Decorative sheet, decorative material using same, and resin composition for surface protective layer

Abstract

To provide a decorative sheet and a decorative material capable of extremely improving suppression of bleed-out and maintenance of long-term weather resistance.SOLUTION: There are provided: a decorative sheet 100 including at least a substrate layer 50 and a surface protective layer 10; and a decorative material. The surface protective layer contains a resin component and ultraviolet absorbers, the content of the ultraviolet absorbers is 10 pts.mass or less based on 100 pts.mass of the resin component, and the resin component contains cyclohexyl (meth)acrylate. The surface protective layer satisfies the following [1] or [2]: [1] it contains a hydroxyphenyltriazine compound (I) and a hydroxyphenyltriazine compound (II) as the ultraviolet absorbers; and [2] it contains the hydroxyphenyltriazine compound (I) and a hydroxyphenyltriazine compound (III) as the ultraviolet absorbers.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet, a decorative material using the same, and a resin composition for a surface protective layer. [Background technology]

[0002] Decorative sheets have been used to decorate and protect the surfaces of interior and exterior components of buildings, interior and exterior components of vehicles such as automobiles, or surfaces of furniture, fixtures, home appliances, etc. Decorative sheets have a configuration having, for example, a surface protective layer on a base layer.

[0003] When these decorative sheets are used outdoors or indoors near windows or other locations exposed to sunlight, they are susceptible to changes in color and deterioration of the resin due to the effects of ultraviolet rays. For this reason, decorative sheets containing ultraviolet absorbing agents have been proposed for the purpose of improving weather resistance.

[0004] As the ultraviolet absorbing agent, benzophenone-based ultraviolet absorbing agents and benzotriazole-based ultraviolet absorbing agents have been used, but they are not necessarily satisfactory in terms of performance. Specifically, when trying to obtain sufficient weather resistance using benzophenone-based ultraviolet absorbing agents and benzotriazole-based ultraviolet absorbing agents, the amount of ultraviolet absorbing agent added increases, and there is a problem that the ultraviolet absorbing agent is easily bleeds. In addition, benzophenone-based ultraviolet absorbing agents and benzotriazole-based ultraviolet absorbing agents are subject to large deterioration over time, making it difficult to maintain weather resistance for a long period of time.

[0005] In recent years, decorative sheets using triazine-based ultraviolet absorbers such as hydroxyphenyltriazine compounds have been proposed as a solution to the problems associated with benzophenone-based and benzotriazole-based ultraviolet absorbers (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 5196042 [Patent Document 2] Patent No. 5540589 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0007] The decorative sheets of Patent Documents 1 and 2 are capable of suppressing bleed-out and have good long-term weather resistance, compared to decorative sheets using benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers. However, although the decorative sheets of Patent Documents 1 and 2 are better at suppressing bleed-out and maintaining long-term weather resistance than conventional decorative sheets, these performance requirements may not be met when used in harsh environments, and further improvements are desired.

[0008] Therefore, an object of the present invention is to provide a decorative sheet and decorative material, and a resin composition for a surface protective layer, which can suppress bleed-out and maintain long-term weather resistance extremely well. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention provides the following <1> to <3>. <1> A decorative sheet having at least a substrate layer and a surface protective layer, the surface protective layer contains a resin component and an ultraviolet absorber, the content of the ultraviolet absorber is 10 parts by mass or less relative to 100 parts by mass of the resin component, and the resin component contains cyclohexyl (meth)acrylate; A decorative sheet, wherein the surface protective layer satisfies the following [1] or [2]. [1] The ultraviolet absorbent contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (II), The content of the hydroxyphenyltriazine compound represented by the following general formula (II) is 50 mass% or less relative to 100 mass% in total of the content of the hydroxyphenyltriazine compound represented by the following general formula (I) and the content of the hydroxyphenyltriazine compound represented by the following general formula (II). [2] The ultraviolet absorbing agent contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (III).

[0010] [ka] [ka] [ka]

[0011] <2> A decorative material having an adherend and the decorative sheet described in [1] above. <3> A resin composition for a surface protective layer, comprising a resin component and an ultraviolet absorber, The content of the ultraviolet absorber per 100 parts by mass of the resin component is 10 parts by mass or less, and the resin component contains cyclohexyl (meth)acrylate, A resin composition for a surface protective layer, which satisfies the above [1] or [2]. Effect of the Invention

[0012] According to the present invention, it is possible to provide a decorative sheet and decorative material, and a resin composition for a surface protective layer, which can suppress bleed-out and maintain long-term weather resistance extremely well. [Brief description of the drawings]

[0013] [Figure 1] 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] [Decorative sheet] The decorative sheet of the present invention is a decorative sheet having at least a substrate layer and a surface protective layer, the surface protective layer contains a resin component and an ultraviolet absorber, the content of the ultraviolet absorber is 10 parts by mass or less relative to 100 parts by mass of the resin component, and the resin component contains cyclohexyl (meth)acrylate; The surface protective layer satisfies the following [1] or [2]. [1] The ultraviolet absorbent contains a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II), The content of the hydroxyphenyltriazine compound represented by the general formula (II) is 50 mass% or less relative to 100 mass% in total of the content of the hydroxyphenyltriazine compound represented by the general formula (I) and the content of the hydroxyphenyltriazine compound represented by the general formula (II). [2] The ultraviolet absorbing agent contains a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (III).

[0015] Fig. 1 is a cross-sectional view showing a representative embodiment of a decorative sheet 100 of the present invention. In Fig. 1, the Z-axis direction indicates the thickness direction, and the plane formed by the X-axis and Y-axis indicates a plane when the decorative material is observed from the Z-axis direction. The decorative sheet 100 in Fig. 1 has a surface protective layer 10 on a base layer 50. The decorative sheet 100 in Fig. 1 also has a decorative layer 40, a transparent resin layer 30, and a primer layer 20 between the base layer 50 and the surface protective layer 10.

[0016] As long as the decorative sheet of the present invention has a basic structure of a surface protective layer on a substrate layer, various laminate configurations can be selected depending on the application, required performance, etc. For example, in the embodiment shown in FIG. 1, the decorative sheet 100 has the following laminate configuration (1), but other specific laminate configurations include the following (2) to (7). In the following (1) to (7), " / " indicates the interface between the layers. The embodiment of each layer will be described later. (1) Base layer 50 / decorative layer 40 / transparent resin layer 30 / primer layer 20 / surface protective layer 10 (2) Base material layer 50 / surface protection layer 10 (3) Base layer 50 / primer layer 20 / surface protective layer 10 (4) Base material layer 50 / transparent resin layer 30 / surface protection layer 10 (5) Base material layer 50 / decorative layer 40 / surface protective layer 10 (6) Base material layer 50 / transparent resin layer 30 / decorative layer 40 / surface protective layer 10 (7) Base material layer 50 / transparent resin layer 30 / decorative layer 40 / primer layer 20 / surface protective layer 10

[0017] In the above (1) to (7), an adhesive layer (adhesive layer A described later) can be interposed between the base layer and the surface protection. In addition, the surfaces of the base layer and the transparent resin layer can be embossed to form uneven shapes such as wood grain vessel grooves, sand grain, matte finish, hairline, and leather grain.

[0018] <Ultraviolet absorbing agent> In the present invention, the hydroxyphenyltriazine compounds represented by the general formula (I), the general formula (II), and the general formula (III) are used as ultraviolet absorbents. The decorative sheet contains, at least in the surface protective layer, a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II) or (III). If the surface protective layer of the decorative sheet does not contain the hydroxyphenyl triazine compound represented by the general formula (I) and the hydroxyphenyl triazine compound represented by the general formula (II) or the general formula (III), the long-term weather resistance cannot be maintained very well. From the viewpoint of more excellent bleed-out suppression and easy expression of long-term weather resistance, it is more preferable that the surface protective layer contains a combination of the hydroxyphenyl triazine compound represented by the general formula (I) and the hydroxyphenyl triazine compound represented by the general formula (III). In addition, as long as the effects of the present invention are not impaired, the three types of hydroxyphenyltriazine compounds represented by the general formulas (I), (II) and (III) can be used in combination; however, it is difficult to obtain an effect of suppressing bleed-out and improving long-term weather resistance that exceeds that obtained by the combination of the above-mentioned two types of compounds.

[0019] The decorative sheet may have one or more layers selected from a decorative layer, a transparent resin layer, and a primer layer between the substrate layer and the surface protective layer. At least one of the substrate layer, the transparent resin layer and the primer layer may contain at least one of the hydroxyphenyltriazine compounds represented by the general formulas (I) to (III). In addition to the surface protective layer, by configuring at least one of the base layer, the transparent resin layer, and the primer layer to contain the hydroxyphenyl triazine compound represented by the general formula (I) and the hydroxyphenyl triazine compound represented by the general formula (II) or the general formula (III), the long-term weather resistance of the entire decorative sheet can be improved. Also, in the case of an embodiment in which the decorative sheet has the above configuration, even if the amount of the hydroxyphenyl triazine compound represented by the general formula (I) and the hydroxyphenyl triazine compound represented by the general formula (II) or the general formula (III) added to the surface protective layer is reduced, the long-term weather resistance of the entire decorative sheet can be improved.

[0020] In the surface protective layer, the content of the hydroxyphenyl triazine compound represented by the general formula (II) is 50% by mass or less relative to the total of the content of the hydroxyphenyl triazine compound represented by the general formula (I) and the content of the hydroxyphenyl triazine compound represented by the general formula (II) (100% by mass). If the content of the hydroxyphenyl triazine compound represented by the general formula (II) exceeds 50% by mass, the suppression of bleed-out is poor, and it is difficult to achieve long-term weather resistance. The content of the hydroxyphenyl triazine compound represented by the general formula (II) relative to the total content of the hydroxyphenyl triazine compounds represented by the general formulas (I) and (II) (100% by mass) is preferably 45% by mass or less, more preferably 40% by mass or less, from the viewpoint of suppressing bleed-out and more easily improving long-term weather resistance. The lower limit of the content of the hydroxyphenyl triazine compound represented by the general formula (II) is not particularly limited as long as it can exhibit long-term weather resistance, but from the viewpoint of easily exhibiting extremely good long-term weather resistance, it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0021] In addition, the content of the hydroxyphenyl triazine compound represented by the general formula (III) in the surface protective layer relative to the total 100% by mass of the content of the hydroxyphenyl triazine compound represented by the general formula (I) and the content of the hydroxyphenyl triazine compound represented by the general formula (III) is not particularly limited as long as it can suppress bleed-out and exhibit long-term weather resistance, but from the viewpoint of more easily improving long-term weather resistance, it is preferably 95% by mass or less, and more preferably 90% by mass or less. In addition, the lower limit of the content of the hydroxyphenyl triazine compound represented by the general formula (III) is not particularly limited as long as it can suppress bleed-out and exhibit long-term weather resistance, but from the viewpoint of easily exhibiting long-term weather resistance, it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0022] When the hydroxyphenyl triazine compound represented by the general formula (I) and the hydroxyphenyl triazine compound represented by the general formula (II) or (III) are contained in at least any one of the substrate layer, the transparent resin layer, and the primer layer, the total content of these hydroxyphenyl triazine compounds (hereinafter, may be referred to as the "total content") varies depending on the thickness of the layer to which the hydroxyphenyl triazine compound is added and the number of layers to which the hydroxyphenyl triazine compound is added, and therefore cannot be generally determined. For example, the contents of the following (1) to (3) can be exemplified.

[0023] (1) When the primer layer contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III), and a resin component, the total content is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the resin component of the primer layer. (2) When the transparent resin layer contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III) and a resin component, the total content is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the resin component of the transparent resin layer. (3) When the base layer contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III), and a resin component, the total content is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass, relative to 100 parts by mass of the resin component of the base layer.

[0024] The decorative sheet of the present invention may contain an ultraviolet absorber other than the hydroxyphenyltriazine compounds represented by the general formulas (I), (II) and (III) as long as the effects of the present invention are not impaired. The total content ratio of the hydroxyphenyltriazine compounds represented by the general formulas (I) and (II) and the total content ratio of the hydroxyphenyltriazine compounds represented by the general formulas (I) and (III) relative to all the ultraviolet absorbers contained in the entire decorative sheet of the present invention is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, and even more preferably 90 mass% or more.

[0025] In addition, in the surface protective layer, the content of the ultraviolet absorber per 100 parts by mass of the resin component is 10 parts by mass or less. If the content exceeds 10 parts by mass, bleeding out is likely to occur, making it difficult to achieve long-term weather resistance. In addition, the bleeding matter may remain on the surface, causing a change in appearance. Here, the content of the ultraviolet absorber means the total amount of the ultraviolet absorber (when multiple types of ultraviolet absorbers are included, the total amount of all ultraviolet absorbers). In the surface protective layer, the content of the ultraviolet absorber per 100 parts by mass of the resin component is preferably 9 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less, from the viewpoint of suppressing bleed-out and further improving long-term weather resistance. In addition, in the surface protective layer, the lower limit of the content of the ultraviolet absorber per 100 parts by mass of the resin component is not particularly limited as long as long-term weather resistance can be exhibited, but from the viewpoint of easily exhibiting extremely good long-term weather resistance, it is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more.

[0026] <Base material layer> Examples of the substrate layer include films, sheets and plates made of various types of paper, plastic, metal, woven fabric, nonwoven fabric, wood and ceramic materials. Usually, a planar substrate layer having a predetermined thickness is called a film, a sheet, and a plate in the order of thickness, but since there is no particular need to distinguish between different thicknesses in the present invention, these names are treated as being interchangeable with each other as appropriate and without any essential difference in this specification. Furthermore, the difference in the names (difference in thickness) does not cause any difference in the interpretation of the claims of the present invention. In this specification, the term "plastic film" is intended to include plastic films, sheets, and plates. Among the base layers, a plastic film is preferred because it can improve the handling properties of the entire decorative sheet. Although plastics generally do not have sufficient weather resistance, the weather resistance of the plastic film as the base layer can be improved by including the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or (III) in the decorative sheet.

[0027] Specific examples of resins that make up plastics include olefin resins such as polyethylene and polypropylene, vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer, polyesters such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate, and the like. Among these, from the viewpoints of weather resistance, water resistance, printability, moldability, and cost, it is preferable to use one or more resins selected from olefin resins, vinyl chloride resins, polyesters, and acrylic resins.

[0028] Among these, olefin-based resins are preferred because they are more likely to exhibit the effects of the present invention. The hydroxyphenyl triazine compound represented by the general formula (I) has the property of being less prone to bleeding out. Therefore, by utilizing this property and using the hydroxyphenyl triazine compound represented by the general formula (I) and the hydroxyphenyl triazine compound represented by the general formula (II) or the general formula (III) in combination, which have different spectral absorption spectra, the surface protective layer can absorb ultraviolet rays in the wavelength range that contributes to the deterioration of the olefin-based resin, protecting the base layer, and maintaining long-term weather resistance. Among the olefin-based resins, polypropylene-based resins are preferred.

[0029] The polypropylene-based resin may be a homopolymer of propylene, i.e., polypropylene, or a copolymer of propylene and another comonomer copolymerizable with propylene (e.g., α-olefins such as ethylene, 1-butene, 1-hexene, and 1-octene; vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more.

[0030] The substrate layer may be colorless and transparent, or may be colored from the viewpoint of design. When the base layer is colored, a colorant such as a dye or a pigment may be added to the base layer. Among these colorants, a pigment is preferred because it is easy to suppress fading. Examples of pigments include white pigments such as zinc oxide, white lead, lithopone, titanium dioxide (titanium white), precipitated barium sulfate, and baryte; black pigments such as carbon black, aomethine azo black pigments, and perylene black pigments; red pigments such as red lead, iron oxide red, quinacridone red, and polyazo red; yellow pigments such as yellow lead, zinc yellow (zinc yellow type 1, zinc yellow type 2), isoindolinone yellow, and nickel-azo complexes; and blue pigments such as ultramarine blue and Prussian blue (potassium ferrocyanide).

[0031] The thickness of the base layer is not particularly limited, but when the base layer is a plastic film, it is preferably 20 to 3200 μm, more preferably 40 to 160 μm, and even more preferably 40 to 100 μm. When the base layer is paper, the basis weight is usually 20 to 150 g / m 2 is preferable, and 30 to 100 g / m 2 is more preferred.

[0032] The shape of the base material layer is not limited to a flat plate shape, but may be a special shape such as a three-dimensional shape. In order to enhance adhesion to other layers of the decorative sheet or to the adherend, one or both sides of the base layer may be subjected to a surface treatment such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment, or a primer layer may be formed.

[0033] <Surface protective layer, resin composition for surface protective layer> The surface protective layer includes a resin component and an ultraviolet absorber. The content of the ultraviolet absorber in the surface protective layer is 10 parts by mass or less per 100 parts by mass of the resin component. The surface protective layer includes cyclohexyl (meth)acrylate as the resin component. The surface protective layer satisfies the above-mentioned [1] or [2]. The embodiment of the ultraviolet absorber in the surface protective layer is as described above.

[0034] The resin composition for surface protection layer forming the surface protection layer contains a resin component and an ultraviolet absorber. The resin composition for surface protection layer contains 10 parts by mass or less of the ultraviolet absorber per 100 parts by mass of the resin component. The resin composition for surface protection layer contains cyclohexyl (meth)acrylate as the resin component. The resin composition for surface protection layer satisfies the following [1] or [2]. [1] The ultraviolet absorbent contains a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II), The content of the hydroxyphenyltriazine compound represented by the general formula (II) is 50 mass% or less relative to 100 mass% in total of the content of the hydroxyphenyltriazine compound represented by the general formula (I) and the content of the hydroxyphenyltriazine compound represented by the general formula (II). [2] The ultraviolet absorbing agent contains a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (III).

[0035] The preferred embodiment of the content of the ultraviolet absorber in the resin composition for surface protection layer is the same as the preferred embodiment of the content of the ultraviolet absorber relative to 100 parts by mass of the resin component of the surface protection layer described above. In addition, the preferred embodiment of the ratio of the content of the hydroxyphenyl triazine compound shown in the general formula (I) of [1] and [2] to the content of the hydroxyphenyl triazine compound shown in the general formula (II) or the general formula (III) in the resin composition for surface protection layer is also the same as the preferred embodiment of the ratio of the content of the hydroxyphenyl triazine compound shown in the general formula (I) to the content of the hydroxyphenyl triazine compound shown in the general formula (II) or the general formula (III) in the surface protection layer described above. Furthermore, other additives that can be contained in the resin composition for surface protection layer are the same as other additives that can be contained in the surface protection layer described later. By using the resin composition for a surface protective layer, even if the decorative material is used in a severe environment, bleeding out of the ultraviolet absorber can be suppressed and long-term weather resistance can be maintained very well.

[0036] In the present invention, the surface protective layer and the resin composition for the surface protective layer must contain cyclohexyl (meth)acrylate as a resin component. In this specification, cyclohexyl (meth)acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. Cyclohexyl (meth)acrylate is preferably a monomer component. By including cyclohexyl (meth)acrylate as a resin component, the affinity of the surface protective layer for water decreases, making it easier to inhibit deterioration of the decorative sheet due to hydrolysis and the like.

[0037] As the content of cyclohexyl (meth)acrylate in the resin component increases, the surface protective layer generally tends to become harder and more brittle. When the surface protective layer becomes harder and more brittle, the processing suitability of the decorative sheet is likely to decrease. Examples of processing include wrapping of the adherend, vacuum molding, V-cut processing, and other processing that causes deformation such as bending, stretching, and distortion. When the processing suitability decreases, microcracks and delamination may occur during the above processing. When microcracks or delaminations are present in the decorative sheet, the microcracks and delaminations grow gradually over time, making the surface protective layer more susceptible to partial peeling. In the areas where the surface protective layer has peeled off, the surface protective layer loses its function of protecting the base layer, etc., accelerating the deterioration of the decorative sheet. The above problem occurs more prominently when exposed to outdoors. For this reason, the content of cyclohexyl (meth)acrylate in the resin component is preferably set within a range in which the above-mentioned problems do not pose a practical hindrance while still enjoying the advantages of containing cyclohexyl (meth)acrylate.

[0038] The amount of cyclohexyl (meth)acrylate in the resin component is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, of the total amount of the resin component. By making it 5% by weight or more, it is possible to easily obtain a deterioration suppression effect due to hydrolysis, etc., and by making it 50% by weight or less, it is possible to impart a deterioration suppression effect to the decorative sheet while suppressing a decrease in hardness of the surface protective layer.

[0039] When it is said that "the resin composition for surface protective layer contains cyclohexyl (meth)acrylate as a resin component," it means that the resin composition has any of the following forms (1) to (3). In any of the forms, after the surface protective layer is formed, cyclohexyl (meth)acrylate exists in a form incorporated in some way into the solid resin component that constitutes the surface protective layer. However, it is permissible that a monomer of cyclohexyl (meth)acrylate or a prepolymer containing the same remains in the surface protective layer, as long as it does not impede the problem to be solved by the present invention. (1) In the resin composition for surface protection layer, cyclohexyl (meth)acrylate is contained in the form of a monomer or in the form constituting a part of a prepolymer. In this case, the monomer, the prepolymer, or a mixture of both constitutes all or part of the curable resin composition, and is cured by a crosslinking reaction or various polymerization reactions to form a surface protection layer as a polymer solid. (2) In the resin composition for the surface protective layer, cyclohexyl (meth)acrylate is polymerized or crosslinked to form a polymer. (3) The resin composition for a surface protective layer contains both of the cyclohexyl (meth)acrylates (1) and (2) above.

[0040] From the viewpoint of improving the scratch resistance of the decorative sheet, the resin composition for the surface protective layer preferably contains a curable resin composition as a resin component. Similarly, from the viewpoint of improving the scratch resistance of the decorative sheet, the surface protective layer preferably contains a cured product of the curable resin composition as a resin component.

[0041] Examples of the curable resin composition include a thermosetting resin composition containing a thermosetting resin, an ionizing radiation curable resin composition containing an ionizing radiation curable resin, and a mixture thereof. A thermosetting resin composition is preferred in that it increases the crosslink density of the surface protective layer while easily improving processability, such as bending. The ionizing radiation curable resin composition is preferred from the viewpoint of increasing the crosslink density of the surface protective layer and improving surface properties such as scratch resistance, etc. Furthermore, from the viewpoint of being able to be applied without a solvent and being easy to handle, among the ionizing radiation curable resin compositions, an electron beam curable resin composition is more preferred.

[0042] The proportion of the curable resin composition relative to all resin components contained in the resin composition for surface protection layer is preferably at least 50 mass%, more preferably at least 70 mass%, and is preferably at most 95 mass%, more preferably at most 90 mass%. Furthermore, the proportion of the cured product of the curable resin composition relative to the total resin components contained in the surface protection layer is preferably at least 50 mass%, more preferably at least 70 mass%, and is preferably at most 95 mass%, more preferably at most 90 mass%.

[0043] The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. These thermosetting resins preferably have two or more functional groups (hydroxyl group, amino group, carboxyl group, epoxy group) in the molecule. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary. Examples of the curing agent include isocyanate-based compounds. The isocyanate-based compound is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule.

[0044] Examples of polyisocyanate compounds include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hydrogenated compounds thereof, isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI).

[0045] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and cures by irradiation with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. In this specification, the (meth)acryloyl group refers to an acryloyl group or a methcroyl group. In addition, in this specification, the (meth)acrylate refers to an acrylate or a methacrylate. In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Specifically, the ionizing radiation curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0046] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable. Here, "(meth)acrylate" means "acrylate or methacrylate". Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group. From the viewpoint of improving processing characteristics, scratch resistance, and weather resistance, the number of functional groups of the polyfunctional (meth)acrylate monomer is preferably from 2 to 8, more preferably from 2 to 6, even more preferably from 2 to 4, and even more preferably from 2 to 3. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0047] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers. Further examples of the polymerizable oligomer include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecule, such as novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0048] These polymerizable oligomers may be used alone or in combination. From the viewpoint of improving processing characteristics, scratch resistance, and weather resistance, one or more selected from urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers are preferred, one or more selected from urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

[0049] From the viewpoint of improving processing characteristics, scratch resistance, and weather resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, even more preferably 4 or less, and even more preferably 3 or less. From the viewpoint of improving processing characteristics, scratch resistance and weather resistance, the weight average molecular weight of these polymerizable oligomers is preferably from 2,500 to 7,500, more preferably from 3,000 to 7,000, and even more preferably from 3,500 to 6,000. In this specification, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0050] In the ionizing radiation curable resin composition, a monofunctional (meth)acrylate can be used in combination for the purpose of reducing the viscosity of the ionizing radiation curable resin composition, etc. These monofunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0051] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing speed, and examples of the accelerator include one or more types selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0052] As described above, the surface protective layer contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III). In addition, the surface protective layer preferably contains other additives such as an antioxidant and a light stabilizer.

[0053] From the viewpoint of a balance between processing characteristics, scratch resistance, and weather resistance, the thickness of the surface protective layer is preferably from 1.5 μm to 20 μm, more preferably from 2 μm to 15 μm, and even more preferably from 3 μm to 10 μm.

[0054] <Primer layer> The decorative sheet preferably has a primer layer in contact with the surface of the surface protective layer on the substrate layer side. The primer layer improves the adhesion between the substrate layer and the surface protective layer (when a transparent resin layer is provided, the adhesion between the transparent resin layer and the surface protective layer), and can easily ensure long-term interlayer adhesion when exposed to the outdoors (so-called weather-resistant adhesion) and improve scratch resistance.

[0055] The primer layer is mainly composed of a resin component, and may contain additives such as an ultraviolet absorber, a light stabilizer, etc., as necessary. The ultraviolet absorber of the primer layer is preferably a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II) or (III).

[0056] Examples of the resin component of the primer layer include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), and cellulose acetate resin. These can be used alone or in combination. The resin component may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins and crosslinking and curing them. Among these, a polyol-based resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate-based curing agent, and an acrylic polyol resin is more preferably crosslinked and cured with an isocyanate-based curing agent.

[0057] The thickness of the primer layer is preferably from 1 μm to 10 μm, and more preferably from 2 μm to 8 μm.

[0058] The decorative sheet may have a back primer layer on the side of the base layer opposite the surface protective layer for the purpose of improving adhesion to an adherend.

[0059] <Transparent resin layer> The decorative sheet may have a transparent resin layer between the substrate layer and the surface protective layer from the viewpoint of increasing strength, etc. When the decorative sheet has a primer layer, the transparent resin layer is preferably located between the substrate layer and the primer layer. When the decorative sheet has a decorative layer, the transparent resin layer is preferably located between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer.

[0060] Resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, etc., among which polyolefin resins are preferred from the viewpoint of processability. The transparent resin layer may be a mixture of these exemplified resins, or may be a laminate of layers made of one or more of these exemplified resins. From the viewpoint of processability, the content of polyolefin resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, of the total resin components of the transparent resin layer.

[0061] Examples of the polyolefin resin of the transparent resin layer include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, etc. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, propylene-butene copolymer are preferred, and polypropylene is more preferred.

[0062] The transparent resin layer may contain additives such as an ultraviolet absorber, a light stabilizer, a colorant, etc. When the transparent resin layer contains an ultraviolet absorber, the ultraviolet absorber is preferably a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II) or (III).

[0063] From the viewpoint of a balance between scratch resistance, processability and weather resistance, the thickness of the transparent resin layer is preferably from 20 to 150 μm, more preferably from 40 to 120 μm, and even more preferably from 50 to 100 μm.

[0064] <Decorative layer> From the viewpoint of improving the design, the decorative sheet preferably has a decorative layer at any position of the decorative sheet. From the viewpoint of improving the weather resistance of the decorative layer, the position where the decorative layer is formed is preferably on the side close to the base layer. For example, when the decorative sheet has a primer layer, the decorative layer is preferably located between the base layer and the primer layer. Also, when the decorative sheet has a transparent resin layer, the decorative layer is preferably located between the base layer and the transparent resin layer.

[0065] The decorative layer may be, for example, a colored layer (so-called solid colored layer) that covers the entire surface, or a pattern layer formed by printing various patterns using ink and a printing machine. The pattern (design) of the pattern layer may be a wood grain pattern such as annual rings or vessel grooves on the surface of a wooden board, a stone grain pattern on the surface of a stone board such as marble or granite, a fabric grain pattern on a cloth surface, a leather grain pattern on a leather surface, a geometric pattern, letters, figures, or a combination of these.

[0066] The ink used for the decorative layer is a suitable mixture of a resin component, a pigment, a colorant such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, an ultraviolet absorber, a light stabilizer, etc. The resin component of the decorative layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol, acrylic resin, polyester, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic copolymer, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins accompanied by a curing agent such as an isocyanate compound.

[0067] As the colorant, a pigment having excellent hiding power and weather resistance is preferable. The same pigments as those exemplified for the base layer can be used. The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the resin constituting the decorative layer.

[0068] The decorative layer may contain additives such as an ultraviolet absorber, a light stabilizer, a colorant, etc. When the decorative layer contains an ultraviolet absorber, the ultraviolet absorber is preferably a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II) or (III). The thickness of the decorative layer may be appropriately selected depending on the desired pattern, but from the viewpoint of concealing the base color of the adherend and improving the design, the thickness is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0069] <Adhesive layer A> When the decorative sheet has a transparent resin layer, it is preferable to form an adhesive layer A between the substrate layer and the transparent resin layer in order to improve the adhesion between the two layers. When a decorative layer is further provided between the base layer and the transparent resin layer, the positional relationship between the adhesive layer A and the decorative layer is not particularly limited. Specifically, the decorative layer, adhesive layer A, and transparent resin layer may be provided in this order from the side closer to the base layer, or the adhesive layer A, decorative layer, and transparent resin layer may be provided in this order from the side closer to the base layer.

[0070] The adhesive layer A can be made of a general-purpose adhesive such as a urethane adhesive, an acrylic adhesive, an epoxy adhesive, a rubber adhesive, etc. Among these adhesives, a urethane adhesive is preferred in terms of adhesive strength. Examples of urethane-based adhesives include adhesives that utilize a two-liquid curing urethane resin that contains various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.

[0071] The thickness of the adhesive layer A is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0072] <Method of manufacturing decorative sheets> The decorative layer, adhesive layer A, primer layer and surface protective layer described above can be formed by applying a coating liquid containing a composition for forming each layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating or comma coating, and drying and curing as necessary. The transparent resin layer can be formed, for example, by hot melt extrusion.

[0073] The decorative sheet may be given (also called shaping) a desired uneven shape (also called an uneven pattern) by embossing or the like. When embossing is performed, for example, the decorative sheet is heated to preferably from 80° C. to 260° C., more preferably from 85° C. to 160° C., and even more preferably from 100° C. to 140° C., and an embossing plate is pressed against the decorative sheet to perform the embossing. The area to be pressed with the embossing plate is preferably the surface protective layer side of the decorative sheet.

[0074] [Cosmetic materials] The decorative material of the present invention comprises an adherend and the decorative sheet of the present invention described above, and specifically, is laminated so that the surface of the adherend that requires decoration faces the substrate layer side of the decorative sheet.

[0075] <Adherent material> Examples of the adherend include plate materials such as flat plates and curved plates made of various materials described later; three-dimensional objects such as cylinders and polygonal prisms made of various materials described later; and sheets and films made of various materials described later. Examples of various materials include wood members such as wood veneers, wood plywood, laminated lumber, particle boards, and wood fiberboards such as MDF (medium density fiberboard) made of various types of wood such as cedar, cypress, pine, and lauan; metal members such as iron, aluminum, copper, and alloys containing one or more of these metals; ceramic members such as glass, ceramics, gypsum, cement, ALC (aerated lightweight concrete), and non-ceramic ceramic materials such as calcium silicate; and resin members such as acrylic resin, polyester, polystyrene, polypropylene, and other polyolefin resins, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, polyvinyl chloride resin, cellulose resin, and rubber. These materials can be used alone or in combination.

[0076] The adherend may be appropriately selected from the above depending on the application. For example, when the application is for interior or exterior building components such as walls, ceilings, and floors, or fittings or fixtures such as window frames, doors, handrails, baseboards, moldings, etc., the adherend is preferably made of at least one member selected from wood members, metal members, and resin members. When the application is for exterior components such as entrance doors, or fittings such as window frames and doors, the adherend is preferably made of at least one member selected from metal members and resin members.

[0077] The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm to 100 mm, more preferably 0.3 mm to 5 mm, and even more preferably 0.5 mm to 3 mm.

[0078] <Adhesive layer B> In order to obtain excellent adhesion, the adherend and the decorative sheet are preferably attached via the adhesive layer B.

[0079] As the adhesive constituting the adhesive layer B, a general-purpose heat-sensitive adhesive, pressure-sensitive adhesive, etc. can be used. The adhesive constituting the adhesive layer B may include one or more types selected from the group consisting of acrylic resin, urethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, polyester, polyamide, etc. Furthermore, the adhesive of the adhesive layer B may include a two-component curing type polyurethane adhesive or polyester adhesive that uses an isocyanate compound or the like as a curing agent.

[0080] The thickness of the adhesive layer B is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 10 μm to 30 μm.

[0081] <Manufacturing method of decorative materials> The decorative material can be manufactured through a process of laminating a decorative sheet and an adherend. This step is a step of laminating the adherend and the decorative sheet of the present invention, with the surface of the adherend that needs to be decorated facing the surface of the decorative sheet on the base layer side. Examples of a method for laminating the adherend and the decorative sheet include a lamination method in which the decorative sheet is pressed against the plate-shaped adherend via the adhesive layer B using a pressure roller.

[0082] When a hot melt adhesive (heat-sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160° C. to 200° C., and for reactive hot melt adhesives, the heating temperature is preferably 100° C. to 130° C. In addition, vacuum forming is generally performed while heating, and the heating temperature is preferably 80° C. to 130° C., and more preferably 90° C. to 120° C.

[0083] The decorative material obtained as described above can be cut as desired, and the surface or end grain can be decorated as desired with grooves, chamfering, etc., using a cutting machine such as a router or cutter. It can be used for various purposes, such as interior components for buildings such as walls, ceilings, and floors, exterior components such as exterior walls, eaves ceilings, roofs, fences, and fences, fittings and fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other fittings and fixtures, as well as surface decorative panels for cabinets in kitchens, furniture, home appliances, and office automation equipment, and interior and exterior components for vehicles. EXAMPLES

[0084] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0085] [Evaluation and measurement methods] <Evaluation of long-term weather resistance> The decorative sheets obtained in each of the Examples and Comparative Examples were subjected to a weathering test in which they were left for 1,200 hours (a cycle of 20 hours of UV irradiation under the irradiation conditions below, followed by 4 hours of condensation under the condensation conditions below was repeated 50 times). The appearance of the decorative material after the weathering test was visually observed and evaluated according to the following criteria. The test equipment and test conditions are as follows: 1: No change in appearance was observed. 2: Very slight change in color or gloss was observed. 3: A slight change in color or gloss was observed. 4: Changes in color tone or gloss were observed. 5: At least one of a significant change in color tone, a significant change in gloss, and cracks was observed. [Test Equipment] Product name "Daipla Metal Weather" manufactured by Daipla Wintes Co., Ltd. [Irradiation conditions] Illuminance: 65mW / m 2 , Black panel temperature: 63℃, chamber humidity: 50%RH, time: 20 hours [Condensation conditions] Illuminance: 0mW / m 2 , Humidity inside the tank: 98%RH, Time: 4 hours

[0086] <Evaluation of bleed-out> The decorative sheets obtained in each of the Examples and Comparative Examples were immersed in a constant temperature bath of 60° C. warm water for one week, then removed and thoroughly dried, after which the appearance was observed and evaluated according to the following criteria. ○: No change in appearance was observed. Δ: Slight changes in appearance such as swelling, bubbles, gloss change, and precipitation of sheet components were observed. ×: Significant changes in appearance such as swelling, bubbles, gloss change, and precipitation of sheet components were observed.

[0087] [Examples 1 to 17, Comparative Examples 1 to 3] A polypropylene resin sheet (thickness: 60 μm) that had been subjected to corona discharge treatment on both sides was prepared as a substrate layer. A printing ink containing 100 parts by mass of a two-component curing acrylic-urethane resin as the resin component and 30 parts by mass of a colorant was applied to one side of the substrate layer by gravure printing to provide a wood grain pattern decorative layer (thickness: 3 μm). Next, a two-component curing urethane-nitrocellulose mixed resin composition was applied to the other side of the substrate layer to form a back primer layer (thickness: 3 μm). A transparent polyurethane resin-based adhesive was applied onto the decorative layer to form an adhesive layer (thickness after drying: 3 μm), and a transparent polypropylene resin was hot-melt extruded using a T-die extruder to form a transparent resin layer (thickness: 80 μm). Next, the surface of the transparent resin layer was subjected to a corona discharge treatment, and then the base solution described below and the hardener solution described below were mixed so that the mass ratio was 10:1 (the ratio of the number of hydroxyl groups in the base solution to the number of isocyanate groups in the hardener solution was approximately 1:2), and ethyl acetate was further added as a solvent component to adjust the solid content to 20 mass%, and the resin composition for surface protection layer was applied and dried to a thickness of 9 μm after drying to form a surface protection layer. Next, embossing was carried out from above the surface protective layer, thereby obtaining the decorative sheets of Examples 1-17 and Comparative Examples 1-3. The decorative sheet thus obtained was subjected to the above-mentioned evaluations, and the evaluation results are shown in Tables 1 to 3.

[0088] <Base solution> A solution containing 80 parts by mass of methyl methacrylate monomer containing a hydroxyl group, 20 parts by weight of cyclohexyl methacrylate, and an ultraviolet absorber (an ultraviolet absorber containing the ultraviolet absorbers shown in Tables 1 to 3 in the amounts shown in Tables 1 to 3), and further adjusted to a solid content of 33 mass% by adding ethyl acetate solvent. <Hardening agent solution> A solution containing hexamethylene diisocyanate adjusted to a solids content of 75% by weight by adding ethyl acetate solvent.

[0089] As ultraviolet absorbents 1 to 3 in Tables 1 to 3, the following hydroxyphenyltriazine compounds were used. Ultraviolet absorber 1 (formula (I) above): [ADEKA STAB LA-46, manufactured by ADEKA Corporation] Ultraviolet absorber 2 (formula (II) above): [Tinuvin 479, manufactured by Chiba Specialty Chemicals Co., Ltd.] Ultraviolet absorber 3 (formula (III) above): [Tinuvin 1600, manufactured by Chiba Specialty Chemicals Co., Ltd.]

[0090] In Tables 1 to 3, "content of Tinuvin 479" means the content (% by mass) of ultraviolet absorber 2 relative to the total 100% by mass of the content of ultraviolet absorber 1 and the content of ultraviolet absorber 2. Similarly, "content of Tinuvin 1600" means the content (% by mass) of ultraviolet absorber 3 relative to the total 100% by mass of the content of ultraviolet absorber 1 and the content of ultraviolet absorber 3. Similarly, "content of Tinuvin 479 or 1600" means the content (% by mass) of ultraviolet absorber 2 or ultraviolet absorber 3 relative to the total 100% by mass of the content of ultraviolet absorber 1 and the content of ultraviolet absorber 2 or ultraviolet absorber 3.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] From Tables 1 and 2, it can be confirmed that the decorative sheets of Examples 1 to 17 are excellent in suppressing bleed-out and are excellent in the evaluation of long-term weather resistance, and therefore can maintain long-term weather resistance very well even when used in a severe environment. On the other hand, from Table 3, it can be seen that the decorative sheet of Comparative Example 1 has a high content of ultraviolet absorber in the surface protective layer, and the decorative sheets of Comparative Examples 2 and 3 have a high content of the hydroxyphenyltriazine compound represented by the general formula (II), so that the results are poor in both suppressing bleed-out and maintaining long-term weather resistance. [Industrial Applicability]

[0095] The decorative sheet of the present invention is extremely good at suppressing bleed-out and maintaining long-term weather resistance, and is therefore suitable for use as a decorative sheet for components that are used in environments exposed to direct sunlight, such as exterior components such as entrance doors, window frames, and door fittings. [Explanation of symbols]

[0096] 100: Decorative sheet 10: Surface protective layer 20: Primer layer 30: Transparent resin layer 40:Decorative layer 50: Base material layer

Claims

1. A decorative sheet having at least a substrate layer and a surface protective layer, the surface protective layer contains a resin component and an ultraviolet absorber, the content of the ultraviolet absorber is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component, and the resin component contains cyclohexyl (meth)acrylate, The decorative sheet, wherein the surface protective layer satisfies the following [1] or [2]. [1] The ultraviolet absorbent contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (II), and the total content of the hydroxyphenyltriazine compounds represented by the general formulas (I) and (II) relative to the entire ultraviolet absorbent is 70 mass% or more, The content of the hydroxyphenyltriazine compound represented by the following general formula (II) is 50 mass% or less relative to 100 mass% in total of the content of the hydroxyphenyltriazine compound represented by the following general formula (I) and the content of the hydroxyphenyltriazine compound represented by the following general formula (II). [2] The ultraviolet absorbing agent contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (III). 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】

2. A decorative sheet as described in claim 1, wherein the surface protective layer satisfies [2].

3. 3. The decorative sheet according to claim 1, further comprising one or more layers selected from a decorative layer, a transparent resin layer, and a primer layer between the substrate layer and the surface protective layer.

4. The decorative sheet according to any one of claims 1 to 3, wherein the substrate layer comprises an olefin-based resin.

5. A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 4.

6. A resin composition for a surface protective layer comprising a resin component and an ultraviolet absorber, a content of the ultraviolet absorber relative to 100 parts by mass of the resin component is 0.01 parts by mass or more and 10 parts by mass or less, and the resin component contains cyclohexyl (meth)acrylate, A resin composition for a surface protective layer that satisfies the following [1] or [2]: [1] The ultraviolet absorbent contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (II), and the total content of the hydroxyphenyltriazine compounds represented by the general formulas (I) and (II) relative to the entire ultraviolet absorbent is 70 mass% or more, The content of the hydroxyphenyltriazine compound represented by the following general formula (II) is 50 mass% or less relative to 100 mass% in total of the content of the hydroxyphenyltriazine compound represented by the following general formula (I) and the content of the hydroxyphenyltriazine compound represented by the following general formula (II). [2] The ultraviolet absorbing agent contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (III). 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】

7. The resin composition for surface protection layer described in claim 6, wherein the resin composition for surface protection layer satisfies [2].

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