Laminate and decorative sheet

Abstract

To provide a decorative sheet having stable weather resistance.SOLUTION: A laminate contains, in a top coat layer 2 at the outermost surface side of a decorative sheet 1, a photo-stabilizer having a pKa of 4.0 to 7.0, and an ultraviolet absorber having a pKa of -4.5 to -5.5 when being irradiated with light.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin laminate such as a resin film, and a decorative sheet using the same for use as an interior building material, an exterior building material such as an entrance door, the surface of fittings, the surface material of home appliances, etc. [Background technology]

[0002] In recent years, many decorative sheets made from olefin resins have been proposed as alternatives to vinyl chloride decorative sheets. These decorative sheets are used to protect architectural interior materials for homes and public facilities, architectural exterior components such as entrance doors, the surfaces of building fixtures, and the surface materials of home appliances. As such, they are exposed to direct sunlight, wind, and rain on a daily basis, and therefore require extremely high weather resistance (see Patent Document 1). The decorative sheet described in Patent Document 1 aims to improve weather resistance by incorporating light stabilizers, UV absorbers, etc. into the top coat layer. However, it is known that over long-term use, the light stabilizers and UV absorbers are lost due to bleeding out of the top coat layer, and the chemical structure of each material is destroyed by oxygen and light, resulting in a loss of functionality. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 4032829 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when attempting to incorporate an ultraviolet absorber or light stabilizer in an amount sufficient to provide sufficient weather resistance into a target resin layer such as a top coat layer, aggregation of the ultraviolet absorber or light stabilizer blended into the resin composition constituting the resin layer may occur. Furthermore, when the chemical structure of the ultraviolet absorber or light stabilizer in the resin composition is broken down and reduced in molecular weight, the decomposed components of the ultraviolet absorber or light stabilizer tend to rise from the surface of the resin layer, which is called bleed-out. This causes problems such as reduced adhesion to other resin layers. Furthermore, the rise to the surface layer can cause problems such as stickiness.

[0005] The present invention has been made in view of the above points, and has as its object to provide a decorative sheet having stable weather resistance. [Means for solving the problem]

[0006] The inventors have conducted various studies to find conditions that prevent the decomposition of the ultraviolet absorber and light stabilizer over time and enable use over a long period of time without deterioration in quality, and have found suitable conditions for the top coat layer. In order to solve the problems, a laminate according to a first aspect of the present invention is a laminate comprising a plurality of resin layers, characterized in that the top coat layer located on the outermost surface side of the laminate contains a light stabilizer having a pKa of 4.0 to 7.0 and an ultraviolet absorber having a pKa of -4.5 to -5.5 when irradiated with light. A decorative sheet according to a first aspect of the present invention is characterized by comprising the above laminate. [Effects of the Invention]

[0007] According to one aspect of the present invention, by using a laminate having the above-described configuration, it is possible to provide a decorative sheet that has stable weather resistance over a long period of time. Here, the light stabilizer is a hindered copolymer having an amino ether group and a molecular weight of 600 or more. By using a triazine or benzotriazole based ultraviolet absorber or by using an ultraviolet absorber having a triazine skeleton or a benzotriazole skeleton and a molecular weight of 400 or more, a decorative sheet with improved weather resistance can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a cross-sectional view illustrating a laminate according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to the drawings. The configuration shown in Fig. 1 is a schematic diagram, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, and the like differ from the actual configuration. Furthermore, the embodiments shown below are merely examples of configurations that embody the technical concept of the present invention, and the technical concept of the present invention is not limited to the materials, shapes, structures, and the like of the components described below. Various modifications can be made to the technical concept of the present invention within the technical scope defined by the claims.

[0010] As shown in FIG. 1, the decorative sheet 1 of this embodiment is configured by arranging an ink layer 5, an adhesive layer 4, a transparent resin layer 3 serving as a surface protection layer, and a top coat layer 2 in this order on a raw fabric layer 6 that constitutes a base material layer. An embossed pattern 3a that constitutes a textured pattern is formed on the upper surface of the transparent resin layer 3. The textured pattern may be formed by a method other than embossing. The transparent resin layer 3 is configured from an olefin resin layer. In the example of FIG. 1, an adhesive resin layer 7 is provided between the transparent resin layer 3 and the adhesive layer 4 to improve adhesion, but the adhesive resin layer 7 need not be provided.

[0011] This decorative sheet 1 is produced, for example, by forming an adhesive layer 4 on a raw resin sheet having an ink layer 5 formed on one side of a raw resin layer 6 to form a first laminate, and by forming a top coat layer 2 containing an ultraviolet absorber and a light stabilizer on a resin sheet having a transparent resin layer 3 and an adhesive resin layer 7 co-extruded thereon to form a second laminate, and then bonding the first laminate and the second laminate together by dry lamination or extrusion lamination, for example. Each layer is described in detail below.

[0012] <Top coat layer> A top coat layer 2, which serves to protect the surface and adjust the gloss, is provided on the outermost layer of the decorative sheet 1. The top coat layer 2 contains an ultraviolet absorber and a light stabilizer. FIG. 1 illustrates an example in which the top coat layer 2 is formed along the surface of the transparent resin layer 3 over the entire surface of the transparent resin layer 3, but this is not limiting. The top coat layer 2 may be formed by applying a resin composition to the recesses of the embossed pattern 3a formed in the transparent resin layer 3 and then scraping the coating liquid with a squeegee or the like, thereby filling only the recesses with the resin composition through wiping. Alternatively, the surface of the top coat layer 2 may be flat, regardless of the recesses of the embossed pattern 3a. The top coat layer 2 only needs to be formed by being embedded in at least the recesses of the embossed pattern 3a. Even in the recesses where the layer thickness is reduced due to the formation of the embossed pattern 3a, the embedded top coat layer 2 can maintain high weather resistance. Forming the top coat layer 2 so that it covers the entire surface of the transparent resin layer 3 can provide a decorative sheet 1 with even better weather resistance.

[0013] (resin material) The resin material as the main component of the top coat layer 2 can be appropriately selected from polyurethane-based, acrylic silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, urea-based, and other resin materials. The type of the adhesive may be, but is not limited to, a one-component type, a two-component type, an ultraviolet curing method, or the like. Here, the term "main component" as used herein refers to a resin material that accounts for 70% by mass or more, and preferably 90% by mass or more, of the material that constitutes the target layer.

[0014] As the resin material used as the main component of the top coat layer 2, a urethane-based resin using isocyanate is preferred from the viewpoints of workability, cost, and the cohesive strength of the resin itself. The isocyanate can be appropriately selected from curing agents such as adducts, biurets, and isocyanurates, which are derivatives of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc., but in consideration of weather resistance, curing agents based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI), which have a linear molecular structure, are preferred.

[0015] In addition, when improving surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays or electron beams. Although known materials such as various monomers and commercially available oligomers can be used as the main material, it is preferable to use polyfunctional monomers such as pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4A), trimethylolpropane triacrylate (TMPTA), and dipentaerythritol hexaacrylate (DPHA), polyfunctional oligomers such as Shikou UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), or mixtures thereof.

[0016] These resins can be used in combination with one another. For example, by using a hybrid type of thermosetting resin and photocuring resin, it is possible to improve surface hardness, suppress shrinkage on curing, and improve adhesion. In this case, the top coat layer 2 may be composed of multiple layers, for example, two layers: a thermosetting layer whose main component is a thermosetting resin, and a photocurable layer whose main component is a photocurable resin such as an ultraviolet-curable resin. By using two curable layers in this way, the surface hardness of the decorative sheet 1 can be improved. In this case, it is preferable that the photocurable layer is on the surface layer side.

[0017] (Light stabilizers and UV absorbers) In this embodiment, the top coat layer 2 contains a light stabilizer having a pKa of 4.0 to 7.0 and an ultraviolet absorber having a pKa of −4.5 to −5.5 when irradiated with light. When the top coat layer 2 is composed of multiple layers, one or more of the multiple layers contain a light stabilizer with a pKa of 4.0 to 7.0 and an ultraviolet absorber with a pKa of -4.5 to -5.5 when irradiated with light. In this case, it is preferable that the other layers contain either a light stabilizer with a pKa of 4.0 to 7.0 or an ultraviolet absorber with a pKa of -4.5 to -5.5 when irradiated with light.

[0018] Furthermore, when the top coat layer 2 is constructed of two layers, a thermosetting layer and a photocurable layer, as described above, it is preferable to blend the above-mentioned ultraviolet absorber and light stabilizer on the thermosetting layer side. In this embodiment, the amounts of the ultraviolet absorber and light stabilizer in the layer in which they are blended are 1.0 to 15.0 parts by mass of the ultraviolet absorber and 0.1 to 5.0 parts by mass of the light stabilizer per 100 parts by mass of the resin material. The light stabilizer is preferably a hindered amine light stabilizer having an amino ether group and a molecular weight of at least 600. The molecular weight of the light stabilizer may be measured, for example, by number average molecular weight.

[0019] The method for measuring the number average molecular weight of the light stabilizer is not particularly limited, but may be determined by gel permeation chromatography. It is preferable to use GPC chromatograph. There are no particular limitations on the GPC measurement device, but the packing material of the GPC column is preferably polystyrene gel, and the eluent is preferably tetrahydrofuran (THF). Furthermore, polystyrene polymers can be used as GPC standards. However, when the light stabilizer is composed of a single substance, if its structure is known, the molecular weight of the light stabilizer may be calculated from the structural formula.

[0020] The ultraviolet absorber is preferably an ultraviolet absorber having a triazine skeleton or a benzotriazole skeleton and a molecular weight of at least 400. The molecular weight of the ultraviolet absorber may be calculated from its structural formula, or may be a number average molecular weight measured by a known method. For example, the ultraviolet absorber is a compound (1) having a hydroxyphenyltriazine skeleton or a compound (2) having a benzotriazole skeleton, as shown below. These are preferably compounds with a maximum absorption wavelength between 270 nm and 400 nm. The ultraviolet absorbers described above become excited by absorbing light, and depending on the skeleton, hydrogen atoms migrate within the molecule. They can return to the ground state by releasing heat. These can be represented by reaction formulas (3) and (4), respectively.

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] Examples of the compound having the hydroxyphenyltriazine skeleton include 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-[2-hydroxy-4-(3-dodecyloxy-2-hydroxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-[2-hydroxy-4-(3-tridecyloxy-2-hydroxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropyloxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-dibiphenyl-s-triazine, 2-[2-hydroxy-4-[1-(i-octyloxycarbonyl)ethyloxy]phenyl]-4,6-dibiphenyl- Examples thereof include s-triazine, 2,4-bis(2-hydroxy-4-octoxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-butoxy-2-hydroxyphenyl)-6-(2,4-dibutoxyphenyl)-s-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine (trade name CYASORB (registered trademark) UV-1164), and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (trade name LA-F70).

[0026] Examples of the compound having the benzotriazole skeleton include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-(2-(octyloxycarbonyl)ethyl)phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole, 2-(2'-hydroxy 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-(dimethylbenzyl)phenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2,2'-methylene-bis(2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-3'-(3,4,5,6-tetrahydrophthalimidylmethyl)-5'-methylbenzyl)phenyl)benzotriazole, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (trade name LA-36), 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol (trade name Tinuvin (registered trademark) 326), and the like.

[0027] Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, and 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol.

[0028] Examples of triazine-based ultraviolet absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Examples include bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0029] Benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. benzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), and the like. Benzoate-based ultraviolet absorbers include phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate, 2,4-di-tert-amylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0030] Examples of cyanoacrylate ultraviolet absorbers include ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate. The light stabilizer is the following hindered amine compound (5), which can capture radicals through the reaction of reaction formula (6).

[0031] [ka]

[0032] [ka]

[0033] Examples of hindered amine light stabilizers include bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis(1,2,2,6,6 -Pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl 4-hydroxybenzylmalonate;Condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid;2,2,6,6-Tetramethylpiperidin-4-yl stearate;2,2,6,6-Tetramethylpiperidin-4-yl dodecanoate;1,2,2,6,6- Pentamethylpiperidin-4-yl stearate; 1,2,2,6,6-pentamethylpiperidin-4-yl dodecanoate; Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; Tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate; Tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 4-Benzoyl-2,2,6,6-tetramethylpiperidine;4-Stearyloxy-2,2,6,6-tetramethylpiperidine;Bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl 2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;3-n-Octyl-7,7,9,9-tetramethyl-1,3,8-triaza Spiro[4.5]decane-2,4-dione;Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate;Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino 2,6-dichloro-1,3,5-triazine;2-Chloro-4,6-bis(4-n-butylamine) Condensation product of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane; Condensation product of 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]Decane-2,4-dione; 3-Dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-Dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-Dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; Mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; N,N'-Bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexyloxy- Condensation products of cyclohexylamino-2,6-dichloro-1,3,5-triazine; condensation products of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine, and 4-butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperandinyl-triazine; and reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrin.

[0034] In addition, N-alkoxy hindered amine light stabilizers include tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate; 1,2,3,4-butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4-piperidinyltridecyl ester; 1,2,3,4-butanetetracarboxylic acid 2,2,6,6-tetramethyl-4-piperidinyltridecyl ester; and 1,2,3,4-butane Examples include 1,2,2,6,6-pentamethyl-4-piperidinyl ester of a polymer of tetracarboxylic acid and 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol; 2,2,6,6-tetramethyl-4-piperidinyl ester of a polymer of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol; and bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate.

[0035] In addition, hydroxyl-substituted N-alkoxy HALS includes 1-(2-hydroxy-2- 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; 1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane; 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; and the reaction product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and dimethyl succinate. Among these hindered amine light stabilizers, representative commercially available examples include Tinuvin 123, Tinuvin 152, Tinuvin NOR 371 FF, Tinuvin XT850 FF, Tinuvin XT855 FF, TINUVIN 5100, TINUVIN 622SF, and Flamestat NOR 116 FF, all manufactured by BASF Japan Ltd., and Adekastab LA-81, all manufactured by ADEKA Corporation. These may be used alone or in combination of two or more.

[0036] When an ultraviolet absorber is incorporated into the top coat layer 2, it is preferably incorporated in an amount of 1.0 to 15.0 parts by mass relative to 100 parts by mass of the resin that is the main component of the top coat layer 2. More preferably, it is incorporated in an amount of 2.5 to 8.0 parts by mass. If the amount of ultraviolet absorber incorporated is less than 1.0 part by mass, the effect of stabilizing the resin against ultraviolet rays may be reduced. On the other hand, if it is more than 15.0 parts by mass, there is a high possibility that bleed-out may occur. When a light stabilizer is incorporated into the top coat layer 2, it is preferably incorporated in an amount of 0.1 to 5.0 parts by mass per 100 parts by mass of the resin that is the main component of the top coat layer 2. More preferably, it is incorporated in an amount of 0.3 to 3.0 parts by mass. If the amount of light stabilizer incorporated is less than 0.1 part by mass, the effect of stabilizing the resin against generated radicals may be reduced. On the other hand, if it is more than 5.0 parts by mass, there is a high possibility that bleed-out may occur.

[0037] (Other compounds) The top coat layer 2 preferably contains a gloss adjuster made of inorganic particles. Examples of the inorganic particles include silica, clay, calcium carbonate, barium sulfate, alumina white, aluminum hydroxide, talc, bentonite, titanium oxide, white carbon such as silicic anhydride, hydrated silicic acid, hydrated calcium silicate, and hydrated aluminum silicate, which are known as colloidal silica, and alumina sol. The particle size of the inorganic particles is preferably 1 μm or more and 20 μm or less, and more preferably 3 μm or more and 10 μm or less. If the particle size is smaller than 1 μm, the gloss adjustment effect may be low. On the other hand, if the particle size is larger than 20 μm, there is a high possibility that the filler will be chipped. The inorganic particles contribute to the design (glossiness) of the decorative sheet, and are blended in an amount appropriate for this purpose. The blending amount is generally 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the resin that is the main component of the top coat layer 2.

[0038] <Transparent resin layer> The transparent resin layer 3 constitutes the base material of the top coat layer 2, and when the ink layer 5 is provided, it serves as a protective layer that protects the ink layer 5. The transparency of the transparent resin layer 3 is sufficient as long as the ink layer 5 is visible. The laminate must at least include the transparent resin layer 3 and the top coat layer 2. When the ink layer 5 is not provided, the transparent resin layer 3 does not need to be transparent. The transparent resin layer 3 is preferably a resin layer whose main resin component is an olefin resin and which contains 0.3 parts by mass or more of a compound having a pKa of 7.0 or less per 100 parts by mass of the resin material. The amount of the compound having a pKa of 7.0 or less to be blended is preferably 15.0 parts by mass or less. The compound having a pKa of 7.0 or less is, for example, the same light stabilizer or ultraviolet absorber as that blended in the top coat layer 2 as described above.

[0039] In the transparent resin layer 3 of this embodiment, an embossed pattern is formed as shown in FIG. The embossed pattern 3a is formed to improve the design. The embossed pattern 3a can be formed by a method of forming the embossed pattern 3a by applying heat and pressure using an embossing plate having a textured pattern before forming the top coat layer 2, or by a method of forming the embossed pattern 3a simultaneously with cooling the sheet using a cooling roll having a textured pattern when forming a film using an extruder.

[0040] The resin material used as the main component of the transparent resin layer 3 is preferably made of an olefin-based resin, and in addition to polypropylene, polyethylene, polybutene, etc., α-olefins (for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, α-olefins (for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene) may be used. Examples of such polyolefins include homopolymers or copolymers of two or more types of α-olefins (such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, etc.) and copolymers of ethylene or α-olefins with other monomers, such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, etc. Furthermore, when it is intended to improve the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

[0041] If necessary, the resin composition constituting the transparent resin layer 3 may contain various functional additives such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster. These various functional additives can be appropriately selected from well-known additives. When non-polar polypropylene is used for the transparent resin layer 3, if the adhesion between the transparent resin layer 3 and the resin layer disposed underneath is low, it is preferable to provide an adhesive resin layer 7. The adhesive resin layer 7 is preferably an acid-modified resin such as polypropylene, polyethylene, or acrylic, and the thickness of the layer is preferably 2 μm to 20 μm from the viewpoint of adhesiveness and heat resistance. Furthermore, from the viewpoint of improving adhesive strength, the adhesive resin layer 7 is preferably formed by co-extrusion lamination with the transparent resin layer 3.

[0042] <Ink layer and adhesive layer> As shown in FIG. 1, an adhesive layer 4 is provided on the lower surface side of the transparent resin layer 3 to improve adhesion between the ink layer 5 on the lower surface side and the transparent resin layer 3. The material of the adhesive layer 4 is not particularly limited, but can be appropriately selected from acrylic, polyester, polyurethane, epoxy, etc. The coating method can be appropriately selected depending on the viscosity of the adhesive, but gravure coating is generally used, and the adhesive is applied by gravure coating to the side of the base fabric layer 6 on which the ink layer 5 is applied, and then laminated with the transparent resin layer 3 and the adhesive resin layer 7. The adhesive layer 4 can be omitted if sufficient adhesive strength can be obtained between the transparent resin layer 3 and the ink layer 5.

[0043] An ink layer 5 is provided on the lower surface side of the adhesive layer 4. The ink layer 5 preferably contains at least a light stabilizer. As the light stabilizer, it is preferable to use a hindered amine-based material. By including a light stabilizer in the ink layer 5, radicals generated by deterioration of the binder resin itself that forms the ink layer 5 or the resins of other layers reduce the chemical components of the pigment in the ink, thereby suppressing fading of the pigment, and maintaining a vividly colored pattern for a long period of time. It can be retained. The ink layer 5 of this embodiment comprises a picture pattern layer 5a and a solid ink layer 5b. At least the picture pattern layer 5a contains a light stabilizer for the above-mentioned purpose. Furthermore, by providing the solid ink layer 5b on the underside of the picture pattern layer 5a, hiding power can be achieved.

[0044] The ink for the design layer 5a can be used as a binder, selected from soluble nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, and other materials, either alone or modified. The binder can be water-based, solvent-based, or emulsion-based, and the curing method can be either a one-component type or a two-component type using a curing agent. Furthermore, the ink can be cured by exposure to active energy rays such as ultraviolet light or electron beams. A particularly common method is to use a urethane-based ink and cure it with isocyanate. In addition to these binders, the ink may contain pigments, colorants such as dyes, extenders, solvents, and various additives, all of which are commonly found in inks. Versatile pigments include condensed azo compounds, insoluble azo compounds, quinacridones, isoindolines, anthraquinones, imidazolone, cobalt, phthalocyanines, carbon, titanium oxide, iron oxide, and pearls such as mica.

[0045] The solid ink layer 5b can basically be made of the same material as the ink used in the picture pattern layer 5a, but if the ink is transparent, opaque pigments, iron oxide, titanium oxide, etc. can be used. Additionally, metals such as silver, copper, and aluminum can be blended to impart hiding power. Generally, flake aluminum is used. The solid ink layer 5b may not be necessary. These ink layers 5 can be formed directly on the base fabric layer 6 by gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, etc. When opacity is imparted by a metal, it is preferable to use a comma coater, knife coater, lip coater, metal vapor deposition, sputtering, or the like. In addition, taking into consideration the adhesiveness of the interface where the resin material or ink is laminated, the surface to be laminated can be activated by performing a surface treatment such as corona treatment, ozone treatment, plasma treatment, electron beam treatment, ultraviolet treatment, or dichromate treatment before applying the resin material or ink, thereby improving the adhesiveness between the layers.

[0046] <Original layer> A base fabric layer 6, which serves as a substrate layer, is provided on the lower surface side of the ink layer 5. The base fabric layer 6 can be arbitrarily selected from paper such as tissue paper, titanium paper, and resin-impregnated paper, synthetic resins such as polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic, or foams of these synthetic resins, rubbers such as ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane, organic or inorganic nonwoven fabrics, synthetic paper, and metal foils such as aluminum, iron, gold, and silver. Furthermore, when an olefin-based resin is used for the raw fabric layer 6, the surface is often in an inactive state, so it is preferable to provide a primer layer (not shown) between the raw fabric layer 6 and the substrate (not shown) to which the decorative sheet 1 is attached. In addition, in order to improve the adhesion between the raw fabric layer 6 made of an olefin-based resin and the substrate, it is preferable that the back surface of the raw fabric layer 6 has been subjected to corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, or the like.

[0047] The primer layer can be made of the same material as the ink layer 5, but the primer layer may be made of a different material. Considering that the sheet 1 will be wound up in web form, it is preferable to include an inorganic filler such as silica, alumina, magnesia, titanium oxide or barium sulfate in order to avoid blocking and to improve adhesion to the adhesive. In the decorative sheet 1 of this embodiment, taking into consideration printing workability, cost, etc., it is desirable that the base layer 6 be 20 μm to 150 μm thick, the adhesive layer 4 be 1 μm to 20 μm thick, the transparent resin layer 3 be 20 μm to 200 μm thick, and the top coat layer 2 be 3 μm to 20 μm thick, and it is preferable that the total thickness of the decorative sheet 1 be within the range of 45 μm to 400 μm.

[0048] <About effects and other details> Since UV absorbers and light stabilizers require intermolecular interactions, it is preferable for them to be in close proximity. Here, we will look at the interaction when a UV absorber with a triazine or benzotriazole skeleton is used with a light stabilizer with a hindered amine skeleton. Generally, the intermolecular interaction between a UV absorber and a light stabilizer occurs between the conjugated system of the UV absorber and the hindered amine skeleton of the light stabilizer. When a UV absorber absorbs light, there is a high probability that an intramolecular hydrogen bond will be formed on the nitrogen of the triazine or benzotriazole skeleton. In other words, the hydrogen on the hydroxyl group is in a state where it is easy to dissociate.

[0049] Furthermore, by using a light stabilizer with a pKa greater than 7.0, the UV absorber, which has absorbed light and is in an excited state, is more likely to undergo a side reaction, such as an acid-base reaction, with the light stabilizer. In other words, the UV absorber and light stabilizer are unable to undergo the reactions of the above-mentioned Reaction Formulas (3), (4), and (6), which would normally occur, and the side reactions increase. In other words, they are more likely to be decomposed by light, leading to a decrease in weather resistance. On the other hand, when a light stabilizer with a pKa of 7.0 or less is used, the UV absorber and light stabilizer are less likely to undergo an acid-base reaction with the hydrogen on the hydroxyl group of the UV absorber, which has absorbed light and is in an excited state, and therefore the UV absorber and light stabilizer are more likely to undergo the reactions of Reaction Formulas (3), (4), and (6). This improves weather resistance to light. In view of this, in this embodiment, a light stabilizer with a pKa of 4.0 to 7.0 and an ultraviolet absorber with a pKa of -4.5 to -5.5 when irradiated with light are contained in the resin composition constituting the top coat layer 2, thereby providing a laminate having a top coat layer 2 with high weather resistance, and a decorative sheet 1 with stable weather resistance can be provided using this laminate.

[0050] Furthermore, as in this embodiment, by using an olefin-based resin for the transparent resin layer 3, which is the base material for the top coat layer 2, and blending 0.3 parts by mass or more of a light stabilizer with a pKa of 7.0 or less, it is possible to prevent a decrease in the weather resistance of the laminate. This is because if the pKa of the light stabilizer is greater than 7.0, a side reaction is likely to occur due to an acid-base reaction near the interface between the top coat layer 2 and the transparent resin layer 3, and the proportion of the light stabilizer in the top coat layer 2 near the transparent resin layer 3 is likely to decrease. For this reason, it is preferable to use a light stabilizer with a pKa of 7.0 or less for the olefin resin. A pKa of 6.0 or less is more preferable. Furthermore, it is preferable that the pKa of the compound blended in the transparent resin layer 3 is 7.0 or less.

[0051] (Method for measuring the pKa of light stabilizers) A 1:1 solution of 0.1N perchloric acid / dioxane in acetonitrile:chloroform was added dropwise to an organic reference substance with a known pKa value in an aqueous system, and the half-neutralization potential (HNP) in a non-aqueous system was titrated. A calibration curve of HNP versus pKa was then created. Light stabilizers were then titrated in the same manner, and the corresponding pKa values ​​were determined from the calibration curve plot.

[0052] (Method for measuring the pKa of ultraviolet absorbers when absorbing light) Here, the ultraviolet absorber was dissolved in acetonitrile so that the absorbance at the maximum absorption wavelength was 1, and nitrogen was bubbled for 15 minutes. After that, 70% perchloric acid was added dropwise to this solution, and the pH of the solution was changed. At that time, the absorption spectrum of the solution was measured, and λmax From the absorbance at x, the UV absorber and the UV absorber benzotriazole at each pH The pKa of the UV absorber at the time of light absorption was calculated from the point at which these values ​​were equal. A Hitachi High-Tech U-4000 spectrophotometer was used to measure the absorption spectrum. [Example]

[0053] Specific examples of the laminate and decorative sheet according to the present invention will be described below. For 100 parts by mass of highly crystalline homopolypropylene resin, 0.5 parts by mass of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF), 0.5 parts by mass of a triazine ultraviolet absorber (CYASORB UV-1164; manufactured by SUNCHEM), and 0.5 parts by mass of a NOR type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) were used. The blended resin was melt-extruded using an extruder to form a 100 μm-thick transparent, highly crystalline polypropylene sheet as a sheet-like transparent resin layer 3. Then, both sides of the obtained transparent resin layer 3 were subjected to a corona treatment to set the wetting tension of the sheet surface to 40 dyn / cm or more.

[0054] On the other hand, a pattern was printed on one side of an 80 μm thick polyethylene sheet (raw material layer 6) with opacity using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) using a gravure printing method to form a pattern layer 5a, and a primer coating was applied to the other side of the raw material layer 6. Thereafter, a transparent resin layer 3 was applied onto the surface of the picture pattern layer 5a of the raw fabric layer 6 using a dry laminating adhesive (Takelac A540, manufactured by Mitsui Chemicals, Inc.; coating amount: 2 g / m 2 The sheets were laminated together by dry lamination with a transparent resin layer 3 therebetween, and an embossed pattern 3a was formed on the surface of the transparent resin layer 3 of the laminated sheets. A top coat layer 2 was formed on the transparent resin layer 3 having the embossed pattern 3a, to obtain a decorative sheet 1 having a total thickness of 190 μm to 200 μm. In each of the following Examples and Comparative Examples, the top coat layer 2 was formed using a composition selected from the following compositions for forming a top coat layer.

[0055] (Topcoat layer-forming composition) The composition for forming the top coat layer is a thermosetting composition, a photocurable composition, or a thermosetting / photocurable hybrid composition, as described below.

[0056] [Thermosetting composition] The thermosetting composition was prepared by blending the following polymer solution A with the following curing agent, gloss adjuster, ultraviolet absorber, and light stabilizer. Polymer solution A In a four-neck flask equipped with a stirrer, a nitrogen inlet tube, and a reflux condenser, 80 g of methyl methacrylate and 20 g of 2-hydroxyethyl methacrylate were introduced, and 100 g of ethyl acetate was added to dissolve them, followed by stirring in an oil bath under a nitrogen atmosphere. Polymerization was initiated by adding isobutyronitrile, and the mixture was heated and stirred for 5 hours in an oil bath at 60°C to obtain a colorless, viscous polymer solution A. Blend: 80 parts by mass Hardener Product name: Duranate 24A-100 Blend: 5 parts by mass Gloss adjuster (inorganic particles) Product name: Sunsphere H122 (AGC Si-Tech Co., Ltd.) Properties: Spherical, average particle size 12 μm, pore volume 2 ml / g Blend: 10 parts by mass UV absorber Product name: Tinuvin 400 (manufactured by BASF) Blend: 5.0 parts by mass Light stabilizers Product name: Tinuvin 123 (manufactured by BASF) Blend: 2.0 parts by mass Dilution solvent Product name: Ethyl acetate Blend: 50 parts by mass

[0057] [Photocurable composition] The photocurable composition was prepared by blending the following monomer with the following photoinitiator, gloss adjuster, and light stabilizer. ·monomer Product name: Dipentaerythritol hexaacrylate Blend: 90 parts by mass Photoinitiators Product name: Irgacure 184 Blend: 8 parts by mass Gloss adjuster (inorganic particles) Product name: Silysia 430 (Fuji Silysia Chemical Ltd.) Properties: Amorphous, average particle size 4μm, pore volume 2.3ml / g Blend: 10 parts by mass UV absorber Product name: Tinuvin 400 (manufactured by BASF) Blend: 5.0 parts by mass Light stabilizers Product name: Tinuvin 123 (manufactured by BASF) Blend: 2.0 parts by mass Dilution solvent Product name: Ethyl acetate Blend: 60 parts by mass

[0058] [Thermal-curable / photo-curable hybrid composition] The heat-curable / photo-curable hybrid composition was prepared by blending the following polymer solution A and monomer with the following curing agent, photoinitiator, gloss adjuster, UV absorber, and light stabilizer. Polymer solution A In a four-neck flask equipped with a stirrer, a nitrogen inlet tube, and a reflux condenser, 80 g of methyl methacrylate and 20 g of 2-hydroxyethyl methacrylate were introduced, and 100 g of ethyl acetate was added to dissolve them, followed by stirring in an oil bath under a nitrogen atmosphere. Polymerization was initiated by adding isobutyronitrile, and the mixture was heated and stirred for 5 hours in an oil bath at 60°C to obtain a colorless, viscous polymer solution A. Blend: 40 parts by mass ·monomer Product name: Dipentaerythritol hexaacrylate Blend: 40 parts by mass Hardener Product name: Duranate 24A-100 Blend: 10 parts by mass Photoinitiators Product name: Irgacure 184 Blend: 10 parts by mass Gloss adjuster (inorganic particles) Product name: Sunsphere H122 (AGC Si-Tech Co., Ltd.) Properties: Spherical, average particle size 12 μm, pore volume 2 ml / g Blend: 10 parts by mass UV absorber Product name: Tinuvin 400 (manufactured by BASF) Blend: 5.0 parts by mass Light stabilizers Product name: Tinuvin 123 (manufactured by BASF) Blend: 2.0 parts by mass Dilution solvent Product name: Ethyl acetate Blend: 50 parts by mass

[0059] Example 1 As the top coat layer 2, a thermosetting composition (amount of coating after drying: 10 g / m 2 ) was applied to obtain a decorative sheet 1 of Example 1 having a layer thickness of 190 μm. <Example 2> A decorative sheet 1 of Example 2 was obtained in the same manner as in Example 1, except that the ultraviolet absorber in the thermosetting composition of Example 1 was replaced with Tinuvin 329 (manufactured by BASF).

[0060] Example 3 A decorative sheet 1 of Example 3 was obtained in the same manner as in Example 1, except that the light stabilizer in the thermosetting composition of Example 1 was replaced with Tinuvin 152 (manufactured by BASF). Example 4 As the top coat layer 2, a photocurable composition (coating amount after drying: 10 g / m 2 ) was applied to obtain a decorative sheet 1 of Example 4 having a layer thickness of 190 μm.

[0061] <Example 5> As the top coat layer 2, a heat-curable / photo-curable hybrid composition (coating amount after drying: 10 g / m2 ) was applied to obtain a decorative sheet 1 of Example 5 having a layer thickness of 190 μm. Example 6 As the top coat layer 2, a thermosetting composition (amount of coating after drying: 10 g / m 2 ), photocurable composition (coating amount after drying: 5 g / m 2 ) were laminated in this order to form a top coat layer 2 consisting of two layers, a thermosetting layer and a photocurable layer, thereby obtaining a decorative sheet 1 of Example 6 having a total thickness of 195 μm.

[0062] Example 7 As the top coat layer 2, a thermosetting composition (amount of coating after drying: 10 g / m 2 ), and a thermosetting / photosetting hybrid composition (application amount after drying: 5 g / m2) were sequentially laminated to form a top coat layer 2 consisting of two layers: a thermosetting layer and a thermosetting / photosetting hybrid layer, thereby obtaining a decorative sheet 1 of Example 7 having a total thickness of 195 μm. Example 8 As the top coat layer 2, a thermosetting composition (amount of coating after drying: 10 g / m 2 ), a heat-curable / photo-curable hybrid composition (coating amount after drying: 5 g / m 2 ), photocurable composition (coating amount after drying: 5 g / m 2 ) were sequentially laminated to form a top coat layer 2 consisting of three layers: a thermosetting layer, a thermosetting-photosetting hybrid layer, and a photosetting layer, thereby obtaining a decorative sheet 1 of Example 8 having a total thickness of 200 μm.

[0063] <Comparative Example 1> A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1, except that the ultraviolet absorber in the thermosetting composition of Example 1 was replaced with Tinuvin 329 and the light stabilizer was replaced with Tinuvin 292 (manufactured by BASF). The ultraviolet absorbers and light stabilizers used are listed in Table 1. Table 1 also lists the evaluation results.

[0064] [Table 1]

[0065] <Evaluation> (Weather resistance (appearance)) The decorative sheets obtained in the examples and comparative examples were set in a metal weatherer manufactured by Daipla Wintes Co., Ltd., and exposed to light conditions (illuminance: 60 mW / cm 2 , black panel temperature 63℃, humidity inside the chamber 50%RH) for 20 hours under condensation conditions (illuminance: 0mW / cm 2 A weathering test was conducted in which the panels were left at a temperature of 25°C and 50% RH for 4 hours (black panel temperature 30°C, internal humidity 98% RH) and then left for 500 or 1000 hours under water spray conditions (10 seconds before and after condensation). After the test, the panels were left at a temperature of 25°C and 50% RH for 2 days, and then the appearance of the panels, such as cracks and yellowing, was visually evaluated according to the following criteria.

[0066] (Coating appearance) ○: No change in appearance at all. △: Fine cracks were found on the surface. ×: Numerous cracks were found on the surface. (Yellowing of the substrate) ○: No change in appearance at all. △: Slight yellowing was observed. ×: Significant yellowing occurred.

[0067] The decorative sheets of each example contained a light stabilizer with a pKa of 4.0 to 7.0 and an ultraviolet absorber with a pKa of -4.5 to -5.5 when irradiated with light, as shown in Table 1. This allowed for the production of decorative sheets that could suppress changes in gloss after weathering tests without generating haze and that were less susceptible to changes in appearance. Furthermore, by setting the molecular weight of the light stabilizer to 600 or more and the molecular weight of the ultraviolet absorber to 400 or more, it was possible to further improve weather resistance. From the above results, it can be seen that the decorative sheet 1 of the example based on the present invention is excellent in weather resistance and design. The decorative sheet of the present invention is not limited to the above-described embodiments and examples, and various modifications are possible within the scope that does not impair the characteristics of the invention. [Explanation of symbols]

[0068] 1 decorative sheet 2. Topcoat layer 3 Transparent resin layer (olefin resin layer) 3a Embossed pattern 4 Adhesive layer 5 Ink layer 5a Pattern layer 5b Solid ink layer 6 Original fabric layer (base material layer) 7 Adhesive resin layer

Claims

1. A laminate consisting of a plurality of resin layers, a top coat layer located on the outermost surface side of the laminate contains a light stabilizer having a pKa of 4.0 to 7.0 and an ultraviolet absorber having a pKa of −4.5 to −5.5 when irradiated with light; the topcoat layer comprises a photocurable layer; the photocurable layer contains the light stabilizer and the ultraviolet absorber, The photocurable layer is a laminate characterized in that it contains a resin having dipentaerythritol hexaacrylate as a constituent component as a photocurable resin.

2. A laminate consisting of a plurality of resin layers, a top coat layer located on the outermost surface side of the laminate contains a light stabilizer having a pKa of 4.0 to 7.0 and an ultraviolet absorber having a pKa of −4.5 to −5.5 when irradiated with light; the topcoat layer comprises a thermoset layer; the thermosetting layer contains the light stabilizer and the ultraviolet absorber, The thermosetting layer is a laminate comprising a thermosetting resin containing methyl methacrylate and 2-hydroxyethyl methacrylate as constituent components.

3. The top coat layer further comprises a thermosetting / photosetting hybrid layer containing a thermosetting resin and a photosetting resin, the thermosetting resin in the thermosetting / photosetting hybrid layer is a resin containing methyl methacrylate and 2-hydroxyethyl methacrylate as constituent components; 2. The laminate according to claim 1, wherein the photocurable resin in the thermosetting / photocurable hybrid layer is a resin containing dipentaerythritol hexaacrylate as a constituent component.

4. The top coat layer further comprises a thermosetting / photosetting hybrid layer containing a thermosetting resin and a photosetting resin, the thermosetting resin in the thermosetting / photosetting hybrid layer is a resin containing methyl methacrylate and 2-hydroxyethyl methacrylate as constituent components; 3. The laminate according to claim 2, wherein the photocurable resin in the thermosetting / photocurable hybrid layer is a resin containing dipentaerythritol hexaacrylate as a constituent component.

5. A laminate as described in claim 3, characterized in that the top coat layer comprises the photocured layer formed on the heat-cured / photocured hybrid layer.

6. A laminate as described in claim 4, characterized in that the top coat layer comprises the thermosetting / photosetting hybrid layer formed on the thermosetting layer.

7. 7. The laminate according to claim 1, wherein the light stabilizer is a hindered amine-based light stabilizer having an amino ether group and a molecular weight of 600 or more.

8. A laminate described in any one of claims 1 to 6, characterized in that the light stabilizer has a structure represented by the following formula (1) or the following formula (2). 【Chemistry 1】 【Chemistry 2】

9. 9. The laminate according to claim 1, wherein the ultraviolet absorber has a triazine skeleton or a benzotriazole skeleton and a molecular weight of 400 or more.

10. A laminate described in any one of claims 1 to 8, characterized in that the ultraviolet absorber has a structure represented by the following formula (3) or the following formula (4). 【Transformation 3】 【Chemistry 4】

11. 11. The laminate according to claim 1, wherein the top coat layer contains a gloss adjuster made of inorganic particles.

12. The film has an olefin resin layer, which is a resin layer whose main component is an olefin resin and contains 0.3 parts by mass or more of a compound having a pKa of 7.0 or less per 100 parts by mass of the resin material; 12. The laminate according to claim 1, wherein the top coat layer is formed on the olefin resin layer.

13. A decorative sheet comprising the laminate according to any one of claims 1 to 12.

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