Decorative sheet and transfer film

Abstract

To provide a decorative sheet excellent in light resistance even when a surface protective layer containing a biomass-derived component is formed, and a transfer film.SOLUTION: A decorative sheet comprising at least a transparent resin layer and a surface-protecting layer, wherein the surface-protecting layer contains a cross-linked curable resin as a main component, an ultraviolet absorber, and a light stabilizer, the cross-linked curable resin contains at least one biomass-derived component and at least one (meth) acrylic monomer, and the ultraviolet absorber contains at least two ultraviolet absorbers having a benzotriazole skeleton.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet and a transfer film. [Background technology]

[0002] Decorative sheets and transfer films with designs are used to decorate building materials, furniture, home appliances, and the like.

[0003] Plastics are often used as the main component of decorative sheets and transfer films. Petroleum-derived plastics are widely used, but these are not desirable from the perspective of reducing environmental impact.

[0004] Therefore, biomass-derived plastics, which are made from renewable biological resources, are being considered for use in decorative sheets as a material that has a lower environmental impact than petroleum-derived plastics.

[0005] For example, Patent Document 1 discloses a decorative sheet comprising, in this order, a colored thermoplastic resin layer, an adhesive resin layer, a transparent thermoplastic resin layer, and a surface protective layer, wherein the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each resin layers formed from a resin composition containing a biomass-derived polyolefin, and the surface protective layer contains a biomass-derived component.

[0006] Furthermore, decorative sheets and transfer films are used to protect architectural interior materials for homes and public facilities, architectural exterior components such as entrance doors, surfaces of building fixtures, and surface materials for home appliances, and therefore may be used outdoors in places exposed to sunlight, wind, and rain, and therefore require extremely high weather resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2023-122232 Summary of the Invention [Problem to be solved by the invention]

[0008] However, from the viewpoint of reducing the environmental impact, if a biomass-derived component is included in the surface protective layer of a decorative sheet, there is a problem in that it is not possible to impart excellent weather resistance by selecting a resin containing a biomass-derived component that constitutes the surface protective layer.

[0009] Therefore, an object of the present invention is to provide a decorative sheet and a transfer film that have excellent light resistance even when a surface protective layer containing a biomass-derived component is formed. [Means for solving the problem]

[0010] The present inventors focused on the resin components and weather resistant agents contained in the surface protective layer and discovered that a decorative sheet with excellent weather resistance can be obtained by having a surface protective layer that contains at least one biomass-derived component and a cross-linked curable resin containing at least one (meth)acrylic monomer, a specific ultraviolet absorber, and a light stabilizer, and thus completed the present invention.

[0011] That is, the present invention provides a decorative sheet comprising at least a transparent resin layer and a surface protective layer, wherein the surface protective layer contains a cross-linked curable resin as a main component, an ultraviolet absorber, and a light stabilizer, the cross-linked curable resin containing at least one biomass-derived component and at least one (meth)acrylic monomer, and the ultraviolet absorber contains at least two ultraviolet absorbers having a benzotriazole skeleton.

[0012] In the decorative sheet of the present invention, the cross-linking curable resin preferably further contains at least one type of urethane (meth)acrylate. In the decorative sheet of the present invention, the at least two types of ultraviolet absorbers having a benzotriazole skeleton preferably include an ultraviolet absorber A having a benzotriazole skeleton with a maximum absorption wavelength of less than 350 nm, and an ultraviolet absorber B having a benzotriazole skeleton with a maximum absorption wavelength of 350 nm or more. In the decorative sheet of the present invention, it is preferable that the total content of the at least two types of ultraviolet absorbers having a benzotriazole skeleton in the surface protective layer is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cross-linking curable resin. In the decorative sheet of the present invention, the light stabilizer in the surface protective layer is preferably a reactive light stabilizer. In the decorative sheet of the present invention, the surface protective layer preferably has a thickness of 3 μm or more and 30 μm or less. In the decorative sheet of the present invention, the surface protective layer preferably further contains an inorganic filler. In the decorative sheet of the present invention, it is preferable to provide a design layer and a base sheet in this order on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided, via an adhesive layer. In the decorative sheet of the present invention, it is preferable that at least one of the substrate sheet, adhesive layer, and transparent resin layer contains a biomass-derived polyolefin. In the decorative sheet of the present invention, it is preferable that the surface having the surface protective layer has an uneven shape.

[0013] The present invention also preferably relates to a transfer film comprising the decorative sheet of the present invention as a transfer layer and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided. [Effects of the Invention]

[0014] The present invention provides a decorative sheet and a transfer film that have excellent light resistance even when a surface protective layer containing a biomass-derived component is formed. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a cross-sectional view that schematically illustrates a preferred example of the decorative sheet of the present invention. [Figure 2] FIG. 2 is a cross-sectional view for explaining a schematic view of another preferred example of the decorative sheet of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016] <Decorative sheet> The decorative sheet of the present invention comprises at least a transparent resin layer and a surface protective layer, the surface protective layer containing a cross-linked curable resin as a main component, an ultraviolet absorber, and a light stabilizer, the cross-linked curable resin containing at least one biomass-derived component and at least one (meth)acrylic monomer, and the ultraviolet absorber containing at least two ultraviolet absorbers having a benzotriazole skeleton.

[0017] FIG. 1 is a cross-sectional view that schematically illustrates one example of the decorative sheet of the present invention. As shown in Figure 1, the decorative sheet 10 comprises a transparent resin layer 3 and a surface protective layer 4, and comprises a pattern layer 2 and a base sheet 1 on the side of the transparent resin layer 3 opposite to the side on which the surface protective layer 4 is provided. The decorative sheet 10 also has an uneven shape 5 on the side on which the surface protective layer 4 is provided.

[0018] FIG. 2 is a cross-sectional view for explaining a schematic view of another preferred example of the decorative sheet of the present invention. As shown in FIG. 2, the decorative sheet 10 is formed by laminating a transparent resin layer 3 and a surface protective layer 4 via an adhesive auxiliary layer 8 (also referred to as a surface adhesive auxiliary layer). In addition, on the side of the transparent resin layer 3 opposite to the side having the surface protective layer 4, an adhesive layer 7, a pattern layer 2, an adhesive auxiliary layer 6 (also called a pattern auxiliary layer), a base sheet 1, and an adhesive auxiliary layer 9 (also called a back surface adhesive auxiliary layer) are laminated in this order. The decorative sheet 10 also has an uneven shape 5 on the side on which the surface protective layer 4 is provided. Each component of the decorative sheet of the present invention will be described in detail below.

[0019] (Surface protective layer) The decorative sheet of the present invention comprises a surface protective layer, which contains a cross-linked curable resin as a main component, an ultraviolet absorber, and a light stabilizer. The cross-linking curable resin may be formed from a composition containing at least one type of (meth)acrylic monomer, and the composition preferably further contains at least one type of urethane (meth)acrylate. In this specification, (meth)acrylate means acrylate and / or methacrylate, and (meth)acrylic means acrylic and / or methacrylic.

[0020] The cross-linked curable resin contains at least one biomass-derived component. The crosslinking effect resin may contain a biomass-derived component as a component different from the at least one (meth)acrylic monomer, the at least one (meth)acrylic monomer may contain a biomass-derived component, or when it further contains at least one urethane (meth)acrylate, the urethane (meth)acrylate may contain a biomass-derived component. The resin component containing the biomass-derived component is not particularly limited, but is preferably at least one (meth)acrylic monomer, and when the crosslinking curable resin further contains at least one urethane (meth)acrylate, it is preferable that at least one resin component of the at least one (meth)acrylic monomer and the urethane (meth)acrylate contains a biomass-derived component.

[0021] From the viewpoint of suitably reducing the environmental load, the cross-linking curable resin preferably has a biomass content of 10% or more. The biomass degree is more preferably 15% or more, even more preferably 30% or more, and particularly preferably 40% or more. The upper limit of the biomass degree is not particularly limited, but is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less, for example.

[0022] In this specification, "biomass content" refers to a value measured by radiocarbon (C14) measurement to determine the content of carbon derived from biomass. Atmospheric carbon dioxide contains a certain proportion of C14 (105.5 pMC), and it is known that the C14 content in plants that grow by absorbing atmospheric carbon dioxide, such as corn, is also about 105.5 pMC. On the other hand, it is also known that fossil fuels contain almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in the total carbon atoms in the layer of the base sheet of the present invention (or in the transparent resin layer described below). That is, the content of C14 in the layer of the base sheet of the present invention (or in the layer of the transparent resin layer) is P C14 The content of biomass-derived carbon in this case is P bio can be calculated as follows: P bio (%)=(P C14 / 105.5)×100

[0023] The (meth)acrylic monomer contained in the cross-linking curable resin that forms the surface protective layer is not particularly limited, but preferably has a molecular weight of more than 300 and less than 1,000. This is because by having the molecular weight within the above range, it is possible to suppress a decrease in productivity during embossing of the decorative sheet of the present invention. The (meth)acrylic monomer more preferably has a molecular weight of 320 or more, and even more preferably 340 or more. The molecular weight of the (meth)acrylic monomer means the molecular weight calculated from the chemical formula.

[0024] As the (meth)acrylic monomer, a petroleum-derived (meth)acrylic monomer can be used, but it is preferable to use a biomass-derived (meth)acrylic monomer.

[0025] Biomass-derived (meth)acrylic monomers include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di( Examples of suitable di(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among these, glycerin tri(meth)acrylate is preferred.

[0026] As the petroleum-derived (meth)acrylic monomer, for example, the following compounds having two or more ethylenically unsaturated bonds, which are known as difunctional or higher monomers (compounds having two or more ethylenically unsaturated bonds), can be used. Specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl 2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-Dimethyl-2,5-hexanediol di(meth)acrylate, 2-Methyl-1,8-octanediol di(meth)acrylate, 2-Butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-Diethyl-1,5-pentanediol di(meth)acrylate, 1,2-Hexanediol di(meth)acrylate, 1,5-Hexanediol di(meth)acrylate, 2,5-Hexanediol di(meth)acrylate, 1,7-Heptanediol Diol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate Decanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol Di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-Pentanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tricyclodecanedimethylol dicaprolactonate di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, bisphenol A tetraethylene oxide adduct di(meth)acrylate, bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct di( Bifunctional monomers such as di(meth)acrylates of polyhydric alcohols such as glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol; hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, etc.; trifunctional monomers such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactonate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; Trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetracaprolactonate tetra(meth)acrylate, diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolhexa Examples of suitable monomers include tetrafunctional or higher functional monomers such as tetramethylolpropane tetra(meth)acrylate, ditrimethylol octane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and tripentaerythritol polyalkylene oxide hepta(meth)acrylate. Among these, preferred examples include trimethylolpropane triacrylate (TMPTA; trifunctional), ditrimethylolpropane tetraacrylate (DITMPTA; tetrafunctional), dipentaerythritol hexaacrylate (DPHA; hexafunctional), and hexanediol diacrylate (HDDA; bifunctional).

[0027] The (meth)acrylic monomer preferably has 2 or more and 6 or less functional groups, more preferably 2 or more and 4 or less, from the viewpoint of suitably imparting scratch resistance and weather resistance to the surface protective layer.

[0028] The (meth)acrylic monomer preferably has a biomass ratio of 20% or more, more preferably 30% or more, and even more preferably 35% or more. When the lower limit of the biomass degree of the (meth)acrylic monomer is within the above range, the biomass degree of the crosslinking curable resin can be suitably increased.

[0029] The cross-linking curable resin may contain two or more types of (meth)acrylic monomers, for example, it may contain two or more types of the above-mentioned suitable (meth)acrylic monomers, or it may contain a (meth)acrylic monomer having a molecular weight of less than 300 and a (meth)acrylic monomer having a molecular weight of 300 or more and less than 1000. In this case, from the viewpoint of suppressing a decrease in productivity during embossing of the decorative sheet of the present invention, it is preferable that the content of the (meth)acrylic monomer having a molecular weight of 300 or more and less than 1000 is greater than the content of the (meth)acrylic monomer having a molecular weight of less than 300.

[0030] The total content of at least one (meth)acrylic monomer in the crosslinking curable resin is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less. If the lower limit of the (meth)acrylic monomer content in the crosslinking curable resin is 50% by mass or more, weather resistance becomes an issue, and if the upper limit is 5% by mass or less, solvent resistance becomes an issue.

[0031] The at least one urethane (meth)acrylate contained in the cross-linking curable resin that forms the surface protective layer is preferably one obtained by reacting a polyol, an isocyanate, and a hydroxy (meth)acrylate.

[0032] Examples of polyols include polyester polyols, polyether polyols, polycarbonate polyols, and polycaprolactone polyols.

[0033] Polyester polyols are the reaction products of polyfunctional alcohols and polyfunctional carboxylic acids, polyether polyols are the reaction products of polyfunctional alcohols and polyfunctional isocyanates, and polycarbonate polyols are the reaction products of polyfunctional alcohols and carbonates. Polycaprolactone polyols can be obtained by ring-opening polymerization of ε-caprolactone with polyfunctional alcohols. The polyfunctional alcohols, polyfunctional carboxylic acids, polyfunctional isocyanates, and carbonates may be known petroleum-derived materials, but the polyfunctional alcohols, polyfunctional carboxylic acids, and polyfunctional isocyanates may also be biomass-derived materials.

[0034] Examples of biomass-derived alcohols include aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugarcane, cassava, and sago palm, and examples thereof include polypropylene glycol, neopentyl glycol, ethylene glycol, diethylene glycol, butylene glycol, and hexamethylene glycol.

[0035] Examples of biomass-derived carboxylic acids that can be used include aliphatic polyfunctional carboxylic acids obtained from plant raw materials such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and examples thereof include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid.

[0036] As the biomass-derived isocyanate, polyfunctional isocyanates obtained from plant raw materials can be used, and examples thereof include dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate.

[0037] As the hydroxy(meth)acrylate, a known hydroxy(meth)acrylate having two or more functional groups may be used.

[0038] The urethane (meth)acrylate preferably has 2 or more and 6 or less functional groups, more preferably 2 or more and 4 or less, from the viewpoint of suitably imparting scratch resistance and weather resistance to the surface protective layer. Furthermore, from the viewpoint of suitably imparting weather resistance, it is preferable to use a caprolactone-based urethane (meth)acrylate obtained by reacting polycaprolactone polyol with isocyanate and hydroxy (meth)acrylate. When two or more urethane (meth)acrylates are contained, it is preferred that the majority of the urethane (meth)acrylate components contain urethane (meth)acrylates having 2 or more and 6 or less functional groups.

[0039] The urethane (meth)acrylate preferably has a biomass content of 40% or more. By ensuring that the biomass degree is within the above range, the biomass degree of the cross-linked curable resin can be suitably increased.

[0040] The urethane (meth)acrylate preferably has a mass average molecular weight (Mw) of 1,000 or more, more preferably 2,000 or more. In this specification, the term "mass average molecular weight (Mw)" refers to an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0041] The cross-linking curable resin may contain two or more types of urethane (meth)acrylate, for example, two or more types of the above-mentioned suitable urethane (meth)acrylates.

[0042] The total content of at least one urethane (meth)acrylate in the crosslinking curable resin is preferably 30% by mass or more, more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less. If the upper limit of the urethane (meth)acrylate content in the crosslinking curable resin is 95% by mass or more, solvent resistance may be a concern, and if the lower limit is 20% by mass or less, weather resistance, impact resistance, etc. may be a concern.

[0043] The surface protective layer of the decorative sheet of the present invention contains an ultraviolet absorber, and the ultraviolet absorber contains at least two types of ultraviolet absorbers having a benzotriazole skeleton. In the present disclosure, the ultraviolet absorbers having at least two types of benzotriazole skeletons are preferably ultraviolet absorbers having at least two or more types of benzotriazole skeletons with different maximum absorption wavelengths.

[0044] Examples of ultraviolet absorbers having a 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-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-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN 928, manufactured by BASF), 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (TINUVIN PS, manufactured by BASF), ester compound of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy(C7-9 side chain and linear alkyl) (TINUVIN384-2, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN900, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-Tetramethylbutyl)phenol (TINUVIN 928, manufactured by BASF), methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction product (TINUVIN 1130, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-p-cresol (TINUVIN P, manufactured by BASF), 2(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN234, manufactured by BASF), 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (TINUVIN326, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (TINUVIN328, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVI N329, manufactured by BASF), a reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol 300 (TINUVIN213, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole (Sumisorb250, manufactured by Sumitomo Chemical Co., Ltd.), etc. can be used.

[0045] The at least two types of ultraviolet absorbers having a benzotriazole skeleton preferably include an ultraviolet absorber A having a benzotriazole skeleton with a maximum absorption wavelength of less than 350 nm, and an ultraviolet absorber B having a benzotriazole skeleton with a maximum absorption wavelength of 350 nm or more. When the ultraviolet absorber contained in the surface protective layer is of the above-mentioned preferred embodiment, ultraviolet absorbers A and B contained in the surface protective layer absorb light in the wavelength range of 280 nm or more and 380 nm or less, at which the surface protective layer and the layer below it are susceptible to photodegradation, and therefore photodegradation of the surface protective layer and the layer below it containing ultraviolet absorbers A and B can be suppressed, providing more effective protection from degradation by ultraviolet light. In particular, when the surface protective layer and the layer below it contain polypropylene, the wavelengths susceptible to photodegradation are 310 nm, 330 nm, and 370 nm, and by containing ultraviolet absorber A having a benzotriazole skeleton and a maximum absorption wavelength of less than 350 nm, and ultraviolet absorber B having a benzotriazole skeleton and a maximum absorption wavelength of 350 nm or more, photodegradation can be effectively suppressed.

[0046] An example of an ultraviolet absorber A having a benzotriazole skeleton and a maximum absorption wavelength of less than 350 nm is 2-(2H-benzotriazol-2-yl)-p-cresol (TINUVIN P, manufactured by BASF), and an example of an ultraviolet absorber B having a benzotriazole skeleton and a maximum absorption wavelength of 350 nm or more is 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (TINUVIN 326, manufactured by BASF). However, without being limited to this combination, an ultraviolet absorber having a benzotriazole skeleton can be used as either ultraviolet absorber A or B depending on the maximum absorption wavelength of the ultraviolet absorber.

[0047] Examples of ultraviolet absorbers A having a benzotriazole skeleton with a maximum absorption wavelength of less than 350 nm include 2-(2H-benzotriazole-2-yl)-p-cresol (TINUVIN P, manufactured by BASF, maximum absorption wavelength 340 nm), 2(2H-benzotriazole-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN 234, manufactured by BASF, maximum absorption wavelength 343 nm), 1-methoxy-2-propyl acetate (TINUVIN 384, manufactured by BASF, maximum absorption wavelength 345 nm), and methyl 5-(2H-benzotriazole-2-yl)-4-hydroxy-3-tert-butylbenzenepropanoate (TINUVIN 1130, manufactured by BASF, maximum absorption wavelength 346 nm). Ultraviolet absorbers A having a benzotriazole skeleton with a maximum absorption wavelength of less than 350 nm preferably have a maximum absorption wavelength of 280 nm or more, more preferably 300 nm or more.

[0048] Examples of ultraviolet absorbers B having a benzotriazole skeleton and a maximum absorption wavelength of 350 nm or more include 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (TINUVIN326, manufactured by BASF, maximum absorption wavelength 353 nm), 2-(2-hydroxyphenyl)-benzotriazole (TINUVIN970, manufactured by BASF, maximum absorption wavelength 378 nm), etc. The ultraviolet absorbers B having a benzotriazole skeleton and a maximum absorption wavelength of 350 nm or more preferably have a maximum absorption wavelength of 380 nm or less, more preferably 370 nm or less.

[0049] In the surface protective layer, the total content of at least two ultraviolet absorbers having a benzotriazole skeleton relative to 100 parts by mass of the crosslinking curable resin is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 2 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. When the lower limit of the total content of the ultraviolet absorbers having a benzotriazole skeleton relative to 100 parts by mass of the crosslinking curable resin is within the above range, weather resistance tends to be further improved, and when the upper limit is within the above range, bleed-out of the ultraviolet absorbers having a benzotriazole skeleton is suppressed, and solvent resistance tends to be improved.

[0050] The UV absorber contained in the surface protective layer may be, for example, an organic UV absorber such as a triazine UV absorber, a benzophenone UV absorber, an oxybenzophenone UV absorber, a salicylic acid ester UV absorber, or a cyano(meth)acrylate UV absorber, or an inorganic UV absorber such as titanium dioxide, cerium oxide, or zinc oxide. When the surface protective layer also contains a UV absorber other than the UV absorber having a benzotriazole skeleton, the total content of the UV absorbers contained in the surface protective layer is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. Having the upper limit of the total content of the UV absorbers within the above range tends to suppress bleed-out of the UV absorber and improve solvent resistance.

[0051] The surface protective layer in the decorative sheet of the present invention contains a light stabilizer. Examples of the light stabilizer include hindered amine light stabilizers. Examples of the hindered amine light stabilizer include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate. tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, and bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxy-benzyl)-2-n-butylmalonate.

[0052] The decorative sheet of the present invention preferably contains a reactive light stabilizer as the light stabilizer contained in the surface protective layer.

[0053] The reactive light stabilizer is not particularly limited, but may be any reactive light stabilizer having an ethylenic double bond polymerizable with a curable compound capable of forming a crosslinked curable resin of the surface protective layer. The surface protective layer may contain one or more reactive light stabilizers, and may contain both reactive and non-reactive light stabilizers.

[0054] Reactive light stabilizers are usually incorporated into and fixed in the cross-linking curable resin system during the formation of the surface protective layer, and therefore can exert a long-term effect, whereas non-reactive light stabilizers can be mobile within the surface protective layer and therefore can exert an immediate effect.

[0055] The number of ethylenic double bonds in the reactive light stabilizer may be one or two or more.

[0056] Examples of reactive light stabilizers having one ethylenic double bond include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy ... -cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, pentamethylpiperidinyl (meth)acrylate, the compound with CAS number 1010692-24-6 and the compound with CAS number 1010692-21-3. Examples of reactive light stabilizers having two or more ethylenic double bonds include 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, the compound with CAS number 1954659-42-7, and the compound with CAS number 1010692-23-5.

[0057] In the surface protective layer, the content of the light stabilizer relative to 100 parts by mass of the cross-linked curable resin is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and preferably less than 15 parts by mass, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and still more preferably 6 parts by mass or less. When the lower limit of the light stabilizer content is 1.0 part by mass or more, light resistance tends to be more effectively improved, and when the upper limit is less than 15 parts by mass, solvent resistance tends to be improved.

[0058] The surface protective layer may contain a light stabilizer, and may contain at least one of the above hindered amine light stabilizers, or may contain one or more of the above reactive light stabilizers, or may contain one or more of the above hindered amine light stabilizers and one or more of the above reactive light stabilizers. When the surface protective layer contains multiple light stabilizers, the content of the light stabilizers per 100 parts by mass of the above cross-linking curable resin can be interpreted as the total content of the light stabilizers. When the light stabilizers contain the above hindered amine light stabilizer and the above reactive light stabilizer, the blending ratio by mass (hindered amine light stabilizer:reactive light stabilizer) is preferably 9:1 to 1:9.

[0059] The surface protective layer preferably contains an inorganic filler. By including an inorganic filler, the gloss of the decorative sheet can be adjusted, and a more luxurious design can be imparted.

[0060] Examples of inorganic fillers include silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, and synthetic silicates.

[0061] The inorganic filler preferably has a particle size of 1 μm or more and 20 μm or less. The particle size is the 50% particle size (d50: median size) when the particle size distribution measured by a dynamic light scattering method is expressed as a volume cumulative distribution.

[0062] The cross-linking curable resin may contain a known photopolymerization initiator, if necessary. The amount of the photopolymerization initiator added is preferably, for example, 0.1% by mass or more and 10% by mass or less based on the mass of the crosslinking curable resin.

[0063] The surface protective layer may contain additives, such as antioxidants, abrasion resistance improvers, infrared absorbers, antistatic agents, leveling agents, thixotropy-imparting agents, coupling agents, antifoaming agents, flame retardants, plasticizers, particles, and antiblocking agents. The amounts of the additives may be appropriately selected depending on the properties of each additive.

[0064] The surface protection layer preferably has a thickness of 3 μm or more and 30 μm or less. When the thickness of the surface protective layer is within the above range, scratch resistance and weather resistance can be suitably imparted. The thickness of the surface protective layer is more preferably 5 μm or more and more preferably 20 μm or less. In addition, when the uneven shape described below is formed, the thickness of the surface protection layer is defined as the length from the part of the surface of the surface protection layer where the uneven shape is not formed to the surface of the surface protection layer on the transparent resin layer side.

[0065] The surface protective layer is preferably formed from a coating agent (composition) that contains at least one biomass-derived component, at least one (meth)acrylic monomer, and further contains an ultraviolet absorber having a triazine skeleton as an ultraviolet absorber, and a reactive light stabilizer as a light stabilizer. The (meth)acrylic monomer (also referred to as a resin component), ultraviolet absorber having a triazine skeleton, and reactive light stabilizer contained in the coating agent can be those described above. If necessary, the coating agent may also contain weathering agents such as ultraviolet absorbers other than the ultraviolet absorbers having a triazine skeleton described above and non-reactive light stabilizers, inorganic fillers, and additives. Such coating agents are also included in the present invention.

[0066] The surface protective layer may be formed by applying a coating agent by a known method and curing it with ionizing radiation. The term "ionizing radiation" refers to electromagnetic waves or charged particles that have enough energy to polymerize or crosslink molecules, and generally refers to electron beams (EB) or ultraviolet rays (UV).

[0067] (Transparent resin layer) The decorative sheet of the present invention comprises a transparent resin layer. The above-mentioned "transparency" means that the design layer may be semi-transparent or colored, as long as it is within a range where the design layer can be seen.

[0068] The transparent resin layer may be made of, for example, an ester-based resin, an olefin-based resin, an acrylic-based resin, a carbonate-based resin, a urethane-based resin, a styrene-based resin, a vinyl chloride-based resin, a vinyl acetate-based resin, a vinyl chloride-vinyl acetate copolymer resin, etc. From the viewpoint of improving moldability and scratch resistance, an ester-based resin or an olefin-based resin such as polypropylene or polyester is preferred.

[0069] The transparent resin layer may contain a biomass-derived component. When the transparent resin layer contains a biomass-derived component, the environmental load can be suitably reduced. In this case, biomass-derived polyolefin (biomass-derived polyethylene, polypropylene, etc.) may be used as the resin constituting the transparent resin layer.

[0070] The transparent resin layer may further contain various additives as needed. Examples include antioxidants, ultraviolet absorbers, light stabilizers, lubricants, nucleating agents, colorants such as dyes and pigments, etc. The amount of the additives to be added may be appropriately selected depending on the properties of each additive.

[0071] The thickness of the transparent resin layer is preferably 40 μm or more and 150 μm or less. By ensuring that the thickness of the transparent resin layer is within the above range, the scratch resistance of the decorative sheet can be suitably improved.

[0072] The method for laminating the transparent resin layer is not limited as long as it is a common method, and examples thereof include a dry lamination method and an extrusion lamination method in which a molten resin is extruded using a T-die to perform lamination. A T-die or the like capable of extruding molten resin can be used as the extrusion mechanism described above.

[0073] The transparent resin layer may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma discharge treatment, ultraviolet (UV) treatment, and flame treatment.

[0074] (Picture layer) The decorative sheet of the present invention preferably has a pattern layer on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided.

[0075] The pattern layer is used to impart a desired pattern (design) to the decorative sheet, and the type of pattern is not limited, etc. Examples include wood grain patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, leather-grained patterns, geometric figures, letters, symbols, abstract patterns, etc.

[0076] The ink used to form the design layer contains a colorant component, a resin component, and a liquid component. The ink may also contain an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, etc.

[0077] Examples of colorant components that can be used include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; scaly foil metal pigments such as aluminum and brass; and scaly foil pearlescent pigments such as titanium dioxide-coated mica and basic lead carbonate. The resin component is not particularly limited and can be any resin selected from the group consisting of urethane resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, nitrocellulose (nitrocellulose) resins, cellulose acetate resins, acrylic-urethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, and chlorinated polypropylene resins, either alone or in combination. As the liquid component, for example, organic solvents such as methyl ethyl ketone, toluene, cyclohexanone, ethyl acetate alcohol, ethanol, and methanol, or water can be used.

[0078] The design layer can be formed by partially printing an ink containing a colorant component, a resin component, and a liquid component using a gravure printing method using an intaglio roll. The design layer may also be formed by partially printing inks of the same or different compositions in different regions and / or by overlapping the same region multiple times.

[0079] The thickness of the design layer is preferably, for example, 0.1 μm or more and 5 μm or less.

[0080] (Base sheet) The decorative sheet of the present invention preferably has a substrate sheet on the side opposite to the side on which the transparent resin layer of the design layer is provided.

[0081] Examples of resins that constitute the substrate sheet include ester-based resins, olefin-based resins, urethane-based resins, acrylic-based resins, polycarbonate-based resins, polystyrene-based resins; vinyl chloride-based resins, vinyl acetate-based resins, and vinyl chloride-vinyl acetate copolymer resins. Of these, ester-based resins and olefin-based resins are preferred, and polyethylene and polypropylene are more preferred.

[0082] The base sheet may contain a biomass-derived component. When the base sheet contains a biomass-derived component, the environmental load can be suitably reduced. In this case, biomass-derived polyolefin (biomass-derived polyethylene, polypropylene, etc.) may be used as the resin constituting the base sheet.

[0083] The substrate sheet may be colored as necessary. The surface may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment, or may be coated with a primer, which is a base coating material, to improve adhesion to adjacent layers.

[0084] The substrate sheet may contain various additives, as needed, such as colorants, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, ultraviolet absorbers, antioxidants, light stabilizers, etc. The amounts of the additives to be added may be appropriately selected depending on the properties of each additive.

[0085] The substrate sheet may be colored as necessary. The surface may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment, or may be coated with a primer, which is a base coating material, to improve adhesion to adjacent layers.

[0086] The thickness of the substrate sheet is, for example, preferably 50 μm or more and less than 100 μm, and more preferably 60 μm or more and 80 μm or less.

[0087] The specific method for forming a film (sheeting) of the substrate sheet is not particularly limited, and examples include the T-die method in which molten resin is extruded and laminated using a T-die, the calendar method, and the circular die method (inflation method, tubular method). Among these, the T-die method is preferred when improving production efficiency (production speed) and alleviating internal stress during sheeting. The calendar method is preferred when making the thickness of the substrate sheet uniform and reducing foreign matter defects.

[0088] (adhesive layer) The decorative sheet of the present invention may have an adhesive layer between the design layer and the transparent resin layer. The adhesive layer is preferably transparent.

[0089] The adhesive that can be used to form the adhesive layer includes, for example, urethane adhesives such as ester urethane and acrylic urethane, acrylic adhesives, epoxy adhesives, and rubber adhesives.

[0090] The adhesive layer may include a biomass-derived component. As the biomass-derived component, for example, the above-mentioned urethane-based adhesive using biomass-derived isocyanate may be used.

[0091] The thickness of the adhesive layer is, for example, 0.1 to 30 μm. The method for forming the adhesive layer is not particularly limited, and any known method may be appropriately selected.

[0092] (adhesion auxiliary layer) If necessary, the decorative sheet of the present invention may have an adhesive auxiliary layer (pattern auxiliary layer) between the base sheet and the pattern layer, an adhesive auxiliary layer (surface adhesive auxiliary layer) between the transparent resin layer and the surface protective layer, or an adhesive auxiliary layer (back surface adhesive auxiliary layer) on the back surface of the base sheet (the side opposite to the side having the pattern layer). The adhesion auxiliary layer functions as a primer layer or an easy-adhesion layer.

[0093] The adhesive auxiliary layer can be formed using, for example, an ester-based resin, a urethane-based resin, an acrylic-based resin, a polycarbonate-based resin, a vinyl chloride-vinyl acetate copolymer, a polyvinyl butyral-based resin, a nitrocellulose-based resin, etc., and one or more of these resins can be used.

[0094] The thickness of the adhesion auxiliary layer is preferably 0.1 μm or more and 30 μm or less, from the viewpoint of suitably suppressing poor adhesion between layers. The method for forming the adhesive auxiliary layer is not particularly limited, and any known method may be appropriately selected.

[0095] The adhesive layer or the adhesive auxiliary layer may contain additives as required. Examples of the additives include lubricants such as silicone resins, waxes, and fluororesins, colorants such as dyes and pigments, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, flame retardants, deodorizers, antibacterial agents, antiviral agents, antiallergens, and antifungal agents. The amount of the additives to be added may be appropriately selected depending on the properties of each additive.

[0096] (Uneven shape) The decorative sheet of the present invention has an uneven shape on the side having the surface protective layer, from the viewpoint of providing a suitable design.

[0097] The uneven shape may reach the transparent resin layer or the adhesive auxiliary layer (adhesive auxiliary layer 6 in FIG. 2), or may be a flat shape (finely uneven shape).

[0098] The maximum height Rz of the uneven shape is preferably, for example, 10 μm or more and 60 μm or less. By setting the maximum height Rz of the uneven shape within the above range, it is possible to suitably impart an excellent design that gives a three-dimensional feel not only visually but also tactilely (to the touch). The "maximum height Rz" means the maximum height Rz specified in JIS B 0601 (2001).

[0099] The method for forming the uneven shape is not particularly limited, and examples thereof include a method of embossing with heat, and a method of transferring the uneven shape using a shaping sheet. Examples of heat embossing include embossing using a well-known sheet-type or rotary embosser. Examples of embossed patterns include sand grain, hairline, matte finish, wood grain vessel grooves, uneven stone surface, cloth surface texture, and linear grooves.

[0100] (others) The decorative sheet of the present invention may, if necessary, have a backer layer on the side of the substrate sheet opposite the design layer. By providing a backer layer, impact resistance can be more suitably imparted.

[0101] The backer layer can be produced by molding the resin composition into a sheet (film) by a calendering method, an inflation method, a T-die extrusion method, or the like.

[0102] The resin forming the backer layer is preferably a thermoplastic resin, such as polypropylene (PP), polyethylene (PE), ethylene-propylene copolymer, acrylic, polyurethane, polyvinyl chloride, polymethylene, polymethylpentene, polyethylene terephthalate (PET), polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, ABS, etc.

[0103] The thickness of the backer layer is preferably, for example, 100 μm or more and 400 μm or less.

[0104] <Manufacturing method of decorative sheet> The method for producing the decorative sheet of the present invention includes a step of applying the coating agent of the present invention onto a transparent resin layer and curing it to form a surface protective layer, and a step of embossing from the side having the surface protective layer. In the decorative sheet manufacturing method of the present invention, the coating agent contains urethane (meth)acrylate and a (meth)acrylic monomer of a specific molecular weight, so that even if a surface protective layer containing biomass-derived components is formed, a decrease in productivity during embossing can be suppressed.

[0105] In the method for producing a decorative sheet of the present invention, the order in which the layers are formed is not particularly important. For example, an adhesive auxiliary layer (pattern auxiliary layer), a pattern layer, an adhesive layer, a transparent resin layer, an adhesive auxiliary layer (surface adhesive auxiliary layer), and a surface protective layer may be formed in this order on one side of the base sheet. Furthermore, the steps of forming each layer do not need to proceed consecutively, and other steps or treatments may be carried out between these steps. Each layer may also be laminated on a releasable support, which will be described later.

[0106] <Release film> The release film of the present invention comprises the decorative sheet of the present invention as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided.

[0107] Examples of the releasable support include ester resins, olefin resins, styrene resins, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and carbonate resins.

[0108] The thickness of the releasable support may be, for example, 10 μm or more and 200 μm or less.

[0109] (decorative panels) The decorative sheet of the present invention may have an adherend laminated on the side of the base sheet opposite to the side having the pattern layer.

[0110] Examples of the adherend include wood boards, gypsum boards, cement boards, ceramic boards, metal boards, resin boards, and fiber-reinforced plastic boards. As a method for laminating the adherend, for example, the adherend may be laminated on the side of the base sheet opposite to the side having the pattern layer via the adhesive layer described above.

[0111] The present specification discloses the following:

[0112] The present invention (1) is a decorative sheet comprising at least a transparent resin layer and a surface protective layer, wherein the surface protective layer contains a cross-linked curable resin as a main component, an ultraviolet absorber, and a light stabilizer, the cross-linked curable resin containing at least one biomass-derived component and at least one (meth)acrylic monomer, and the ultraviolet absorber contains at least two ultraviolet absorbers having a benzotriazole skeleton. The present invention (2) is the decorative sheet according to the present disclosure (1), wherein the cross-linking curable resin further contains at least one urethane (meth)acrylate. The present invention (3) is a decorative sheet according to the present disclosure (1) or (2), wherein the at least two types of ultraviolet absorbers having a benzotriazole skeleton include an ultraviolet absorber A having a benzotriazole skeleton with a maximum absorption wavelength of less than 350 nm, and an ultraviolet absorber B having a benzotriazole skeleton with a maximum absorption wavelength of 350 nm or more. The present invention (4) is a decorative sheet according to any one of the present disclosures (1) to (3), wherein the surface protective layer has a total content of the at least two types of ultraviolet absorbers having a benzotriazole skeleton of 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cross-linked curable resin. The present invention (5) is a decorative sheet according to any one of the present disclosures (1) to (4), in which the light stabilizer is a reactive light stabilizer. The present invention (6) is the decorative sheet according to any one of the present disclosures (1) to (5), wherein the surface protective layer has a thickness of 3 μm or more and 30 μm or less. The present invention (7) is the decorative sheet according to any one of the present disclosures (1) to (6), wherein the surface protective layer further contains an inorganic filler. The present invention (8) is a decorative sheet according to any one of the present disclosures (1) to (7), which comprises a pattern layer and a base sheet, in this order, on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided, via an adhesive layer. The present invention (9) is the decorative sheet according to the present disclosure (8), wherein at least one of the substrate sheet, the adhesive layer, and the transparent resin layer contains a biomass-derived polyolefin. The present invention (10) is a decorative sheet according to any one of the present disclosures (1) to (9), which has an uneven shape on the side provided with the surface protective layer. The present invention (11) is a transfer film comprising a decorative sheet according to any one of the present disclosures (1) to (10) as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided. [Example]

[0113] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0114] Example 1 A colored substrate layer formed of a resin composition containing a biomass-derived polyolefin was prepared, and used as a substrate sheet. A back adhesive auxiliary layer (containing 53% by mass of ester-based polyurethane resin and 3% by mass of soluble nitrocellulose) was formed on one side of the base sheet so as to cover the entire surface by solid printing with an ink containing an organic solvent using a gravure printing method with an intaglio roll. On the other side of the base sheet, a 2 μm thick pattern auxiliary layer mainly composed of an acrylic-urethane resin was formed by solid printing with an ink containing an organic solvent using a gravure printing method with an intaglio roll so as to cover the entire surface, and then a 2 μm thick pattern layer (wood grain pattern) mainly composed of an acrylic-urethane resin was formed by partial printing with an ink containing a colorant and an organic solvent using a gravure printing method with an intaglio roll. An ester-based polyurethane was applied to the side of the pattern layer opposite the pattern auxiliary layer to form a 10 μm thick adhesive layer, and a 60 μm thick transparent olefin sheet was dry laminated onto the adhesive layer to form a transparent resin layer. Furthermore, a surface adhesion auxiliary layer made of an acrylic-urethane copolymer resin having a thickness of 2 μm was formed on the side of the transparent resin layer opposite the adhesive layer, and a coating agent was applied onto the surface adhesion auxiliary layer by gravure coating. After that, the coating agent was cured by irradiating it with ionizing radiation to form a surface protection layer having a thickness of 5 μm. Finally, the surface having the surface protective layer was embossed by heat and pressure to form a concave-convex shape, thereby producing a decorative sheet. The coating agent used to form the surface protection layer contained 30 parts by mass of biomass-derived glycerin triacrylate "Aronix M-930" (molecular weight: 348, manufactured by Toa Gosei Co., Ltd.) and 70 parts by mass of petrochemical-derived bifunctional urethane acrylate "RECRYL 270" (mass average molecular weight: 3000, manufactured by Daicel-Allnex Co., Ltd.) as resin components. In addition, 20 parts by mass of matte silica was blended per 100 parts by mass of the resin component, 2.0 parts by mass of a benzotriazole-based ultraviolet absorber (TINUVIN P manufactured by BASF, maximum absorption wavelength 340 nm) and 2.0 parts by mass of a benzotriazole-based ultraviolet absorber (TINUVIN326 manufactured by BASF, maximum absorption wavelength 353 nm) were blended as ultraviolet absorbers per 100 parts by mass of the resin component, and 1.0 part by mass of a hindered amine-based light stabilizer (TINUVIN123 manufactured by BASF) was blended as a light stabilizer per 100 parts by mass of the resin component.

[0115] Example 2 A decorative sheet was produced in the same manner as in Example 1, except that the light stabilizer incorporated into the coating agent used to form the surface protective layer was changed to a reactive light stabilizer (Sanol LS-3410, Nippon Nyukazai Co., Ltd.) at 1.0 part by mass per 100 parts by mass of the resin component.

[0116] Example 3 A decorative sheet was produced in the same manner as in Example 1, except that the ultraviolet absorbers incorporated into the coating agent used to form the surface protective layer were changed to 15 parts by mass of a benzotriazole-based ultraviolet absorber (TINUVIN P, manufactured by BASF, maximum absorption wavelength 340 nm) per 100 parts by mass of the resin component, and 15 parts by mass of a benzotriazole-based ultraviolet absorber (TINUVIN 326, manufactured by BASF, maximum absorption wavelength 353 nm) per 100 parts by mass of the resin component.

[0117] (Comparative Example 1) A decorative sheet was manufactured in the same manner as in Example 1, except that the ultraviolet absorber incorporated into the coating agent used to form the surface protective layer was changed to a benzotriazole-based ultraviolet absorber (TINUVIN P manufactured by BASF, maximum absorption wavelength 340 nm) in an amount of 2.0 parts by mass per 100 parts by mass of the resin component.

[0118] <Evaluation method>

[0119] (1) Weather resistance Using the ultra-accelerated weathering tester described below, the decorative sheets obtained in the Examples and Comparative Examples were subjected to 17 cycles (408 hours in total) of ultra-accelerated weathering tests (a test in which one cycle consisted of 20 hours of ultraviolet irradiation under the irradiation conditions described below, followed by 4 hours of condensation under the condensation conditions described below). After 408 hours had passed, the appearance of the decorative sheets was visually evaluated according to the following criteria. The evaluation results are shown in Table 1.

[0120] <Ultra-accelerated weathering test equipment> Ultra-accelerated weather resistance test equipment (product name: METAL WEATHER, model: KW-R7TP-A, manufactured by Daipla Wintes Co., Ltd.) <Irradiation conditions> Black panel temperature: 63℃ ·Illuminance: 65mW / cm 2 ·Battle humidity: 50%RH Duration: 20 hours <Condensation conditions> ·Illuminance: 0mW / cm 2 ·Battle humidity: 98%RH Duration: 4 hours

[0121] <Evaluation criteria> ++: No change in appearance was observed across the entire decorative sheet. +: Slight whitening occurred on the appearance of the decorative sheet. -: Significant changes in appearance occurred in the decorative sheet. In the above test, a "++" or "+" rating was considered a pass, and a "-" rating was considered a fail.

[0122] (2) Solvent resistance The surface protective layers of the decorative sheets obtained in the examples and comparative examples were subjected to a rubbing test using methyl ethyl ketone (MEK) (load 1500 g, contact area 5 cm 2 (300g / cm 2 The surface protective layer after the rubbing test was visually evaluated according to the following criteria. The evaluation results are shown in Table 1.

[0123] <Evaluation criteria> ++: No change in the appearance of the surface protective layer was observed. +: In terms of the appearance of the surface protective layer, there was a slight change in gloss in part, or slight whitening in part. - : Change in gloss or whitening occurred in the appearance of the surface protective layer. In the above test, a "++" or "+" rating was considered a pass, and a "-" rating was considered a fail.

[0124] [Table 1]

[0125] From Table 1, it was confirmed that by containing at least two types of ultraviolet absorbers having a benzotriazole skeleton in the cross-linked curable resin constituting the surface protective layer, a decorative sheet with excellent weather resistance can be obtained, even if it contains at least one type of biomass-derived component and at least one type of (meth)acrylic monomer. Furthermore, checking Example 3 in Table 1, it was confirmed that when the total amount of ultraviolet absorber blended was 30 parts by mass relative to 100 parts by mass of the cross-linked curable resin constituting the surface protection layer, the solvent resistance of the surface protection layer deteriorated. [Explanation of symbols]

[0126] 1 Base sheet 2. Picture layer 3 Transparent resin layer 4 Surface protective layer 5 Uneven shape 6 Adhesive auxiliary layer (pattern auxiliary layer) 7 Adhesive layer 8 Adhesion auxiliary layer (surface adhesion auxiliary layer) 9 Adhesion auxiliary layer (back side adhesion auxiliary layer) 10 Decorative Sheet

Claims

1. At least a transparent resin layer and a surface protective layer are provided, the surface protection layer contains a cross-linked curable resin as a main component, an ultraviolet absorber, and a light stabilizer; the cross-linked curable resin contains at least one biomass-derived component and at least one (meth)acrylic monomer; The decorative sheet contains at least two types of ultraviolet absorbers having a benzotriazole skeleton as the ultraviolet absorber.

2. 2. The decorative sheet according to claim 1, wherein said cross-linking curable resin further comprises at least one type of urethane (meth)acrylate.

3. 3. The decorative sheet according to claim 1 or 2, wherein the at least two types of ultraviolet absorbers having a benzotriazole skeleton include an ultraviolet absorber A having a benzotriazole skeleton with a maximum absorption wavelength of less than 350 nm, and an ultraviolet absorber B having a benzotriazole skeleton with a maximum absorption wavelength of 350 nm or more.

4. 3. The decorative sheet according to claim 1, wherein the surface protective layer contains at least two types of ultraviolet absorbers having a benzotriazole skeleton in a total amount of 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cross-linked curable resin.

5. 3. The decorative sheet according to claim 1, wherein the light stabilizer is a reactive light stabilizer.

6. 3. The decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 3 μm or more and 30 μm or less.

7. The decorative sheet according to claim 1 or 2, wherein the surface protective layer further contains an inorganic filler.

8. 3. The decorative sheet according to claim 1, further comprising a pattern layer and a base sheet in this order, on the side of said transparent resin layer opposite to the side on which said surface protective layer is provided, via an adhesive layer.

9. The decorative sheet according to claim 8 , wherein at least one of the substrate sheet, the adhesive layer, and the transparent resin layer contains a biomass-derived polyolefin.

10. The decorative sheet according to claim 1 or 2, wherein the surface on which the surface protective layer is provided has an uneven shape.

11. A transfer film comprising the decorative sheet according to claim 1 or 2 as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided.

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