die, the injection molding die is closed, and the fluidized resin is injected into the injection molding die to integrate the resin and the molding sheet.

[0163] During the vacuum forming process of the insert molding method, the decorative sheet can also be heated to form the sheet. The heating temperature is not particularly limited and can be appropriately selected based on the type of resin forming the decorative sheet and its thickness. For example, when using an ABS resin film as the base layer 1, the temperature can typically be around 120-200°C. Furthermore, during the integration process, the temperature of the fluidized resin is not particularly limited but can typically be around 180-320°C.

[0164] In addition, in the simultaneous decoration method by injection molding, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum forming mold provided with a suction hole for injection molding. After pre-molding (offline pre-molding) using the female mold, the injection molding mold is closed, and the flowing resin is injected into the mold to be solidified. Simultaneously with the injection molding, the decorative sheet of the present invention is integrated with the outer surface of the resin molded product, thereby manufacturing a decorative resin molded product.

[0165] More specifically, the decorative resin molded article of the present invention can be produced by an injection molding and simultaneous decoration method including the following steps.

[0166] A preforming step is performed in which, for the decorative sheet of the present invention, the base material layer 1 side of the decorative sheet is placed opposite to the molding surface of a movable mold having a molding surface of a predetermined shape, the decorative sheet is heated to soften it, and vacuum suction is applied from the movable mold side to cause the softened decorative sheet to adhere closely to the molding surface of the movable mold, thereby preforming the decorative sheet;

[0167] an integration step of closing a movable mold and a fixed mold having the decorative sheet sealed along the molding surface, injecting and filling a fluidized resin into a mold cavity formed by the two molds, and curing the resin molded body to form a resin molded body, and integrating the resin molded body with the decorative sheet by laminating; and

[0168] The removal step is to separate the movable mold from the fixed mold and remove the resin molded body formed by laminating all the layers of the decorative sheet.

[0169] In the pre-molding process of the injection molding and simultaneous decoration method, the heating temperature of the decorative sheet is not particularly limited and can be appropriately selected based on the type of resin constituting the decorative sheet and the thickness of the decorative sheet. When a polyester resin film or acrylic resin film is used as the base layer 1, the heating temperature can generally be approximately 70 to 130°C. Furthermore, during the injection molding process, the temperature of the fluidized resin is not particularly limited but can generally be approximately 180 to 320°C.

[0170] In addition, the decorative resin molded article of the present invention can also be produced by a decorative method such as vacuum pressing, in which the decorative sheet of the present invention is attached to a pre-prepared three-dimensional resin molded body (molded resin layer 4). In the vacuum pressing method, the decorative sheet of the present invention and the resin molded body are first placed in a vacuum pressing machine comprising a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side, with the decorative sheet on the first vacuum chamber side and the resin molded body on the second vacuum chamber side, and with the base material layer 1 side of the decorative sheet facing the resin molded body side. The two vacuum chambers are then evacuated. The resin molded body is placed on a lifting platform on the second vacuum chamber side that can be raised and lowered. Next, the first vacuum chamber is pressurized, and the molded body is pressed against the decorative sheet using the lifting platform. The pressure difference between the two vacuum chambers is used to stretch the decorative sheet while attaching it to the surface of the resin molded body. Finally, the two vacuum chambers are opened to atmospheric pressure, and the excess portion of the decorative sheet is trimmed as needed, thereby obtaining the decorative resin molded article of the present invention.

[0171] In vacuum pressing, prior to pressing the molded body onto the decorative sheet, a heating step is preferably included to soften the decorative sheet and improve its formability. Vacuum pressing methods that include this step are sometimes specifically referred to as vacuum heat pressing. The heating temperature in this step can be appropriately selected based on factors such as the type of resin constituting the decorative sheet and its thickness. When using a polyester resin film or acrylic resin film as the base layer 1, the heating temperature is typically between 60°C and 200°C.

[0172] In the decorative resin molded article of the present invention, a resin suitable for the intended use may be selected to form the molded resin layer 4. The molded resin forming the molded resin layer 4 may be a thermoplastic resin or a thermosetting resin.

[0173] Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. Among these, ABS resin is preferred due to its particularly excellent adhesion to the substrate layer 1. These thermoplastic resins may be used alone or in combination of two or more.

[0174] Examples of thermosetting resins include polyurethane resins and epoxy resins. These thermosetting resins may be used alone or in combination of two or more.

[0175] The decorative resin molded article of the present invention can be used as, for example, interior or exterior decorative materials for vehicles such as automobiles; window and door sashes such as window frames and door frames; interior decorative materials for walls, floors, ceilings, and other buildings; housings for home appliances such as television receivers and air conditioners; containers, etc.

[0176] Example

[0177] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.

[0178] (Production of decorative sheets)

[0179] [Example 1]

[0180] A black ABS stock roll was prepared as the base layer. Using an ink made by mixing a colorant with a copolymer of vinyl chloride and vinyl acetate, a 1μm thick full-surface coloring layer (hidden layer) and a 4μm thick wood grain pattern layer were applied in this order by gravure printing. The wood grain pattern was formed so that the winter wood grain area was darker.

[0181] Next, an ink containing Resin Composition A (70% by mass of a bifunctional polyurethane acrylate (weight-average molecular weight 30,000) with a polycarbonate backbone and 30% by mass of polyurethane beads (average particle size 20 μm, particle size 5-60 μm (90% of all organic particles are within the 5-60 μm particle size range)) was applied using raised printing with a patterned plate with a plate depth of 90 μm. This resulted in a raised layer (20 μm thick) partially formed on the patterned layer. The raised pattern was a wood grain pattern, formed so that its area ratio relative to one surface of the substrate layer was 25%.

[0182] Next, using an ink containing 70% by mass of a bifunctional urethane acrylate (weight-average molecular weight 30,000) with a polycarbonate backbone and 30% by mass of silica particles (average particle size 2 μm) as a matting agent, gravure printing (full-surface printing) was performed from the top of the raised layer onto the entire surface, forming a 5 μm thick first resin layer. The first resin layer was set to a gloss of 1.0 (60° gloss).

[0183] Next, using an ink containing 6% by mass of silica particles (average particle size 2 μm) as a matting agent and 94% by mass of a bifunctional urethane acrylate (weight-average molecular weight 30,000) with a polycarbonate backbone, the winter pattern portion of the pattern layer, excluding the wood grain pattern, was gravure-printed to create a pattern that matched the wood grain pattern. This resulted in a 2 μm-thick second resin layer. The second resin layer was set to a gloss of 10.0 (60° gloss).

[0184] Finally, the surface was irradiated with electron beams at an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the ionizing radiation curable resin, thereby obtaining a decorative sheet.

[0185] [Example 2]

[0186] In forming the raised layer of Example 1, an ink containing resin composition B "70% by mass of a bifunctional polyurethane acrylate (weight-average molecular weight 30,000) having a polycarbonate skeleton and 30% by mass of polyurethane beads (average particle size 15 μm, particle size 4 to 50 μm) as organic particles" is used instead of resin composition A. The coating is performed by raised printing using a pattern plate with a plate depth of 70 μm, and a raised layer (thickness 15 μm) is partially formed on the pattern layer. Except for this, the same operation as in Example 1 is carried out to obtain a decorative sheet.

[0187] [Example 3]

[0188] A decorative sheet was obtained in the same manner as in Example 1 except that the raised layer was formed so that the area ratio of the raised layer to one surface of the base material layer became 15%.

[0189] [Example 4]

[0190] A decorative sheet was obtained in the same manner as in Example 1 except that the raised layer was formed so that the area ratio of the raised layer to one surface of the base material layer became 5%.

[0191] [Example 5]

[0192] A decorative sheet was obtained in the same manner as in Example 1 except that the raised layer was formed so that the area ratio of the raised layer to one surface of the base material layer became 3%.

[0193] [Example 6]

[0194] A decorative sheet was obtained in the same manner as in Example 1 except that the raised layer was formed so that the area ratio of the raised layer to one surface of the base material layer became 35%.

[0195] [Example 7]

[0196] In the formation of the raised layer of Example 1, an ink containing resin composition C "70% by mass of an ionizing radiation-curable resin (pentaerythritol triacrylate: thermoplastic resin = 30:70 (mass ratio) containing pentaerythritol triacrylate and a thermoplastic resin (a homopolymer of methyl methacrylate, with a weight-average molecular weight of 100,000) and 30% by mass of polyurethane beads (average particle size of 20 μm, particle size of 5 to 60 μm) as organic particles" is used instead of resin composition A. The raised layer (thickness 20 μm) is partially formed on the pattern layer by coating using raised printing using a pattern plate with a plate depth of 90 μm. Except for this, the same operation as in Example 1 is carried out to obtain a decorative sheet.

[0197] [Example 8]

[0198] In forming the raised layer of Example 1, an ink containing resin composition D "70% by mass of a bifunctional polyurethane acrylate (weight-average molecular weight 30,000) having a polycarbonate skeleton and 30% by mass of polyurethane beads (average particle size 10 μm, particle size 3 to 40 μm) as organic particles" is used instead of resin composition A. The coating is performed by raised printing using a pattern plate with a plate depth of 50 μm, and a raised layer (thickness 10 μm) is partially formed on the pattern layer. Except for this, the same operation as in Example 1 is carried out to obtain a decorative sheet.

[0199] [Example 9]

[0200] In forming the raised layer of Example 1, an ink containing resin composition E "70% by mass of a bifunctional polyurethane acrylate (weight-average molecular weight 30,000) having a polycarbonate skeleton and 30% by mass of polyurethane beads (average particle size 50 μm, particle size 10-80 μm) as organic particles" is used instead of resin composition A. The coating is performed by raised printing using a pattern plate with a plate depth of 90 μm, and a raised layer (thickness 50 μm) is partially formed on the pattern layer. Except for this, the same operation as in Example 1 is carried out to obtain a decorative sheet.

[0201] [Example 10]

[0202] In the production of the decorative sheet of Example 1, a decorative sheet was obtained in the same manner as in Example 1, except that a third resin layer was laminated on the pattern layer. The third resin layer was formed by gravure printing (full-surface printing) on the entire surface of the pattern layer using an ink containing 70% by mass of a bifunctional urethane acrylate (weight-average molecular weight 30,000) having a polycarbonate backbone and 30% by mass of silica particles (average particle size 2 μm) as a matting agent, to form a 5 μm thick third resin layer. The raised layer, first resin layer, and second resin layer were formed on the third resin layer in the same manner as in Example 1.

[0203] [Reference Example 1]

[0204] A decorative sheet was obtained in the same manner as in Example 1, except that the ridge layer was provided on the second resin layer instead of the pattern layer.

[0205] [Comparative Example 1]

[0206] In forming the raised layer of Example 1, an ink containing the particle-free resin composition F "bifunctional polyurethane acrylate (weight-average molecular weight 10,000) having a polycarbonate skeleton" is used instead of the resin composition A, and the coating is performed by raised screen printing using a pattern plate with a plate depth of 90 μm to partially form a raised layer (thickness 20 μm) on the pattern layer. Except for this, the same operation as in Example 1 is carried out to obtain a decorative sheet.

[0207] [Comparative Example 2]

[0208] A decorative sheet was obtained in the same manner as in Comparative Example 1 except that the thickness of the raised layer was adjusted to 50 μm by raised printing using a pattern plate with a plate depth of 90 μm.

[0209] <Evaluation of the design of decorative sheets>

[0210] The design properties of the decorative sheets were evaluated as follows, considering the deviation from the desired design and the wood grain design. Each decorative sheet obtained above was visually inspected from the surface on the second resin layer side (opposite to the substrate layer) and evaluated for design properties according to the following criteria. The results are shown in Table 1.

[0211] A: The desired design can be achieved, and the wood grain design is excellent;

[0212] B: Due to the influence of the raised layer, the design deviates slightly from the desired one, but the wood grain design is good.

[0213] C: Due to the influence of the raised layer, there are some deviations from the desired design. The design of the wood grain is average and there is no problem in practical use.

[0214] D: Due to the influence of the raised layer, the desired design is greatly deviated, and the design of the wood grain is poor.

[0215] <Evaluation of the touch of the decorative sheet>

[0216] The touch of each of the decorative sheets obtained above before and after molding was evaluated as follows.

[0217] (Touch before molding)

[0218] The surface of each decorative sheet obtained above on the second resin layer side (the side opposite to the base material layer) was touched with a finger, and the touch was evaluated according to the following criteria.

[0219] A: I clearly felt the bumps and depressions;

[0220] B: Feeling the bumps;

[0221] C: The surface is slightly uneven, and can be considered a decorative piece with a tactile feel.

[0222] D: The unevenness is barely perceptible and cannot be considered a decorative sheet with a tactile feel.

[0223] (Touch after molding)

[0224] Each decorative sheet obtained above is heated by an infrared heater until the sheet temperature reaches 160°C to soften it. Next, vacuum forming is performed using a vacuum forming mold (maximum stretching ratio 100%) to form it into the internal shape of the mold. After the molded decorative sheet is cooled, it is removed from the mold. Thereafter, injection resin is injected into the mold cavity of the mold, and the decorative sheet and injection resin are molded as a whole, and then taken out from the mold to obtain a decorative resin molded product (molded decorative sheet). For the molded decorative sheet, touch the surface of the second resin layer side (the side opposite to the substrate layer) with your fingers, and evaluate the touch according to the following criteria. The results are shown in Table 1.

[0225] A: I clearly felt the bumps and depressions;

[0226] B: Feeling the bumps;

[0227] C: The surface is slightly uneven, and can be considered a decorative piece with a tactile feel.

[0228] D: The unevenness is barely perceptible and cannot be considered a decorative sheet with a tactile feel.

[0229] <Touch after wear test>

[0230] For the decorative resin molded article obtained above, a wear resistance test was performed on the surface of the second resin layer side (the side opposite to the substrate layer) using a method based on the provisions of JIS K7204. As for the test conditions, the load of the two wear wheels (CS-10F) was set to 500g respectively, and the rotation speed was set to 100 rpm. For the decorative resin molded article after the wear test, the surface of the wear test part was touched with a finger, and the touch was evaluated according to the following criteria. The evaluation criteria for wear resistance are as follows. The results are shown in Table 1.

[0231] A: I clearly felt the bumps and depressions;

[0232] B: Feeling the bumps;

[0233] C: The surface is slightly uneven, and can be considered a decorative piece with a tactile feel.

[0234] D: The unevenness is barely perceptible and cannot be considered a decorative sheet with a tactile feel.

[0235] Sunscreen-resistant cosmetics

[0236] 0.1 g of commercially available sunscreen cosmetics was evenly applied to a 50 mm x 50 mm section on the surface of each decorative sheet obtained above (on the second resin layer side (opposite to the substrate layer)). The sheet was then placed in a 55°C oven for 4 hours. The decorative sheet was removed and the surface rinsed with detergent. The condition of the area coated with the sunscreen cosmetics (test surface) was visually observed. The chemical resistance of the sunscreen cosmetics was evaluated according to the following criteria. The sunscreen cosmetics used were commercially available SPF 50 and contained 3% 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)-1,3-propanedione, 10% 3,3,5-trimethylcyclohexyl salicylate, 5% 2-ethylhexyl salicylate, and 10% 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. The results are shown in Table 1.

[0237] A: No cracks, whitening, swelling, gloss loss, peeling or other abnormalities were observed on the test surface, indicating a good appearance.

[0238] B: Slight whitening was observed on a portion of the test surface, but there was no practical problem.

[0239] C: Whitening or gloss change was confirmed on part of the test surface, but it is acceptable for practical use;

[0240] D: Significant whitening or gloss change was observed on the entire test surface, which is problematic for practical use.

[0241] <Insecticide resistance>

[0242] For the surface of each decorative sheet obtained above (the second resin layer side (the side opposite to the substrate layer)), 0.05g of a commercially available insecticide was evenly applied to a portion 50mm long by 50mm wide. It was placed in an oven at 55°C for 4 hours. The decorative sheet was removed, the surface was rinsed with detergent, and the state of the portion coated with the insecticide (test surface) was visually observed. The insecticide was evaluated for chemical resistance according to the following criteria. The insecticide is a commercially available product containing 25% DEET (N,N-diethyl-m-toluamide) and 75% other ingredients. The results are shown in Table 1.

[0243] A: No cracks, whitening, swelling, gloss loss, peeling or other abnormalities were observed on the test surface, indicating a good appearance.

[0244] B: Slight gloss change was observed on a portion of the test surface, but there was no practical problem.

[0245] C: Whitening or gloss change was confirmed on part of the test surface, but it is acceptable for practical use;

[0246] D: Significant cracking, whitening, or gloss change in the coating film was observed on the entire test surface, which is problematic for practical use.

[0247]

[0248] The decorative sheets of Examples 1-10 each comprise at least a substrate layer, a partially provided raised layer, and a first resin layer in this order, wherein the first resin layer contains a matting agent and the raised layer contains particles. The decorative sheets of Examples 1-10 are decorative sheets having both excellent tactile feel and design.

[0249] Explanation of symbols

[0250] 1…base material layer

[0251] 2…Uplift layer

[0252] 11…First resin layer

[0253] 12…Second resin layer

[0254] 13…Third resin layer

[0255] 3… pattern layer

[0256] 4…Molding resin layer

[0257] 10…Decorative pieces

[0258] 20…Decorative resin molded products.

Claims

1. A decorative sheet, characterized in that: The invention comprises at least a base material layer, a partially provided raised layer and a first resin layer in this order, The first resin layer is formed of a cured product of an ionizing radiation curable resin composition X, The ionizing radiation curable resin composition X comprises an ionizing radiation curable resin A1, and the ionizing radiation curable resin A1 comprises a polyfunctional polycarbonate (meth)acrylate C1, or The ionizing radiation curable resin composition X comprises an ionizing radiation curable resin B1 and a thermoplastic resin D1, wherein the ionizing radiation curable resin B1 comprises a polyfunctional (meth)acrylate monomer E1. The first resin layer contains a matting agent, The thickness of the first resin layer is not less than 2 μm and not more than 5 μm. The ridge layer is formed of a cured product of an ionizing radiation curable resin composition Y, The ionizing radiation curable resin composition Y comprises an ionizing radiation curable resin A2, and the ionizing radiation curable resin A2 comprises a multifunctional polycarbonate (meth)acrylate C2, or The ionizing radiation curable resin composition Y comprises an ionizing radiation curable resin B2 and a thermoplastic resin D2, wherein the ionizing radiation curable resin B2 comprises a polyfunctional (meth)acrylate monomer E2. The raised layer contains organic particles, The average particle size of the particles contained in the raised layer is 15 μm or more and 60 μm or less. The average thickness of the raised layer is the same as the average particle size of the organic particles. The surface of the decorative sheet has a concavo-convex shape.

2. The decorative sheet according to claim 1, wherein: The average thickness of the ridge layer is 50 μm or less.

3. The decorative sheet according to claim 1 or 2, wherein: The first resin layer is formed on the entire surface of one side of the decorative sheet.

4. The decorative sheet according to claim 1 or 2, wherein: A second resin layer is provided on the side of the first resin layer opposite to the ridge layer side.

5. The decorative sheet according to claim 1, wherein: The organic particles are at least one of polyurethane beads and acrylic beads.

6. The decorative sheet according to claim 1 or 2, wherein: A pattern layer is provided between the base layer and the ridge layer.

7. The decorative sheet according to claim 1 or 2, wherein: The average thickness of the raised layer is less than 50 μm.

8. A decorative resin molded article, characterized in that: The invention comprises at least a molding resin layer, a base material layer, a partially provided protruding layer and a first resin layer in this order, The first resin layer is formed of a cured product of an ionizing radiation curable resin composition X, The ionizing radiation curable resin composition X comprises an ionizing radiation curable resin A1, and the ionizing radiation curable resin A1 comprises a polyfunctional polycarbonate (meth)acrylate C1, or The ionizing radiation curable resin composition X comprises an ionizing radiation curable resin B1 and a thermoplastic resin D1, wherein the ionizing radiation curable resin B1 comprises a polyfunctional (meth)acrylate monomer E1. The first resin layer contains a matting agent, The thickness of the first resin layer is not less than 2 μm and not more than 5 μm. The ridge layer is formed of a cured product of an ionizing radiation curable resin composition Y, The ionizing radiation curable resin composition Y comprises an ionizing radiation curable resin A2, and the ionizing radiation curable resin A2 comprises a multifunctional polycarbonate (meth)acrylate C2, or The ionizing radiation curable resin composition Y comprises an ionizing radiation curable resin B2 and a thermoplastic resin D2, wherein the ionizing radiation curable resin B2 comprises a polyfunctional (meth)acrylate monomer E2. The raised layer contains organic particles, The average particle size of the particles contained in the raised layer is 15 μm or more and 60 μm or less. The average thickness of the raised layer is the same as the average particle size of the organic particles. The surface of the decorative sheet has a concavo-convex shape.

9. The decorative resin molded article according to claim 8, wherein: The average thickness of the ridge layer is 50 μm or less.

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