Decorative sheets and decorative materials

Abstract

To provide a decorative sheet and a decorative material which can suppress lowering of weather resistance, even when a deep recess is formed on the surface.SOLUTION: There is provided a decorative sheet 10 in which a pattern layer 12, a transparent resin layer 15, and a surface protective layer 16 are laminated in this order, and recesses are formed in the surface protective layer 16 and the transparent resin layer 15, wherein the surface roughness on the surface side is 40 μm or more and 200 μm or less, a ratio of the surface roughness on the rear side to the surface roughness on the surface side is 20% or more and 60% or less, and the transparent resin layer 15 contains 0.1 pt.mass or more and 30 pts.mass or less of an ultraviolet absorber with respect to 100 pts.mass of a resin, and 0.1 pt.mass or more and 30 pts.mass or less of a photostabilizer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to decorative sheets and decorative materials used for interior materials such as wall materials for buildings such as houses, exterior materials for furniture, and interiors of vehicles such as automobiles. [Background technology]

[0002] In decorative sheets used for interior materials such as wall materials for buildings like houses, exterior materials for furniture, and the interiors of vehicles like automobiles, forming an embossed uneven surface can create a tactile feel and also provide visual shadows. Therefore, for example, forming an embossed uneven surface on a wood grain vessel pattern can realistically represent the rough surface of wood both tactilely and visually, resulting in a decorative sheet with a luxurious feel and a highly designed appearance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-149732 [Patent Document 2] Patent Publication No. 2021-167513 [Patent Document 3] Japanese Patent Application Publication No. 2019-064093 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when large embossments with concave and convex shapes are formed on the surface of a decorative sheet, the thickness of the concave portions becomes thin, which tends to cause a decrease in weather resistance.

[0005] In view of the above, an object of the present invention is to provide a decorative sheet and a decorative material that can suppress a decrease in weather resistance even when deep recesses are formed on the surface. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, the decorative sheet of the present invention is a decorative sheet in which a pattern layer, a transparent resin layer, and a surface protective layer are laminated in this order, and recesses are formed in the surface protective layer and the transparent resin layer, and is characterized in that the surface roughness of the front side is 40 μm or more and 200 μm or less, and the ratio of the surface roughness of the back side to the surface roughness of the front side is 20% or more and 60% or less, and the transparent resin layer contains 0.1 parts by mass or more and 30 parts by mass or less of an ultraviolet absorber and 0.1 parts by mass or more and 30 parts by mass or less of a light stabilizer per 100 parts by mass of resin.

[0007] Furthermore, the decorative sheet according to the present invention is preferably the decorative sheet described above, wherein the ultraviolet absorber is at least one of a benzophenone type, a benzotriazole type, and a triazine type, and the light stabilizer is an N-OR type hindered amine type.

[0008] Furthermore, in the decorative sheet according to the present invention, it is preferable that the thickness of the transparent resin layer is 50 μm or more and 150 μm or less.

[0009] Furthermore, the decorative sheet of the present invention is preferably the decorative sheet described above, wherein the surface protective layer contains 1 part by mass or more and 30 parts by mass or less of an ultraviolet absorber and 1 part by mass or more and 30 parts by mass or less of a light stabilizer per 100 parts by mass of resin.

[0010] Furthermore, the decorative sheet according to the present invention is preferably the decorative sheet described above, wherein the ultraviolet absorber is at least one of a benzophenone type, a benzotriazole type, and a triazine type, and the light stabilizer is an N-OR type hindered amine type.

[0011] Furthermore, in the decorative sheet according to the present invention, it is preferable that the thickness of the surface protective layer is 1 μm or more and 20 μm or less.

[0012] Furthermore, the decorative sheet of the present invention is preferably the decorative sheet described above, in which a colored resin layer, the pattern layer, the transparent resin layer, and the surface protection layer are laminated in this order, the colored resin layer containing polyvinyl chloride resin, and the transparent resin layer containing at least one of polyvinyl chloride resin and acrylic resin.

[0013] Furthermore, the decorative sheet of the present invention is preferably the decorative sheet described above, in which a colored resin layer, the pattern layer, the transparent resin layer, and the surface protection layer are laminated in this order, and the colored resin layer and the transparent resin layer contain polyolefin resin.

[0014] On the other hand, in order to solve the above-mentioned problems, the decorative material of the present invention is characterized by comprising the above-mentioned decorative sheet and a substrate laminated on the side opposite the surface protective layer of the decorative sheet. [Effects of the Invention]

[0015] According to the decorative sheet and decorative material of the present invention, the surface roughness of the front side is 40 μm or more and 200 μm or less, and the ratio of the surface roughness of the back side to the surface roughness of the front side is 20% or more and 60% or less, and the transparent resin layer contains 0.1 parts by mass or more and 30 parts by mass or less of an ultraviolet absorber and 0.1 parts by mass or more and 30 parts by mass or less of a light stabilizer per 100 parts by mass of resin, so that even if deep recesses are formed on the surface, a decrease in weather resistance can be suppressed. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a cross-sectional view showing a schematic structure of a first embodiment of a decorative sheet according to the present invention. [Figure 2] FIG. 2 is a cross-sectional view showing the schematic structure of a decorative material that uses the decorative sheet of FIG. [Figure 3] FIG. 2 is a cross-sectional view showing the schematic structure of a second embodiment of a decorative sheet according to the present invention. [Figure 4] FIG. 4 is a cross-sectional view showing the schematic structure of a decorative material that uses the decorative sheet of FIG. DETAILED DESCRIPTION OF THE INVENTION

[0017] Embodiments of the decorative sheet and decorative material according to the present invention will be described with reference to the drawings. Note that the present invention is not limited to the following embodiments described with reference to the drawings, and various technical matters described in each embodiment can be combined, substituted, omitted, etc. as needed.

[0018] [First embodiment] A first embodiment of a decorative sheet and decorative material according to the present invention will be described with reference to FIGS.

[0019] <Overall configuration of decorative sheet 10> As shown in FIG. 1, decorative sheet 10 has a pattern layer 12 that forms a pattern on a colored resin layer 11 made of a colored resin. A transparent resin layer 15 made of a transparent resin is provided on pattern layer 12. A surface protection layer 16 made of a transparent resin is provided on transparent resin layer 15. Decorative sheet 10 has a thickness T 10 However, it is preferable that the thickness is 80 μm or more and 350 μm or less.

[0020] <Colored resin layer 11> The colored resin layer 11 is colored opaquely and has hiding properties, allowing it to conceal color variations and defects on the back side, and allows the hue to be appropriately selected as the base color of the design layer 12. The colored resin layer 11 contains polyvinyl chloride (PVC) resin. Such colored resin layer 11 is preferably a colored PVC resin layer. PVC resin is flexible and suitable for printing, thermoplastic, has good moldability and processability, and can be reused as a recycled material.

[0021] The colored resin layer 11 is colored by mixing a colorant such as a pigment into a resin material such as PVC and kneading it together. While organic or inorganic pigments can be used as the colorant, inorganic pigments are preferred. In other words, the colored resin layer 11 preferably contains an inorganic substance as the colorant. Examples of the colorant include one or more inorganic substances such as calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0022] The colored resin layer 11 may further contain additives such as fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters, as needed.

[0023] The colored resin layer 11 has a thickness T 11 is preferably 30 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 50 μm or more and 100 μm or less. If it is less than 30 μm, flare or the like is likely to occur during production, which is likely to cause a decrease in productivity, and is therefore not very preferable. If it exceeds 150 μm, it is likely to cause a decrease in processability such as bending, and there is a risk of incurring an increase in production costs, which is also not very preferable.

[0024] <Picture layer 12> The pattern layer 12 is provided between the colored resin layer 11 and the transparent resin layer 15, and allows a pattern to be added to impart a design. Examples of patterns for the pattern layer 12 include wood grain patterns, stone grain patterns, fabric patterns, abstract patterns, geometric patterns, letters, symbols, solid colors, etc., or combinations thereof. The pattern layer 12 is formed by printing with printing ink or paint using various printing methods such as gravure printing and offset printing, or by applying various coating methods such as gravure coating and roll coating.

[0025] Printing inks, paints, etc. are formed by dissolving or dispersing a colorant such as a dye or pigment together with a binder resin in a dilution medium. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica. Examples of binder resins include urethane resins, acrylic resins, vinyl chloride acetate resins, polyimide resins, and soluble nitrocellulose.

[0026] The design layer 12 may contain functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, hardeners, hardening accelerators, and hardening retarders to impart various functions.

[0027] The pattern layer 12 has a thickness T 12 It is preferable that the thickness is 1 μm or more and 10 μm or less. If it is less than 1 μm, it becomes difficult to print clearly, which is not preferable. If it exceeds 10 μm, it is likely to cause a decrease in printing workability and may lead to an increase in manufacturing costs, which is not preferable.

[0028] <Transparent resin layer 15> The transparent resin layer 15 is provided to improve weather resistance, etc., and has a degree of transparency that allows for see-through, such as colorless transparency, colored transparency, or translucency, so that the design layer 12 can be seen. The transparent resin layer 15 contains at least one of PVC resin and acrylic resin. Such transparent resin layer 15 is preferably a transparent PVC resin layer or a transparent acrylic resin layer. PVC is flexible and suitable for printing, thermoplastic, has good moldability and processability, and can be reused as a recycled material.

[0029] The transparent resin layer 15 contains an ultraviolet absorber (UVA) and a light stabilizer (HALS). That is, the transparent resin layer 15 is preferably a transparent PVC resin or a transparent acrylic resin containing UVA and HALS. Such a transparent resin layer 15 can exhibit excellent weather resistance.

[0030] Examples of UVAs include benzophenone (BP)-based, benzotriazole (BT)-based, triazine (TA)-based, etc. Examples of BP-based agents include octabenzone, its modified products, polymers, and derivatives.

[0031] Examples of BT-based compounds include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and mixtures, modified products, polymers, and derivatives thereof.

[0032] Examples of TA-based compounds include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

[0033] Examples of HALS include N-OR type hindered amine radical scavengers, etc. Specific examples include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidylstearate, 1,2,2,6,6-pentamethyl-4-piperidylstearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetramethyl-4-piperidylstearate ... Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2 ,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octyl Amino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,Examples of suitable cyclohexane derivatives include 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, and the reaction product of 2-aminoethanol with a reaction product of bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate cyclohexane and N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide.

[0034] The combined use of such an N-OR type hindered amine-based HALS and a TA-based UVA is highly preferable because it can further improve weather resistance.

[0035] The transparent resin layer 15 preferably contains 0.1 to 30 parts by weight of UVA per 100 parts by weight of resin. Less than 0.1 parts by weight is undesirable because it is difficult to fully exhibit weather resistance. More than 30 parts by weight is undesirable because it is prone to bleed-out and deterioration of physical properties.

[0036] The transparent resin layer 15 preferably contains 0.1 to 30 parts by mass of HALS per 100 parts by mass of resin. Less than 0.1 parts by mass is undesirable because it is difficult to fully exhibit weather resistance. More than 30 parts by mass is undesirable because it is prone to bleed-out and a deterioration in physical properties.

[0037] The transparent resin layer 15 has a thickness T 15is preferably 50 μm or more and 150 μm or less, more preferably 50 μm or more and 100 μm or less, and even more preferably 60 μm or more and 80 μm or less. If it is less than 50 μm, it becomes difficult to fully exhibit weather resistance, which is not preferable. If it exceeds 150 μm, it is likely to cause a decrease in processability such as bending, and there is a risk of incurring an increase in manufacturing costs, which is not preferable.

[0038] <Surface protective layer 16> The surface protective layer 16 is provided to impart functions such as weather resistance, scratch resistance, contamination resistance, and design properties, and has a degree of transparency that allows for see-through, such as colorless transparency, colored transparency, or translucency, so that the picture layer 12 can be seen through the transparent resin layer 15. Examples of materials for the surface protective layer 16 include acrylic, urethane, acrylic silicone, fluorine-based, and epoxy-based resin compositions, with acrylic resins being particularly preferred.

[0039] Examples of the monomer component of the acrylic resin composition include cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, cyclohexylethyl (meth)acrylate, cyclohexylpropyl (meth)acrylate, cyclohexylbutyl (meth)acrylate, dimethylcyclohexane mono(meth)acrylate, dimethylcyclohexane di(meth)acrylate, trimethylcyclohexane mono(meth)acrylate, trimethylcyclohexane di(meth)acrylate, trimethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane mono(meth)acrylate, tetramethylcyclohexane di(meth)acrylate, tetramethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane tetra(meth)acrylate, dicyclohexylmethyl (meth)acrylate, dicyclohexylmethyl (meth)acrylate, phenoxycyclohexylmethyl (meth)acrylate, and methoxycyclohexylmethyl (meth)acrylate.

[0040] Among these monomer components, those having isomers can be used either individually or as a mixture. The inclusion of these monomer components can reduce affinity for water and suppress deterioration due to hydrolysis, etc. Note that (meth)acrylate refers to acrylate or methacrylate.

[0041] The content of (meth)acrylate is preferably in the range of 5% by mass to 50% by mass of all monomer components constituting the acrylic resin composition, i.e., of the monomer components of the acrylic resin composition that is the main component of the surface protective layer 16. If it is less than 5% by mass, it becomes difficult to sufficiently suppress deterioration, which is not preferable. If it exceeds 50% by mass, it is likely to cause a decrease in the various performance properties of the surface protective layer 16, such as improved surface hardness maintenance, improved stain resistance, and surface gloss adjustment, which is not preferable. Here, the above-mentioned "main component" means that the content of the acrylic resin composition constituting the surface protective layer 16 is 50% by mass or more relative to the total mass of the surface protective layer 16.

[0042] The surface protection layer 16 can be formed by applying a coating liquid of an acrylic resin composition containing the above-mentioned (meth)acrylate as a monomer component. Examples of methods for curing the applied coating liquid include a one-component curing type, a two-component curing type that uses a curing agent, and an active energy ray curing type that cures by irradiating with ultraviolet light or ionizing radiation. Among these, two-component curing types and active energy ray curing types are preferred in consideration of weather resistance, and two-component curing types that crosslink by isocyanate curing are preferred in consideration of post-processing properties.

[0043] The two-component curing acrylic resin composition is preferably a composition containing, for example, an acrylic resin having two or more functional groups, such as hydroxyl groups, amino groups, or carboxyl groups, in one molecule, and a polyisocyanate compound having two or more isocyanate groups in one molecule that can react with the functional groups. In particular, a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound is particularly preferred.

[0044] The acrylic polyol may be, for example, a (meth)acrylic acid ester copolymer containing hydroxyethyl (meth)acrylate as a monomer component in addition to cyclohexyl (meth)acrylate.

[0045] Examples of the polyisocyanate compound include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and hydrogenated compounds thereof, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, and biuret types obtained by combining these compounds.

[0046] Furthermore, it is also possible to use a composition in which a plurality of different types of polyisocyanates are mixed. Among these, taking into consideration weather resistance, HDI, HDI trimer type, TMP adduct type, and biuret type are preferred.

[0047] The amount of polyisocyanate compound mixed with the acrylic polyol is preferably set so that the equivalent ratio of hydroxyl groups to isocyanate groups is about 1 / 1 to 1 / 3. If the equivalent of hydroxyl groups is greater than the equivalent of isocyanate groups, sufficient crosslinking becomes difficult, which may cause a decrease in the functionality of the surface protective layer 16, which is undesirable.

[0048] On the other hand, in the case of an active energy ray curable type, a known monomer or oligomer having a (meth)acryloyl group can be used as the acrylic resin composition, and in addition to these monomers or oligomers, the above-mentioned (meth)acrylate can be contained.

[0049] Furthermore, the surface protection layer 16 contains UVA and HALS, similar to the transparent resin layer 15 described above, in order to further improve weather resistance.

[0050] As in the case of the transparent resin layer 15, examples of UVAs include BP-based, BT-based, and TA-based. Among them, TA-based compounds are preferred because the TA skeleton suppresses bleeding and is chemically more stable than the BP-based and BT-based skeletons, allowing UV absorption performance to be maintained for a long period of time. Hydroxyphenyltriazine (HPTA)-based compounds are particularly preferred.

[0051] Examples of HPTAs include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethylhexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy- [phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and the like can be mentioned.

[0052] The surface protective layer 16 preferably contains UVA in a range of 1 to 30 parts by mass per 100 parts by mass of the resin composition (e.g., an acrylic resin composition). Less than 1 part by mass is not preferred because it is difficult to sufficiently improve weather resistance. More than 30 parts by mass is not preferred because it is likely to cause a decrease in physical properties other than weather resistance of the surface protective layer 16.

[0053] When 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (for example, UVA "Tinuvin (registered trademark) 479 (product number)" manufactured by BASF Japan Ltd., hereinafter referred to as "UVAα") is used, the amount of the compounded resin is preferably in the range of 1 to 20 parts by mass, more preferably in the range of 5 to 15 parts by mass, and even more preferably in the range of 8 to 12 parts by mass, per 100 parts by mass of the resin composition.

[0054] Furthermore, when UVAα is used in combination with 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (for example, UVA "ADK STAB (registered trademark) LA-46 (product number)" manufactured by ADEKA CORPORATION / hereinafter referred to as "UVAβ"), even better weather resistance can be achieved.

[0055] This is because "UVAβ" has a high ability to absorb ultraviolet light in the short wavelength range, which is relatively high energy among ultraviolet light, and is chemically stable compared to other ultraviolet absorbers that absorb light in approximately the same wavelength range. Therefore, when used in combination with "UVAα," the wavelength range in which ultraviolet light is absorbed is broadened.

[0056] In such a combination, when the mixed amount of UVAβ is 100 parts by mass, it is preferable to mix UVAα in a range of 10 parts by mass to 200 parts by mass, more preferably in a range of 20 parts by mass to 100 parts by mass, and even more preferably in a range of 40 parts by mass to 80 parts by mass.

[0057] On the other hand, examples of HALS include N-OR type hindered amine radical scavengers, etc., similar to those used in the transparent resin layer 15. The combined use of such N-OR type hindered amine HALS and triazine type UVA is highly preferred, as it can further improve weather resistance.

[0058] The surface protective layer 16 preferably contains 1 to 30 parts by mass of HALS per 100 parts by mass of the resin composition. If the content is less than 1 part by mass, it is difficult to fully exhibit weather resistance, which is not preferred. If the content is more than 30 parts by mass, bleeding out is likely to occur and physical properties may be reduced, which is not preferred.

[0059] The surface protective layer 16 may further contain various additives, such as a heat stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as required.

[0060] As mentioned above, the surface protective layer 16 can be formed by applying a coating liquid. The surface protective layer 16 is formed when the amount of the coating liquid applied (mass of the coating film after drying) is 1 g / m 2 More than 20g / m 2 It is preferable that it is 3 g / m or less. 2 More than 18g / m 2 It is more preferable that it is 3 g / m or less. 2 More than 15g / m 2 In other words, the surface protection layer 16 has a thickness T 16 However, it is preferably 1 μm or more and 20 μm or less, more preferably 3 μm or more and 18 μm or less, and even more preferably 3 μm or more and 15 μm or less.

[0061] Application amount: 1g / m 2 less than the thickness T 16 If the thickness is less than 1 μm, it becomes difficult to fully exhibit weather resistance, which is not preferable. 2 That is, the thickness T 16 If the thickness exceeds 20 μm, productivity and processability such as bending workability are likely to decrease, and recyclability may be impaired, which is not preferable.

[0062] <Concave and convex parts> 1, the decorative sheet 10 according to this embodiment has a plurality of recesses 16a recessed inward on the surface of the surface protective layer 16. Recesses 15a corresponding to the shapes of the recesses 16a of the surface protective layer 16 are formed on the surface protective layer 16 side (surface side) of the transparent resin layer 15. Protrusions 15b corresponding to the positions and shapes of the recesses 15a are formed on the picture layer 12 side (back side) of the transparent resin layer 15.

[0063] On the transparent resin layer 15 side (front side) of the design layer 12, recesses 12a are formed corresponding to the shapes of the protrusions 15b of the transparent resin layer 15. On the colored resin layer 11 side (back side) of the design layer 12, protrusions 12b are formed corresponding to the positions and shapes of the recesses 12a.

[0064] On the pattern layer 12 side (front surface side) of the colored resin layer 11, recesses 11a are formed corresponding to the shapes of the protrusions 12b of the pattern layer 12. On the back surface side of the colored resin layer 11, protrusions 11b are formed corresponding to the positions of the recesses 11a.

[0065] The recesses 11a, 12a, 15a, 16a and the protrusions 11b, 12b, 15b can be formed as follows: An embossing roll, on the circumferential surface of which an embossing plate with a plurality of convex protrusions is attached, and a rubber roll, on the circumferential surface of which an elastic rubber blanket is attached, are placed in contact with each other and rotated synchronously.

[0066] At the same time, the decorative sheet 10 is fed between the embossing roll and the rubber roll so that the front side (surface protective layer 16 side) of the decorative sheet 10 faces the embossing roll, in other words, so that the back side (colored resin layer 11 side) faces the rubber roll. As a result, the protrusions of the embossing plate of the embossing roll press the decorative sheet 10 from the front side (surface protective layer 16 side), forming recesses 11a, 12a, 15a, 16a and protrusions 11b, 12b, 15b in the decorative sheet 10.

[0067] <Surface roughness and embossing strike-through rate> At this time, the depth and height of the recesses 11a, 12a, 15a, 16a and the protrusions 11b, 12b, 15b can be set by adjusting the pressure between the embossing roll and the rubber roll, and the hardness and thickness of the rubber blanket of the rubber roll. In other words, the surface roughness Rz(f) of the front side (surface protective layer 16 side) and the surface roughness Rz(b) of the back side (colored resin layer 11 side) of the decorative sheet 10 can be adjusted appropriately.

[0068] Here, the height of the convex portions 11b protruding from the back side of the colored resin layer 11 is smaller than the depth of the concave portions 16a formed by the embossing plate. This is because the resin portion pressed by the protrusions of the embossing plate deforms not only in the pressing direction of the embossing plate but also in a direction intersecting the pressing direction, preventing the resin from moving only in the pressing direction. As a result, the surface roughness Rz(b) of the back side (colored resin layer 11 side) of the decorative sheet 10 is smaller than the surface roughness Rz(f) of the front side (surface protective layer 16 side) (Rz(f) > Rz(b)). Furthermore, because the resin also deforms in a direction intersecting the pressing direction, the thickness around the concave portions increases, and the reduction in thickness of the concave portions is smaller than the difference (Rz(f) - Rz(b)) between the surface roughness Rz(f) of the front side and the surface roughness Rz(b) of the back side.

[0069] The surface roughness Rz(f) of the front side and the surface roughness Rz(b) of the back side are values ​​determined in accordance with the maximum height Rz specified in the Japanese Industrial Standard "JIS B 0601."

[0070] In the decorative sheet 10 according to this embodiment, the surface roughness Rz(f) of the front side is set to 40 μm or more and 200 μm or less. If it is less than 40 μm, it will not be possible to produce a decorative sheet with a high-quality and stylish design, and if it exceeds 200 μm, the sheet thickness in the recessed portions will be too thin, which will easily cause a decrease in weather resistance.

[0071] In particular, the surface roughness Rz(f) of the front side is preferably 100 μm or more and 180 μm or less. If it is 100 μm or more, a decorative sheet with a very luxurious and highly designed appearance can be obtained, and if it is 180 μm or less, deterioration of weather resistance can be suppressed while maintaining the design.

[0072] Furthermore, in the decorative sheet 10 according to this embodiment, the embossing strike-through rate Tr (= (Rz(b) / Rz(f)) × 100), which is the ratio of the backside surface roughness Rz(b) to the frontside surface roughness Rz(f) (Rz(b) / Rz(f)), is 20% or more and 60% or less. If it is less than 20%, the thickness of the recesses 11a, 12a, 15a, 16a and the protrusions 11b, 12b, 15b of the decorative sheet 10 will be too thin, resulting in a decrease in weather resistance, while if it exceeds 60%, the unevenness on the backside of the decorative sheet 10 will be too great, which may cause a decrease in adhesion to the substrate.

[0073] In particular, the embossing strike-through rate Tr is preferably 30% or more and 50% or less. When it is 30% or more, sufficient weather resistance can be exhibited, and when it is 50% or less, sufficient adhesion to the substrate can be exhibited.

[0074] <Thickness> The thickness T of each layer 11, 12, 15, and 16 11 ,T 12 ,T 15 ,T 16 is the length between each of the front surfaces (upper surfaces in FIG. 1) and rear surfaces (lower surfaces in FIG. 1) before the embossing process. 10 is the length between the surface before the above-mentioned embossing, i.e., the surface of the upper surface protection layer 16 (top surface in Figure 1), and the back surface, i.e., the back surface of the lower colored resin layer 11 (bottom surface in Figure 1).

[0075] <Method for manufacturing decorative sheet 10> The decorative sheet 10 according to this embodiment can be manufactured as follows: A colored resin layer 11 is formed into a sheet shape by mixing and kneading a colorant such as a pigment into a resin material such as PVC, and a pattern is printed with ink to form a pattern layer 12. Furthermore, a surface protective layer 16 is formed on a transparent resin layer 15 formed into a sheet shape by mixing and kneading UVA or HALS into PVC or acrylic resin, and a coating liquid of an acrylic resin composition mixed with UVA or HALS is applied and cured.

[0076] The design layer 12 and the transparent resin layer 15 are then laminated together and heated while undergoing doubling embossing using the embossing roll and rubber roll described above, thereby bonding the design layer 12 and the transparent resin layer 15 and simultaneously forming recesses 11a, 12a, 15a, and 16a and protrusions 11b, 12b, and 15b, thereby obtaining the decorative sheet 10 according to this embodiment.

[0077] <Overall structure of decorative material 100> In the decorative material 100 according to this embodiment, which uses such a decorative sheet 10, as shown in Figure 2, the colored resin layer 11 of the decorative sheet 10 is bonded to a substrate 101 via an adhesive layer 102. In other words, the substrate 101 is laminated on the side of the decorative sheet 10 opposite the surface protective layer 16.

[0078] <Substrate 101> Materials for the substrate 101 include metals such as steel plate and aluminum plate, wood materials such as wood veneer, wood plywood, laminated lumber, particle board, hard fiberboard, and medium-density fiberboard (MDF), and resins such as PVC resin. Substrates 101 made of PVC resin have high thermal insulation properties and are in high demand as window frame fittings (sashes). Furthermore, in decorative materials 100 in which the substrate 101 is made of PVC resin, the decorative sheet 10 is mostly made of PVC, so that the substrate 101 can be dissolved and reused together with the decorative sheet 10, further improving recyclability.

[0079] <Adhesive layer 102> The adhesive layer 102 is a layer for bonding the substrate 101 and the colored resin layer 11 of the decorative sheet 10. Examples of adhesives that can be used for the adhesive layer 102 include urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, and polyester-based adhesives. In particular, a two-component curing urethane-based adhesive that combines polyester polyol and polyisocyanate is preferred. The adhesive layer 102 has a thickness that allows the protrusions 11b of the colored resin layer 11 of the decorative sheet 10 to be embedded therein, thereby bonding the decorative sheet 10 and the substrate 101 together, and is preferably, for example, 10 μm or more and 200 μm or less.

[0080] <Actions and Effects of the Decorative Sheet 10 and the Decorative Material 100> In this embodiment, the surface roughness Rz(f) of the front side of the decorative sheet 10 is 40 μm or more and 200 μm or less, and the embossing strike-through rate Tr of the decorative sheet 10 is 20% or more and 60% or less. Furthermore, the transparent resin layer 15 contains 0.1 parts by mass or more and 30 parts by mass or less of UVA and 0.1 parts by mass or more and 30 parts by mass or less of HALS per 100 parts by mass of resin. Therefore, even if the front side of the decorative sheet 10 is embossed with a large uneven shape such as a wood grain vascular pattern, that is, even if the recesses 16a of the surface protective layer 16 are formed large (deep), the thickness reduction of the recessed portions of the decorative sheet 10 can be greatly suppressed, and a decrease in weather resistance can be suppressed.

[0081] Therefore, the decorative sheet 10 and decorative material 100 of this embodiment can realistically express the rough surface condition of wood both tactilely and visually, thereby creating a luxurious feel with a highly designed appearance while maintaining weather resistance.

[0082] Furthermore, if the colored resin layer 11 and the transparent resin layer 15 are made of PVC, the recyclability of the decorative material 100, in which the decorative sheet 10 is attached to the substrate 101 made of PVC resin, which is in increasing demand as window frame fittings (sashes), can be further improved.

[0083] [Second embodiment] A second embodiment of the decorative sheet and decorative material according to the present invention will be described with reference to Figures 3 and 4. However, for parts similar to those in the previously described embodiment, the same reference numerals as those used in the description of the previously described embodiment will be used, and explanations that overlap with those in the previously described embodiment will be omitted.

[0084] <Overall configuration of decorative sheet 20> As shown in FIG. 3, the decorative sheet 20 has a pattern layer 12 that forms a pattern on a colored resin layer 21 made of a colored resin. An anchor layer 23 made of a transparent resin is provided on the pattern layer 12. A transparent adhesive layer 24 made of a transparent adhesive resin is provided on the anchor layer 23. A transparent resin layer 25 made of a transparent resin is provided on the transparent adhesive layer 24. A surface protection layer 16 made of a transparent resin is provided on the transparent resin layer 25. A base layer 27 made of a resin is provided on the back surface (lower surface in FIG. 3) of the colored resin layer 21. The decorative sheet 20 has a thickness T 20 However, it is preferable that the thickness is 85 μm or more and 400 μm or less.

[0085] <Colored resin layer 21> Like the colored resin layer 11 of the above-described embodiment, the colored resin layer 21 is colored opaquely and has concealing properties, making it possible to conceal color variations and defects on the back surface, and also to select an appropriate hue as the base color of the design layer 12. The colored resin layer 21 contains a polyolefin resin such as polyethylene (PE) resin or polypropylene (PP) resin. Such a colored resin layer 21 is preferably a colored polyolefin resin layer.

[0086] The colored resin layer 21 has a thickness T 21 However, the thickness T of the colored resin layer 21 in the above-described embodiment 11 Similarly, the thickness is preferably 30 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 50 μm or more and 100 μm or less. Otherwise, the colored resin layer 21 is similar to the colored resin layer 11 of the above-described embodiment.

[0087] <Anchor Layer 23> The anchor layer 23 is provided to improve adhesion to the colored resin layer 21 via the pattern layer 12, and has transparency such as colorless transparency, colored transparency, or translucency, so that the pattern layer 12 can be seen. Examples of materials for the anchor layer 23 include polyurethane resin. The anchor layer 23 has a thickness T 23 It is preferable that the thickness is 1 μm or more and 10 μm or less.

[0088] <Transparent adhesive layer 24> The transparent adhesive layer 24 is provided to bond the transparent resin layer 25 and the anchor layer 23, and has transparency such as colorless transparency, colored transparency, or translucency, so that the design layer 12 can be seen through the anchor layer 23. Examples of materials for the transparent adhesive layer 24 include polyolefin resin. The transparent adhesive layer 24 has a thickness T 24 It is preferable that the thickness is 1 μm or more and 20 μm or less.

[0089] <Transparent resin layer 25> The transparent resin layer 25 has transparency such as colorless transparency, colored transparency, or translucency, allowing the design layer 12 to be seen through the transparent adhesive layer 24 and the anchor layer 23. The transparent resin layer 25 contains a polyolefin resin such as PE resin or PP resin. Such a transparent resin layer 25 is preferably a transparent polyolefin resin layer.

[0090] The transparent resin layer 25 has a thickness T 25 However, the thickness T of the transparent resin layer 15 in the above-described embodiment 15 Similarly, the thickness is preferably 50 μm or more and 150 μm or less, more preferably 50 μm or more and 100 μm or less, and even more preferably 60 μm or more and 80 μm or less. Otherwise, the transparent resin layer 25 is similar to the transparent resin layer 15 of the above-described embodiment.

[0091] <Base layer 27> The underlayer 27 is provided to improve the adhesion between the substrate 101 and the colored resin layer 21 and the corrosion resistance of the substrate 101. Examples of materials for the underlayer 27 include polyurethane resin. The underlayer 27 may contain an anti-rust pigment to further improve the corrosion resistance. The underlayer 27 has a thickness T 27 It is preferable that the thickness is 1 μm or more and 10 μm or less.

[0092] That is, the decorative sheet 10 according to the above-described embodiment is a case in which a colored resin layer 11 made of PVC resin and a transparent resin layer 15 made of PVC resin or acrylic resin are applied, whereas the decorative sheet 20 according to the present embodiment is a case in which a colored resin layer 21 and a transparent resin layer 25 made of polyolefin resin are applied.

[0093] <Concave and convex parts> 3, the decorative sheet 20 according to this embodiment has a plurality of recesses 16a formed on the surface of the surface protective layer 16. Recesses 25a corresponding to the shapes of the recesses 16a of the surface protective layer 16 are formed on the surface protective layer 16 side (surface side) of the transparent resin layer 25. Protrusions 25b corresponding to the positions and shapes of the recesses 25a are formed on the transparent adhesive layer 24 side (back side) of the transparent resin layer 25.

[0094] On the transparent resin layer 25 side (surface side) of the transparent adhesive layer 24, recesses 24a are formed corresponding to the shapes of the protrusions 25b of the transparent resin layer 25. On the anchor layer 23 side (back side) of the transparent adhesive layer 24, protrusions 24b are formed corresponding to the positions and shapes of the recesses 24a. On the transparent adhesive layer 24 side (surface side) of the anchor layer 23, recesses 23a are formed corresponding to the shapes of the protrusions 24b of the transparent adhesive layer 24.

[0095] Convex portions 23b are formed on the pattern layer 12 side (rear side) of the anchor layer 23 so as to correspond to the positions and shapes of the concave portions 23a. Concave portions 12a are formed on the anchor layer 23 side (front side) of the pattern layer 12 so as to correspond to the shapes of the convex portions 23b of the anchor layer 23. Convex portions 12b are formed on the colored resin layer 21 side (rear side) of the pattern layer 12 so as to correspond to the positions and shapes of the concave portions 12a.

[0096] On the pattern layer 12 side (surface side) of the colored resin layer 21, recesses 21a are formed corresponding to the shapes of the protrusions 12b of the pattern layer 12. On the base layer 27 side (back side) of the colored resin layer 21, protrusions 21b are formed corresponding to the positions and shapes of the recesses 21a. On the colored resin layer 21 side (surface side) of the base layer 27, recesses 27a are formed corresponding to the shapes of the protrusions 21b of the colored resin layer 21. On the back side of the base layer 27, protrusions 27b are formed corresponding to the positions of the recesses 27a.

[0097] The recesses 21a, 12a, 23a, 24a, 25a, 16a, and 27a and the protrusions 21b, 12b, 23b, 24b, 25b, and 27b can be formed in the same manner as in the above-described embodiment.

[0098] <Surface roughness and embossing strike-through rate> In the decorative sheet 20 according to this embodiment, like the decorative sheet 10 according to the previously described embodiment, the surface roughness Rz(f) of the front side is 40 μm or more and 200 μm or less, and particularly preferably 100 μm or more and 180 μm or less. Furthermore, in the decorative sheet 20 according to this embodiment, like the decorative sheet 10 according to the previously described embodiment, the embossing strike-through rate Tr is 20% or more and 60% or less, and particularly preferably 30% or more and 50% or less.

[0099] <Thickness> The thickness T of each layer 21, 23 to 25, 27 21 ,T 23 ~T 25 ,T 27As in the case of the above-described embodiment, the thickness T of the decorative sheet 20 is the length between the front surface (upper surface in FIG. 3) and the back surface (lower surface in FIG. 3) before embossing. 20 As in the above-described embodiment, the length is the length between the surface before embossing, i.e., the surface (top surface in Figure 3) of the upper surface protection layer 16, and the back surface, i.e., the back surface (bottom surface in Figure 3) of the lower base layer 27.

[0100] <Method for manufacturing decorative sheet 20> The decorative sheet 20 according to this embodiment can be manufactured as follows: A colored resin layer 21 is formed into a sheet shape by mixing and kneading a coloring agent such as a pigment into a polyolefin resin, and a pattern is printed with ink on the front side of the colored resin layer 21 to form the pattern layer 12. At the same time, a base layer 27 is formed on the back side of the colored resin layer 21 by printing an ink such as polyurethane resin. Then, a coating liquid such as polyurethane resin is applied onto the pattern layer 12 to form the anchor layer 23.

[0101] Next, a transparent adhesive layer 24 and a transparent resin layer 25 are laminated on the anchor layer 23 by co-extrusion of a polyolefin resin or the like, and then a coating liquid of an acrylic resin composition is applied to the transparent resin layer 25 and cured to form the surface protective layer 16. Then, the surface protective layer 16 is embossed using the embossing roll and rubber roll described above to form recesses 21a, 12a, 23a, 24a, 25a, 16a, and 27a and protrusions 21b, 12b, 23b, 24b, 25b, and 27b. This allows the decorative sheet 20 according to this embodiment to be obtained.

[0102] <Overall structure of decorative material 200> In the decorative material 200 according to this embodiment, which uses such a decorative sheet 20, as shown in Figure 4, the base layer 27 of the decorative sheet 20 is bonded to a substrate 101 via an adhesive layer 102. In other words, the substrate 101 is laminated on the side of the decorative sheet 20 opposite the surface protection layer 16.

[0103] <Actions and Effects of the Decorative Sheet 20 and the Decorative Material 200> In this embodiment, as in the previously described embodiments, the surface roughness Rz(f) of the front side of the decorative sheet 20 is 40 μm or more and 200 μm or less, and the embossing strike-through rate Tr of the decorative sheet 20 is 20% or more and 60% or less. Furthermore, the transparent resin layer 25 contains 0.1 parts by mass or more and 30 parts by mass or less of UVA and 0.1 parts by mass or more and 30 parts by mass or less of HALS per 100 parts by mass of resin. Therefore, even if the front side of the decorative sheet 20 is embossed with a large uneven shape such as a wood grain vascular pattern, i.e., the recesses 16a of the surface protective layer 16 are formed large (deep), it is possible to significantly prevent a decrease in the thickness of the recessed portions of the decorative sheet 20 and to prevent a decrease in weather resistance, as in the previously described embodiments.

[0104] Therefore, with the decorative sheet 20 and decorative material 200 of this embodiment, similar to the decorative sheet 10 and decorative material 100 of the previously described embodiment, the rough surface condition of wood can be realistically expressed both tactilely and visually, thereby creating a luxurious feel with a highly designed design while being weather resistant.

[0105] [Other embodiments] In the above-described embodiment, the decorative sheets 10, 20 have been described as having the colored resin layers 11, 21, but the present invention is not limited to this. In other embodiments, for example, the colored resin layers 11, 21 can be omitted, and a decorative sheet can be provided in which a pattern layer 12 is provided on the back side of the transparent resin layers 15, 25 and a surface protection layer 16 is provided on the front side of the transparent resin layers 15, 25.

[0106] In this case, depending on the design of the design layer 12, if the back side of the design layer 12 is visible, causing inconvenience, it is preferable to provide a concealing layer on the back side of the design layer 12 using an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0107] Furthermore, in the above-described embodiment, the decorative sheets 10, 20 were described in which the surface protective layer 16 was formed by applying a coating liquid of an acrylic resin composition onto the transparent resin layer 15, 25, and then the recesses were formed by embossing, but the present invention is not limited to this. In another embodiment, for example, it is also possible to form recesses by embossing the transparent resin layer 15, 25, and then apply a coating liquid of an acrylic resin composition and wipe it, thereby providing the surface protective layer 16 on the surface of the transparent resin layer 15, 25 and inside the recesses.

[0108] In the above-described embodiment, only the surface protective layer 16 is provided on the transparent resin layers 15 and 25, but the present invention is not limited to this. In another embodiment, for example, a gloss-adjusting layer that matches the pattern of the pattern layer 12 may be further provided on the surface protective layer 16 to further enhance the design and luxury feel. [Example]

[0109] Examples of the decorative sheet and decorative material according to the present invention will be specifically described below, but the present invention is not limited to the specific examples described below.

[0110] [Preparation of test specimens and comparison specimens] <Test specimen 1> Colored PVC resin sheet (thickness (T 11 A pattern was printed on the colored resin layer 11 with ink for PVC resin using a mixed resin of acrylic resin and vinyl chloride-vinyl acetate copolymer resin as a binder to form a pattern layer 12 (thickness (T 12 In addition, a PVC sheet (thickness (T) 1 μm) containing TA-type UVA (0.5 parts by mass) and N-OR type hindered amine-type HALS (0.5 parts by mass) was formed. 15 ) 80 μm) was used as the transparent resin layer 15, and a coating liquid of an acrylic resin composition containing TA-type UVA and N-OR type hindered amine-based HALS and having the following composition ratio was applied (3 g / m) on the transparent resin layer 15. 2 ) and hardening, the surface protection layer 16 (thickness (T16 ) 3 μm).

[0111] 《Surface protective layer》 Main ingredient: Methyl methacrylate (95) / 2-hydroxyethyl methacrylate (5) 90 parts by mass of copolymer Hardener: 10 parts by weight of "Takenate (registered trademark) D170 (product number)" manufactured by Mitsui Chemicals, Inc. UVA: 9 parts by weight of "Tinuvin (registered trademark) 479 (product number)" manufactured by BASF Japan Ltd. HALS: 1 part by weight of "Tinuvin (registered trademark) 123 (product number)" manufactured by BASF Japan Ltd. Solvent: 240 parts by weight of ethyl acetate

[0112] Then, the design layer 12 and the transparent resin layer 15 are laminated together and heated while undergoing doubling embossing using an embossing roll and a rubber roll, thereby forming a decorative sheet 10 (thickness (T 10 ) 164 μm) specimen 1 was prepared.

[0113] <Test specimen 2> PVC sheet (thickness (T 15 A coating liquid of an acrylic resin composition containing UVA (0.1 parts by mass) and HALS (0.1 parts by mass) was applied (1 g / m) onto the transparent resin layer 15. 2 ) and hardening, the surface protection layer 16 (thickness (T 16 Otherwise, the same procedure as in the case of specimen 1 was carried out to obtain a decorative sheet 10 (thickness (T 10 ) 132 μm) specimen 2 was prepared.

[0114] <Test specimen 3> PVC sheet (thickness (T 15A coating liquid of an acrylic resin composition containing UVA (1 part by mass) and HALS (1 part by mass) was applied (15 g / m) onto the transparent resin layer 15. 2 ) and hardening, the surface protection layer 16 (thickness (T 16 Otherwise, the same procedure as in the case of specimen 1 was carried out to obtain a decorative sheet 10 (thickness (T 10 ) 156 μm) specimen 3 was prepared.

[0115] <Test piece 4> PVC sheet (thickness (T 15 A coating liquid of an acrylic resin composition containing UVA (10 parts by mass) and HALS (10 parts by mass) was applied (18 g / m) onto the transparent resin layer 15. 2 ) and hardening, the surface protection layer 16 (thickness (T 16 Otherwise, the same procedure as in the case of specimen 1 was carried out to obtain a decorative sheet 10 (thickness (T 10 ) 199 μm) specimen 4 was prepared.

[0116] <Test specimen 5> PVC sheet (thickness (T 15 A coating liquid of an acrylic resin composition containing UVA (30 parts by mass) and HALS (30 parts by mass) was applied (20 g / m) onto the transparent resin layer 15. 2 ) and hardening, the surface protection layer 16 (thickness (T 16 Otherwise, the same procedure as in the case of specimen 1 was carried out to obtain a decorative sheet 10 (thickness (T 10 ) 251 μm) specimen 5 was prepared.

[0117] <Test piece 6> Specimen 6 of the decorative sheet 10 was prepared in the same manner as specimen 1, except that a PVC sheet (transparent resin layer 15) containing BT-type UVA instead of TA-type UVA and a coating liquid of an acrylic resin composition (surface protective layer 16) were applied.

[0118] <Test specimen 7> Specimen 7 of the decorative sheet 10 was prepared in the same manner as specimen 1, except that a PVC sheet (transparent resin layer 15) containing BP-based UVA instead of TA-based UVA and a coating liquid of an acrylic resin composition (surface protective layer 16) were applied.

[0119] <Test piece 8> Specimen 8 of the decorative sheet 10 was produced in the same manner as specimen 1, except that the transparent resin layer 15 was an acrylic resin sheet instead of PVC.

[0120] <Test specimen 9> Colored PP resin sheet (thickness (T 21 A pattern is printed on the surface of the colored resin layer 21 with an ink for polyolefin resin using polyurethane resin as a binder to form a pattern layer 12 (thickness (T 12 ) 1 μm) is formed, and a base layer 27 (thickness (T 27 After providing the pattern layer 12 with a coating liquid of polyurethane resin, an anchor layer 23 (thickness (T 23 )1μm).

[0121] Next, the PP resin is extruded to form a transparent adhesive layer 24 (thickness (T 24 While forming the transparent resin layer 25 (thickness (T ) 10 μm), a PP resin containing a TA-based UVA (0.5 parts by mass) and an N-OR type hindered amine-based HALS (0.5 parts by mass) was co-extruded to form the transparent resin layer 25 (thickness (T 25 After the transparent resin layer 25 is laminated on the anchor layer 23 while being laminated on the transparent adhesive layer 24, a coating liquid of the same acrylic resin composition as that of the test piece 1 is applied to the transparent resin layer 25 and cured to form a surface protective layer 16 (thickness (T 16) 3 μm).

[0122] Then, the surface protective layer is embossed using an embossing roll and a rubber roll to form a decorative sheet 20 (thickness (T 20 ) 155 μm) specimen 9 was prepared.

[0123] <Comparative example 1> UVA and HALS-free (additive-free) PVC sheet (thickness (T 15 Comparative decorative sheet 1 (thickness 122 μm) was prepared in the same manner as specimen 2, except that a transparent resin layer (thickness 40 μm) was used and a surface protective layer was formed by applying a coating liquid of an acrylic resin composition that did not contain UVA or HALS (additive-free).

[0124] <Comparative body 2> Comparative specimen 2 of decorative sheet (thickness 132 μm) was produced in the same manner as specimen 2, except that the surface roughness Rz(f) and Rz(b) were set to the values ​​shown in Table 1.

[0125] <Comparative body 3> Comparative specimen 3 of decorative sheet (thickness 251 μm) was produced in the same manner as specimen 5, except that the surface roughness Rz(f) and Rz(b) were set to the values ​​shown in Table 1.

[0126] [Characteristic Value] <Surface roughness Rz(f), Rz(b)> The surface roughness Rz(f) of the front side and the surface roughness Rz(b) of the back side of the test specimens 1 to 9 and the comparative specimens 1 to 3 were measured in accordance with the maximum height Rz specified in the Japanese Industrial Standard "JIS B 0601."

[0127] <Embossing strike-through rate Tr> The embossing strike-through rate Tr (= (Rz(b) / Rz(f)) × 100) was calculated from the measured surface roughness Rz(f) and Rz(b) for each of the test specimens 1 to 9 and the comparative specimens 1 to 3. The results are shown in Table 1.

[0128] [Evaluation method] <Design> The design of test specimens 1 to 9 and comparative specimens 1 to 3 was evaluated visually and by touch. The results are shown in Table 2. In Table 2, "◎" indicates that a strong three-dimensional effect and texture were obtained both visually and tactilely, "◯" indicates that a strong three-dimensional effect and texture were obtained only by touch, and "×" indicates that almost no three-dimensional effect and texture were obtained by both visually and tactilely.

[0129] <Weather resistance> Test specimens 1 to 9 and comparative specimens 1 to 3 were subjected to a 504-hour weathering test using an ultra-accelerated weathering tester ("Metal Weather (registered trademark)" manufactured by Daipla Wintes Co., Ltd.) under the following conditions: 20 hours of UV light exposure and 4 hours of condensation were repeated. The weathering resistance of test specimens 1 to 9 and comparative specimens 1 to 3 was evaluated by determining the color difference ΔE on the front side before and after the test. The results are shown in Table 2 below. In Table 2, "◎" indicates that the color difference ΔE was less than 2 (ΔE<2), "◯" indicates that the color difference ΔE was 2 or more but less than 4 (2≦ΔE<4), and "×" indicates that the color difference ΔE was 4 or more (ΔE≧4).

[0130] <Test conditions> ·UV light illuminance: 65mW / cm 2 Black panel temperature: 63°C

[0131] <Recyclability> Test specimens 1 to 9 and comparative specimens 1 to 3 were each attached to a PVC substrate. These were then crushed into pellets and remolded onto substrates to evaluate their recyclability. The results are shown in Table 2 below. In Table 2, a "○" indicates that the specimens could be molded almost as well as new PVC materials, demonstrating good recyclability, while an "×" indicates that the specimens presented practical problems compared to new PVC materials, making them unsuitable for recycling.

[0132] [result] The physical property values ​​of test specimens 1 to 9 and comparative specimens 1 to 3 are shown in Table 1, and the evaluation results are shown in Table 2.

[0133] [Table 1]

[0134] [Table 2]

[0135] As can be seen from Tables 1 and 2, Comparative Sample 1, which does not contain UVA or HALS in the surface protective layer, achieved a design rating of "Good" but weather resistance rating of "Poor." Comparative Sample 2, which had a surface roughness Rz(f) of less than 40 μm and an embossing strike-through rate Tr of less than 20%, achieved a weather resistance rating of "Good" but design rating of "Poor." On the other hand, Comparative Sample 3, which had a surface roughness Rz(f) of more than 200 μm and an embossing strike-through rate Tr of more than 60%, achieved a design rating of "Good" but weather resistance rating of "Poor."

[0136] In contrast, specimens 1 to 9 were rated "○" or better for both design and weather resistance. In particular, specimens 1 and 3 to 9, whose transparent resin layer contained UVA and HALS in an amount of 0.5 to 30 parts by mass, received a "◎" for weather resistance. Among these, specimens 3 to 5, whose surface roughness Rz(f) was 100 μm to 200 μm and whose embossing strike-through rate Tr was 40% to less than 60%, also received a "◎" for design. Note that specimen 9, which used PP resin for the transparent resin layer and surface protective layer, received a "×" for recyclability.

[0137] From the above, the effects of the decorative sheet and decorative material according to the present invention could be confirmed. [Industrial Applicability]

[0138] The decorative sheet and decorative material of the present invention can suppress a decrease in weather resistance even when deep recesses are formed on the surface, and therefore can be used extremely beneficially in various industries including the construction industry. [Explanation of symbols]

[0139] 10 Decorative Sheet 11 Colored resin layer 11a Recess 11b Convex part 12 Picture layer 12a Recess 12b Convex part 15 Transparent resin layer 15a Recess 15b Convex part 16 Surface protective layer 16a Recess 20 Decorative Sheet 21 Colored resin layer 21a Recess 21b Convex part 23 Anchor layer 23a Recess 23b Convex part 24 Transparent adhesive layer 24a Recess 24b Convex part 25 Transparent resin layer 25a Recess 25b Convex part 27 Base layer 27a Recess 27b Convex part 100,200 Cosmetic materials 101 Substrate 102 Adhesive layer

Claims

1. A decorative sheet comprising a pattern layer, a transparent resin layer, and a surface protective layer laminated in this order, and recesses formed in the surface protective layer and the transparent resin layer, The surface roughness of the front side is 40 μm or more and 200 μm or less, and The ratio of the surface roughness of the back side to the surface roughness of the front side is 20% or more and 60% or less, the transparent resin layer contains, relative to 100 parts by mass of resin, 0.1 parts by mass or more and 30 parts by mass or less of an ultraviolet absorber and 0.1 parts by mass or more and 30 parts by mass or less of a light stabilizer; The position and shape of the convex portion formed on the back side correspond to the concave portion formed on the front side, the surface protective layer contains, relative to 100 parts by mass of a resin, 10 parts by mass or more and 30 parts by mass or less of an ultraviolet absorber and 10 parts by mass or more and 30 parts by mass or less of a light stabilizer; the surface protective layer contains, as the resin, a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate; the ultraviolet absorber contained in the surface protective layer is only one type of triazine-based ultraviolet absorber, The light stabilizer contained in the surface protective layer is a light stabilizer represented by the following formula (1): A decorative sheet characterized by: 【Chemistry 1】

2. The ultraviolet absorber contained in the transparent resin layer is at least one of a benzophenone type, a benzotriazole type, and a triazine type, and the light stabilizer is an N-OR type hindered amine type.

2. The decorative sheet according to claim 1.

3. The transparent resin layer has a thickness of 50 μm or more and 150 μm or less.

2. The decorative sheet according to claim 1.

4. The surface protection layer has a thickness of 1 μm or more and 20 μm or less.

2. The decorative sheet according to claim 1.

5. a colored resin layer, the pattern layer, the transparent resin layer, and the surface protection layer are laminated in this order; the colored resin layer contains a polyvinyl chloride resin, The transparent resin layer contains at least one of a polyvinyl chloride resin and an acrylic resin.

2. The decorative sheet according to claim 1.

6. a colored resin layer, the pattern layer, the transparent resin layer, and the surface protection layer are laminated in this order; The colored resin layer and the transparent resin layer contain a polyolefin resin.

2. The decorative sheet according to claim 1.

7. A decorative sheet according to any one of claims 1 to 6, and a substrate laminated on the side of the decorative sheet opposite the surface protective layer. A cosmetic material characterized by:

Images