Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material which satisfactorily control mechanical characteristics throughout a layer even when formed using a polyvinyl chloride resin, and secure good working suitability and productivity.SOLUTION: A decorative sheet 1 is formed by stacking at least a colored raw fabric layer 2, a pattern layer 3, a transparent resin layer 4 and a surface protective layer 5 in this order, wherein the colored raw fabric layer 2 is formed of a colored polyvinyl chloride resin, the transparent resin layer 4 is formed of a transparent polyvinyl chloride resin, and contains at least one of a polyester-based plasticizer and a phthalic acid-based plasticizer, and an addition amount of the plasticizer in the transparent resin layer 4 is within the range of 20 PHR or more and 30 PHR or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to decorative sheets and decorative materials. [Background technology]

[0002] 2. Description of the Related Art Conventionally, decorative sheets used for decorating interior materials for housing and the like that are made of polyvinyl chloride resin are known (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-278173 Summary of the Invention [Problem to be solved by the invention]

[0004] In the past, it was pointed out that sheets made of polyvinyl chloride resin may emit gases containing dioxins, which are considered to be harmful substances, when burned. For this reason, as interest in environmental issues increased, the use of decorative sheets made of polyvinyl chloride resin was temporarily restricted, and the use of decorative sheets made of olefin resins as an alternative to polyvinyl chloride decorative sheets increased.

[0005] However, in recent years, improvements in incineration equipment and exhaust gas treatment technology have helped to reduce the generation of harmful substances, and polyvinyl chloride resin is being reconsidered.In addition, more than half of the raw materials for polyvinyl chloride resin are made from salt, and the petrochemical-derived ethylene polymerization ratio is lower than that of olefin-based resins, so it is also said to be a resource-saving resin.

[0006] Furthermore, with growing awareness of zero-energy homes (ZEH), there is growing demand for highly insulated resin sashes and window frames that use polyvinyl chloride resin, and while it is conceivable to decorate these base materials using decorative sheets, there are issues with olefin-based resin sheets, such as the difficulty of recycling them. In contrast, polyvinyl chloride resin has the advantage of being easily processable and easily recycled, and from the perspective of reducing the environmental impact, the demand for decorative sheets using polyvinyl chloride resin is increasing. For this reason, it is expected that the use of decorative sheets made of polyvinyl chloride resin (polyvinyl chloride sheets) in combination with the resin sashes and window frame base materials that use polyvinyl chloride resin as described above will make a significant contribution to reducing the environmental impact.

[0007] Normally, when a polyvinyl chloride sheet is attached to a substrate such as a sash or exterior material, the sheet is often wrapped (bent) around the substrate. For this reason, the mechanical properties of the decorative sheet have a significant impact on its suitability for processing (wrapping, etc.) (suitability for processing) and productivity (ease of handling during production). Specifically, suitability for processing includes suppression of cracking and whitening at corners during wrapping, and good adhesion to the substrate. Here, the physical properties (suitability for processing and productivity) obtained by mechanical properties are called mechanical properties.

[0008] For example, decorative sheets with mechanical properties that are too high (too stiff) in terms of yield strength and elastic modulus will have poor adhesion when attached to a substrate, while decorative sheets with too low yield strength and elastic modulus will tend to stretch on the production line, which may reduce production stability when printing or laminating patterns. In addition, decorative sheets with excessively high breaking elongation among mechanical properties tend to stretch easily, just as sheets with low yield strength tend to stretch easily, and if the breaking elongation is excessively low, the sheet becomes hard and may crack during wrapping, resulting in a loss of design. In addition, the mechanical properties of decorative sheets are temperature dependent, and they must be stably controlled to ensure good mechanical properties (processability and productivity) throughout the year.

[0009] The present disclosure has been made in consideration of the above circumstances, and aims to provide a decorative sheet and decorative material that, even when formed using polyvinyl chloride resin, has well-controlled mechanical properties throughout the year and ensures good processability and productivity. [Means for solving the problem]

[0010] In order to solve the above problems, a decorative sheet according to one embodiment of the present disclosure comprises at least a colored base fabric layer, a pattern layer, a transparent resin layer, and a surface protection layer laminated in this order, the colored base fabric layer being formed from a colored polyvinyl chloride resin, the transparent resin layer being formed from a transparent polyvinyl chloride resin and containing at least one of a polyester-based plasticizer or a phthalic acid-based plasticizer, and the amount of plasticizer added in the transparent resin layer being within the range of 20 PHR or more and 30 PHR or less.

[0011] A decorative material according to another aspect of the present disclosure is characterized in that it comprises a substrate for a decorative material, and the above-mentioned decorative sheet bonded to the substrate for a decorative material. Effect of the Invention

[0012] According to one aspect of the present disclosure, an object is to provide a decorative sheet and decorative material that, even when formed using polyvinyl chloride resin, has well-controlled mechanical properties throughout the year and ensures good processability and productivity. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a cross-sectional view illustrating a decorative material according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] As a result of extensive research, the inventors have discovered that by selecting the appropriate type and amount of plasticizer, it is possible to stably control mechanical properties (in this example, elastic modulus, yield strength, and breaking elongation) throughout the year. This has led to the invention of a decorative sheet in which mechanical properties are well controlled throughout the year, ensuring good processing suitability and productivity.

[0015] Hereinafter, the decorative sheet and decorative member according to the embodiment of the present disclosure will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. are different from the actual ones. As long as it is within the scope of the present disclosure, it is not necessary to stack in the order shown in the drawings. In addition, layers not shown in the drawings may be added. In addition, the embodiments shown below are examples of configurations for embodying the technical idea of ​​the present disclosure, and the technical idea of ​​the present disclosure is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present disclosure can be modified in various ways within the technical scope defined by the claims described in the claims. In addition, the directions of "left and right" and "up and down" in the following description are merely defined for the convenience of explanation and do not limit the technical ideas of the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left".

[0016] The configuration of the decorative material 10 will be described below with reference to FIG. As shown in FIG. 1, the decorative material 10 comprises a decorative sheet 1 and a substrate 8 which is a substrate for a decorative material and a substrate to which the decorative sheet 1 is attached. In this example, the decorative sheet 1 is laminated on one surface (the upper surface in FIG. 1) of the substrate 8. That is, the decorative material 10 comprises the substrate 8 and the decorative sheet 1 laminated on one surface of the substrate 8. The specific configurations of the decorative sheet 1 and the substrate 8 will be described later.

[0017] (Composition of decorative sheet) As shown in FIG. 1, the decorative sheet 1 comprises a colored base layer 2, a design layer 3, a transparent resin layer 4, a surface protective layer 5, and an embossed portion . Specifically, in the decorative sheet 1, a pattern layer 3, a transparent resin layer 4, and a surface protective layer 5 are laminated in this order on a colored raw fabric layer 2 (one side of the colored raw fabric layer 2). An embossed portion 7 is formed on the surface (the side opposite to the transparent resin layer 4) of the surface protective layer 5, which is the outermost layer of the decorative sheet 1. Note that in the decorative sheet 1 according to this embodiment, the pattern layer 3 is not an essential component and can be provided as necessary.

[0018] (Colored original fabric layer) The colored raw fabric layer 2 is configured to be a support for the decorative sheet 1. In this embodiment, the colored raw fabric layer 2 is colored opaquely and has concealing properties. As a result, the colored raw fabric layer 2 can conceal color variations and defects on the substrate surface when, for example, the decorative sheet 1 is bonded to a predetermined substrate to form a decorative member.

[0019] The material for the colored raw fabric layer 2 is a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and is also suitable for printing. That is, in the decorative sheet 1 according to this embodiment, the colored raw fabric layer 2 is a colored polyvinyl chloride resin layer formed of a colored polyvinyl chloride resin (colored polyvinyl chloride resin). By forming the raw fabric layer from PVC, the leftover material of the decorative sheet 1 during the production of the decorative material 10 or the used decorative sheet 1 can be melted and extruded with an extruder or the like and reused as a recycled base material. Furthermore, PVC is easier to reuse by melting than olefin-based resins. In other words, by forming the colored base fabric layer 2 of the decorative sheet 1 according to this embodiment from PVC, it is possible to improve processability and recyclability.

[0020] As the vinyl chloride resin, a homopolymer of a vinyl chloride monomer, that is, polyvinyl chloride, or a copolymer obtained by copolymerizing a vinyl chloride monomer with a monomer copolymerizable with the vinyl chloride monomer can also be used. Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; maleic esters such as butyl maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; vinyl cyanides such as acrylonitrile and methacrylonitrile; olefins such as ethylene, propylene, butylene and styrene; dienes such as isoprene and butadiene; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides; allyl phthalates such as diallyl phthalate, etc. These monomers may be used alone or in combination of two or more kinds.

[0021] In addition, the colored raw fabric layer 2 as an opaquely colored polyvinyl chloride colored sheet (colored film) can have a hue appropriately selected as the base color of the picture layer 3. In addition, when utilizing the texture of the surface of the base material 8, which is a base material for a decorative material, the colored raw fabric layer 2 is preferably a colored polyvinyl chloride resin layer having a transparency to the extent that the surface of the base material 8 can be seen through.

[0022] For example, the colored raw fabric layer 2 can be colored by mixing or kneading a coloring agent such as a pigment into the resin material (polyvinyl chloride) that constitutes the colored raw fabric layer 2. As the coloring agent, organic or inorganic pigments can be used, but it is preferable to use an inorganic pigment. In other words, the colored raw fabric layer 2 preferably contains an inorganic substance as a coloring agent. For example, the colored raw fabric layer 2 preferably contains one or more inorganic substances selected from calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. This improves the thermal stability of the decorative sheet 1 body. Furthermore, since the inclusion of an inorganic substance improves the concealing property, it is possible to conceal color variations on the surface of the substrate during processing in which the decorative sheet 1 is bonded to the substrate, thereby improving the design.

[0023] In addition, if necessary, one or more additives selected from various additives such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters may be added to the colored raw material layer 2.

[0024] (Picture layer) The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored raw fabric layer 2, and is a layer for adding a pattern to impart design. More specifically, the pattern layer 3 is provided between the colored raw fabric layer 2 and the transparent resin layer 4. Note that the pattern layer 3 may be omitted if it can be substituted by coloring the colored raw fabric layer 2. The design layer 3 is formed using printing ink, paint, etc. The printing ink, paint, etc. forming the design layer 3 is formed by dissolving or dispersing a colorant such as a dye or pigment together with a suitable binder resin in a suitable dilution solvent. Examples of the pigment include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, mica, and other pearl pigments.

[0025] The printing ink or paint forming the design layer 3 is applied by using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating. As the binder resin, for example, urethane-based resin, acrylic-based resin, vinyl chloride acetate-based resin, polyimide-based resin, nitrocellulose, or a mixture thereof can be used, but the binder resin is not limited to these. Any pattern can be used as the design, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, letters, symbols, solid colors, or combinations thereof. In order to improve the concealment of the decorative sheet 1, a concealing layer may be provided between the design layer 3 and the colored base fabric layer 2. The concealing layer is formed, for example, using an opaque printing ink or paint that contains a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0026] The thickness of the pattern layer 3 is preferably within the range of 1 μm or more and 10 μm or less. This is because when the thickness of the pattern layer 3 is 1 μm or more, printing can be made clear. Also, when the thickness of the pattern layer 3 is 10 μm or less, printing workability is improved when producing the decorative sheet 1, and production costs can be reduced. In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, hardeners, hardening accelerators, and hardening retarders may be added to the design layer 3 in order to impart various functions. In addition, the pattern layer 3 may be configured to have, for example, a solid colored base fabric layer to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer to add a pattern to impart design appeal.

[0027] (Transparent resin layer) The transparent resin layer 4 is a layer for improving the weather resistance of the decorative sheet 1. In the decorative sheet 1 according to this embodiment, the material of the transparent resin layer 4 is a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and is suitable for printing. That is, in the decorative sheet 1 according to this embodiment, the transparent resin layer 4 is a transparent polyvinyl chloride resin layer formed of a transparent polyvinyl chloride resin (transparent polyvinyl chloride resin). As described above, PVC can be used as a recycled base material by melting and extruding, and is easier to reuse by melting than olefin-based resins. The vinyl chloride resin used for the transparent resin layer 4 can be the same as that for the colored raw fabric layer 2. In other words, by forming the colored base fabric layer 2 and the transparent resin layer 4 of the decorative sheet 1 according to this embodiment from PVC, it is possible to reliably improve processability and recyclability. The transparent resin layer 4 is preferably transparent enough to see through the pattern layer 3 provided on the surface (the lower surface in FIG. 1) on the colored raw fabric layer 2 side. For example, it may be colorless and transparent, colored and transparent, or translucent.

[0028] [Plasticizer] The transparent resin layer 4 contains a plasticizer to appropriately control the hardness of the vinyl chloride resin and improve the mechanical properties of the decorative sheet 1. The plasticizer is not particularly limited as long as it is compatible with the vinyl chloride resin, and examples thereof include phthalic acid plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), etc.; adipic acid plasticizers such as dibutyl adipate; phosphate plasticizers such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate, etc.; trimellitic acid plasticizers such as tributyl trimellitate, trioctyl trimellitate, etc.; various known polyester plasticizers such as adipic acid polyesters; citric acid esters such as acetyl tributyl citrate, acetyl trioctyl citrate, etc.; and the like. Among them, from the viewpoint of improving long-term adhesion as well as processability, and from the viewpoint of improving processability, phthalic acid plasticizers, adipic acid plasticizers, and polyester plasticizers are preferred, phthalic acid plasticizers and polyester plasticizers are more preferred, and from the viewpoint of durability, it is even more preferred to use high molecular weight polyester plasticizers. These plasticizers may be used alone or in combination of two or more kinds.

[0029] The amount of plasticizer added to the transparent resin layer 4 is, for example, within the range of 20% (20 parts) to 30% (30 parts) relative to 100% transparent polyvinyl chloride resin (100 parts transparent polyvinyl chloride resin). That is, the amount of plasticizer added is, for example, within the range of 20 PHR to 30 PHR. This allows the mechanical properties (in this example, elastic modulus, yield strength, and breaking elongation) of the decorative sheet 1 to be well and stably controlled throughout the year (for example, in a temperature environment of 0 to 40°C) even when formed using polyvinyl chloride resin.

[0030] [Ultraviolet absorber] In this embodiment, the transparent resin layer 4 contains an ultraviolet absorbing agent. That is, in the decorative sheet 1 according to this embodiment, the transparent resin layer 4 is preferably formed of a transparent polyvinyl chloride resin and contains an ultraviolet absorbing agent. This can impart excellent weather resistance to the transparent resin layer 4. More specifically, the transparent resin layer 4 preferably contains at least one of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber as the ultraviolet absorber. This provides excellent weather resistance to the transparent polyvinyl chloride resin forming the transparent resin layer 4, improving the weather resistance of the decorative sheet 1. This makes it possible to suppress discoloration when used outdoors for a long period of time, and the decorative sheet 1 using polyvinyl chloride can be suitably used as an exterior sheet for outdoor use. The amount of ultraviolet absorber added to the transparent resin layer 4 may be determined according to the desired weather resistance, but it is preferable that the amount is, for example, 0.5 parts by mass or more per 100 parts by mass of the transparent vinyl chloride resin that constitutes the transparent resin layer 4. This can reliably improve the weather resistance of the decorative sheet 1.

[0031] (Benzotriazole-based UV absorber) Examples of "benzotriazole-based" ultraviolet absorbents 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 the like, as well as mixtures, modified products, polymers, and derivatives thereof.

[0032] (Triazine-based UV absorber) As the triazine-based ultraviolet absorbent, for example, a hydroxyphenyltriazine-based ultraviolet absorbent is used. By using a hydroxyphenyltriazine-based ultraviolet absorbent, the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically stable compared to the skeletons of benzotriazole-based ultraviolet absorbents and benzophenone-based ultraviolet absorbents, making it possible to maintain ultraviolet absorption performance for a long period of time.

[0033] Examples of the triazine-based ultraviolet absorber used in the transparent resin layer 4 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.

[0034] (Light stabilizer) In this embodiment, the transparent resin layer 4 may contain a light stabilizer as a weather resistance agent. This can suppress deterioration of the vinyl chloride resin in an outdoor environment (e.g., photodiscoloration), and ensure good weather resistance of the decorative sheet 1. In other words, the transparent resin layer 4 may contain a light stabilizer and an ultraviolet absorbing agent. As the light stabilizer, it is preferable to use a hindered amine light stabilizer (HALS).

[0035] Examples of the hindered amine-based light stabilizer used in the transparent resin layer 4 include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl (meth)acrylate, 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, methyl(1,2, 2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxy-benzyl)-2-n-butylmalonate, and the like. Among these, hindered amine light stabilizers derived from decanedioic acid (sebacic acid), such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxyl-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, are preferred.

[0036] The content of the hindered amine radical scavenger in the transparent resin layer 4 is preferably in the range of 0.5 parts by mass to 10 parts by mass, more preferably in the range of 1 part by mass to 8 parts by mass, and even more preferably in the range of 3 parts by mass to 6 parts by mass, relative to 100 parts by mass of the transparent vinyl chloride resin constituting the transparent resin layer 4. This can reliably improve weather resistance, inhibit bleed-out of the weather resistance agent, and suppress effects on other physical properties of the transparent resin layer 4.

[0037] The thickness of the transparent resin layer 4 is preferably in the range of 50 μm to 150 μm, more preferably in the range of 50 μm to 100 μm, and even more preferably in the range of 60 μm to 80 μm. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 is reliably improved, and the unevenness of the substrate to which the layer is attached (substrate 8 in this example) is absorbed, resulting in a good application finish of the decorative sheet 1. Furthermore, when the thickness of the transparent resin layer 4 is 150 μm or less, the transparent resin layer 4 is not formed thicker than necessary, improving processability (e.g., bending processability) and reducing the manufacturing cost of the decorative sheet 1.

[0038] <Surface protective layer> The surface protective layer 5 according to this embodiment is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 1. There are no particular limitations on the material constituting the surface protective layer 5, and it can be appropriately selected from, for example, urethane-based, acrylic-based, acrylic silicone-based, fluorine-based, and epoxy-based resin materials. The surface protective layer 5 may contain various additives, such as an ultraviolet absorbing agent, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst trap, a colorant, a light scattering agent, and a gloss adjusting agent, as necessary. Hereinafter, an example of the surface protective layer 5 according to the present embodiment will be described with reference to a specific example.

[0039] The surface protection layer 5 according to this embodiment may be mainly composed of an acrylic resin composition containing, for example, cyclohexyl (meth)acrylate as a monomer component. In this embodiment, cyclohexyl (meth)acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By containing cyclohexyl (meth)acrylate as a monomer component, it is possible to reduce affinity for water and suppress deterioration due to hydrolysis or the like.

[0040] The content of cyclohexyl (meth)acrylate is preferably in the range of 5% by mass or more and 50% by mass or less among all the monomer components of the acrylic resin composition, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protective layer 5. By making the content of cyclohexyl (meth)acrylate 5% by mass or more, a sufficient deterioration suppression effect can be obtained. In addition, by making the content of cyclohexyl (meth)acrylate 50% by mass or less, it is possible to impart high weather resistance over time without significantly changing the various performances of the surface protective layer 5 of the decorative sheet, such as improved surface hardness maintenance, improved stain resistance, and surface gloss adjustment. Here, the above-mentioned "main component" means that the content of the acrylic resin composition constituting the surface protective layer 5 is 50% by mass or more with respect to the mass of the entire surface protective layer 5.

[0041] Examples of monomer components of the acrylic resin composition that can be used for the surface protective layer 5 according to this embodiment include, in addition to 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, methoxycyclohexylmethyl(meth)acrylate, and the like. Among these, those containing isomers may be each isomer alone and / or each isomer mixture.

[0042] In this embodiment, the surface protective layer 5 may be formed by applying a coating liquid containing the above-mentioned acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component and a weathering agent such as an ultraviolet absorber described below to the outermost surface of the decorative sheet. For example, the surface protective layer 5 may be formed by applying a coating liquid containing the above-mentioned acrylic resin composition and a weathering agent to the transparent resin layer 4 having the embossed portion 7, and then by wiping the coating liquid to embed the coating liquid in the embossed portion 7. As a method for curing the coating liquid for forming the surface protective layer 5, for example, any of a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type which is cured by exposure to ultraviolet light or ionizing radiation, etc., can be used. In consideration of weather resistance, the two-component curing type or the active energy ray curing type is preferred, and in consideration of post-processability after being laminated to various substrates to become a decorative member, a two-component curing type which is crosslinked by isocyanate curing is desirable.

[0043] As the two-component curing type acrylic resin composition, for example, a composition containing an acrylic resin having two or more functional groups selected from hydroxyl groups, amino groups, and 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 is preferred. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule, and a polyisocyanate compound.

[0044] As the acrylic polyol having two or more hydroxyl groups in one molecule, in addition to the above-mentioned cyclohexyl (meth)acrylate, for example, a (meth)acrylic acid ester copolymer containing hydroxyethyl (meth)acrylate as a monomer component can be used. On the other hand, as the polyisocyanate compound having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer type, TMP adduct type, biuret type, etc., synthesized by a known technique using one or more compounds selected from these. In addition, a composition in which one or more types selected from these different types of polyisocyanates are mixed can be used. Among them, HDI, or HDI trimer type, TMP adduct type, and biuret type are preferable from the viewpoint of weather resistance. The content of the isocyanate compound relative to the resin component can be set arbitrarily, but it is preferable to set the equivalent ratio of hydroxyl group / isocyanate group to about 1 / 1 to 1 / 3. In particular, if the equivalent of hydroxyl group is greater than the equivalent of isocyanate group, crosslinking does not proceed sufficiently and the desired performance is not imparted to the surface protective layer 5, and therefore it is not preferable to set the equivalent ratio of hydroxyl group / isocyanate group to about 1 / 1 to 1 / 3. There may not be.

[0045] When the coating liquid for forming the surface protective layer 5 is cured by active energy ray curing, known monomers, oligomers, etc. having a (meth)acryloyl group can be used as the active energy ray curable acrylic resin composition, and the above-mentioned cyclohexyl (meth)acrylate can be blended in addition to these monomers and oligomers.

[0046] [Ultraviolet absorber] In order to further improve the weather resistance of the decorative sheet 1, weather resistance agents such as ultraviolet absorbers and radical scavengers may be added to the surface protective layer 5. As the ultraviolet absorber, for example, known ones such as benzotriazole-based, hydroxyphenyltriazine-based, and benzophenone-based ones can be used. If a hydroxyphenyltriazine-based ultraviolet absorber is selected among them, it becomes possible to maintain ultraviolet absorbing performance for a long period of time because the triazine skeleton suppresses bleeding and the triazine skeleton is chemically stable compared to the skeletons of benzotriazole-based and benzophenone-based ultraviolet absorbers.

[0047] Examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 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-[(hexyl)oxy]phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic 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. In this embodiment, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter, for convenience, referred to as "ultraviolet absorber A") may be contained in the surface protective layer 5. Note that 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, which is the ultraviolet absorber A, is generally known as the main component of "Tinuvin 479: manufactured by BASF Japan Ltd."

[0048] In this embodiment, the amount of the hydroxyphenyltriazine-based ultraviolet absorber added is preferably within a range of 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the acrylic resin composition. By setting the amount of the ultraviolet absorber added to 1 part by mass or more, the weather resistance improving effect is exerted, and by setting the amount to 30 parts by mass or less, the influence on physical properties other than the weather resistance of the surface protective layer 5 can be suppressed to a practically problem-free level. In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber to be added to the surface protective layer 5, the amount added is preferably in the range of 1 part by mass to 20 parts by mass, more preferably in the range of 5 parts by mass to 15 parts by mass, and even more preferably in the range of 8 parts by mass to 12 parts by mass, relative to 100 parts by mass of the acrylic resin composition. By making the amount of ultraviolet absorber A 1 part by mass or more, an effect of improving weather resistance is exerted, and by making it 20 parts by mass or less, the influence on physical properties other than the weather resistance of the surface protective layer 5 can be suppressed to a level that does not cause practical problems.

[0049] In this embodiment, the ultraviolet absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter referred to as "ultraviolet absorber B" for convenience) are used together as the hydroxyphenyltriazine ultraviolet absorber in the surface protective layer 5, thereby providing even more excellent weather resistance. This is because the ultraviolet absorber B has a high ultraviolet absorption capacity in the short wavelength region, which is relatively high energy among ultraviolet rays, and is chemically stable compared to other ultraviolet absorbers that absorb approximately the same wavelength region, and therefore the wavelength region in which ultraviolet rays are absorbed is broadened by using them together. Note that 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is the ultraviolet absorber B, is generally known as the main component of "ADEKA STAB LA-46: manufactured by ADEKA Corporation".

[0050] In this embodiment, the amount of ultraviolet absorbent A added is preferably within a range of 10 parts by mass to 200 parts by mass, more preferably within a range of 20 parts by mass to 100 parts by mass, and even more preferably within a range of 40 parts by mass to 80 parts by mass, relative to 100 parts by mass of ultraviolet absorbent B. By setting the amount of ultraviolet absorbent A added within the above numerical range, even better weather resistance can be imparted.

[0051] (Another example of an ultraviolet absorber) The above describes the hydroxyphenyltriazine-based ultraviolet absorbers that can be added to the surface protective layer 5, but the hydroxyphenyltriazine-based ultraviolet absorbers that can be used in this embodiment are not limited to these. The surface protective layer 5 according to this embodiment may contain, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1). The surface protective layer 5 may also contain an ultraviolet absorber having a structure represented by the following general formula (2). Specifically, it may contain 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl)]-6-(4-methoxyphenyl)-s-triazine represented by the following formula (3), or it may contain a hydroxyphenyltriazine-based ultraviolet absorber represented by the following formula (4).

[0052] [ka]

[0053] In the general formula (1), R1 to R3 each independently represent a hydrogen atom, a methyl group, a phenyl group, or an alkoxy group, and at least two of them are alkoxy groups having 8 to 18 carbon atoms and not including a carbonyl group; R4 and R5 each independently represent a hydroxyl group, a methyl group, or a hydrogen atom; R6 to R8 each independently represent a methyl group or Indicates a hydrogen atom.

[0054] [ka]

[0055] In general formula (2), R1 and R2 each represent an alkoxy group having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 each represent a hydrogen atom.

[0056] [ka]

[0057] [ka]

[0058] Furthermore, by using a hydroxyphenyltriazine-based UV absorber in combination with a benzotriazole-based UV absorber, the interaction between them can provide even better weather resistance. This is because the benzotriazole-based UV absorber has an absorption peak on the longer wavelength side than the hydroxyphenyltriazine-based UV absorber, and the combined use further widens the wavelength range in which UV rays are absorbed. The amount of the benzotriazole-based UV absorber added is preferably within the range of 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the acrylic resin composition. By adding 1 part by mass or more, the desired effect can be obtained, and by adding 30 parts by mass or less, the bleeding out of the weather resistance agent can be suppressed. However, since the benzotriazole-based UV absorber has an absorption peak on the longer wavelength side, it may be yellowish, and when attention is required for the hue, it is better to suppress the amount added.

[0059] Examples of benzotriazole-based ultraviolet absorbers include, but are not limited to, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole, and the like.

[0060] (Radical scavenger) In this embodiment, the surface protective layer 5 may further contain a light stabilizer in addition to the ultraviolet absorber as a weather resistance agent. This can further improve the weather resistance performance of the decorative sheet 1. In other words, the surface protective layer 5 preferably contains an ultraviolet absorber (e.g., a triazine-based ultraviolet absorber) and a light stabilizer. For example, by further using a hindered amine radical scavenger as a light stabilizer, the weather resistance of the decorative sheet 1 can be further improved. Examples of hindered amine radical scavengers that can be used in this embodiment 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, 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-morpholino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-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-triazine-6-yl]-1,5,8-12-tetraazadodecane, 1,6,Examples of the reaction product include, but are not limited to, 11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-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, 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, and 2-aminoethanol.

[0061] The amount of the hindered amine-based radical scavenger to be added is preferably in the range of 1 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of the acrylic resin composition. By adding 1 part by mass or more, the desired effects can be obtained, and by adding 30 parts by mass or less, bleeding out of the weather resistance agent can be suppressed and the effects on other physical properties of the surface protective layer 5 can be suppressed.

[0062] In the present embodiment, if the amount of UV absorber added is the same, a thicker surface protective layer 5 can provide better weather resistance, but the flexibility of the decorative sheet 1 is impaired, and problems such as the tendency for cracks to form in the surface layer of the decorative sheet 1 during post-processing are more likely to occur. Conversely, if the thickness is made thinner, there is a problem that the weather resistance is impaired. For this reason, the thickness of the surface protective layer 5 is preferably in the range of 2 μm to 20 μm.

[0063] In the present embodiment, the surface protective layer 5 may be provided by any of various known coating methods, such as gravure coating, reverse coating, gravure reverse coating, die coating, flow coating, etc. Furthermore, the surface protective layer 5 in the present embodiment may contain various additives, such as an antifriction agent, an antiblocking agent, and an antistatic agent, as necessary.

[0064] <Embossed section> As shown in Fig. 1, an embossed portion 7 is provided on the outermost surface of the decorative sheet 1 according to this embodiment. By providing the embossed portion 7 on the outermost surface, it is possible to improve fingerprint resistance while maintaining the matte feel of the surface of the decorative sheet 1. The embossed portion 7 can be formed into various uneven shapes, such as wood grain duct grooves, stone slab surface unevenness (granite cleavage surface, etc.), cloth surface texture, matte finish, sand grain, hairline, and linear grooves, to impart a given design to the surface of the decorative sheet 1. The embossed portion 7 can be formed into various uneven shapes, for example, according to the design of the picture layer 3 or the desired design. The embossed portion 7 is formed on the surface (outermost surface) side of the surface protective layer 5, which is the outermost layer of the decorative sheet 1, and forms a concave-convex pattern. In this embodiment, the above-mentioned surface protective layer 5 is embedded in the embossed portion 7 that forms the concave-convex pattern. This point will be described below.

[0065] In the decorative sheet 1 according to this embodiment, the embossed portion 7 is provided in the transparent resin layer 4. That is, the transparent resin layer 4 is a layer in which the embossed portion 7 is formed. The shape of the uneven pattern provided on the surface of the transparent resin layer 4 is not particularly limited, but the shape of the embossed portion 7 constituting the uneven pattern is preferably such that the opening diameter increases from the back side (in this example, the design layer 3) of the transparent resin layer 4 toward the front side (surface protective layer 5). With such a shape, it becomes easier to fill the embossed portion 7 with the surface protective layer composition (coating liquid) by wiping.

[0066] Moreover, the side surface on which the embossed portion 7 is formed is preferably an inclined surface. If the side surface on which the embossed portion 7 is formed is an inclined surface, it becomes easier to fill the embossed portion 7 with the surface protection layer composition (coating liquid) by wiping. In addition, the entire side surface forming the embossed portion 7 may be covered with the surface protection layer 5 . The depth of the embossed portion 7 is preferably within a range of 1 μm to 50 μm in the thickness direction of the transparent resin layer 4. When the depth of the embossed portion 7 is within the above-mentioned numerical range, the surface protective layer composition (coating liquid) can be easily embedded in the embossed portion 7 by wiping, and peeling of the surface protective layer can be prevented.

[0067] The width of the embossed portion 7 is preferably within a range of 1 μm to 20 μm. When the width of the embossed portion 7 is within the above-mentioned numerical range, the surface protective layer composition (coating liquid) can be easily embedded in the embossed portion 7 by wiping, and the surface protective layer embedded in the embossed portion 7 can be prevented from peeling off.

[0068] In addition, it is preferable that the embossed portion 7 is completely filled (packed) with the surface protective layer composition (coating liquid), and the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is preferably 10% or more. If the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 10% or more, the weather resistance of the embossed portion 7 can be improved. That is, if the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 10% or more, the occurrence of whitening and breakage in the conduit portion can be reduced. In addition, as described above, the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is preferably 100%, but it is more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 80% or less, and it is more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 60% or less. If the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 80% or less, a sufficient tactile sensation can be obtained in the embossed portion 7. Furthermore, by setting the filling rate of the surface protection layer 5 to 100% relative to the volume of the embossed portion 7, the surface of the surface protection layer 5 filled in the embossed portion 7 and the surface of the transparent resin layer 4 in the area not including the embossed portion 7 can be made flush, so to speak.

[0069] <Mechanical properties of decorative sheets> The mechanical properties (in this example, elastic modulus, yield strength, and breaking elongation) of the decorative sheet 1 according to this embodiment will be described below. In this embodiment, the mechanical properties are controlled by the type and amount of plasticizer added to the transparent resin layer 4.

[0070] [Elastic modulus] The decorative sheet 1 according to this embodiment has an elastic modulus of 70 MPa or more and 1500 MPa or less at 2.5% displacement at each temperature of 0°C, 20°C, and 40°C. This allows the mechanical properties of the decorative sheet 1 to be good. Specifically, the decorative sheet 1 has a hardness suitable for production and processing, and has good processability, which can improve the adhesion of the decorative sheet 1 when it is attached to a substrate. In addition, the production stability during printing and lamination can be improved. If the elastic modulus at 2.5% displacement is less than 70 MPa, the sheet becomes easily stretched, and there is a concern that the production stability during printing and lamination of a pattern will decrease. In addition, if the elastic modulus at 2.5% displacement exceeds 1500 MPa, the adhesion during attachment to a substrate will decrease.

[0071] [Yield point strength] The decorative sheet 1 according to this embodiment has a yield strength in the range of 20 MPa to 80 MPa at temperatures of 0°C, 20°C, and 40°C. This allows the decorative sheet 1 to have good mechanical properties. Specifically, the decorative sheet 1 has a hardness suitable for production and processing, and has good processing suitability, which can improve the adhesion of the decorative sheet 1 when it is attached to a substrate. In addition, the production stability during printing and lamination can be improved. If the yield strength is less than 20 MPa, the sheet is likely to stretch, and there is a concern that the production stability during printing and lamination of a pattern will decrease. In addition, if the yield strength exceeds 1500 MPa, the adhesion during attachment to a substrate will decrease.

[0072] [Elongation at break] The decorative sheet 1 according to this embodiment has a breaking elongation in the range of 10% to 450% at each temperature of 0°C, 20°C, and 40°C. This allows the decorative sheet 1 to have good mechanical properties. Specifically, the decorative sheet 1 has a hardness suitable for production and processing, and has good processing suitability, which can improve the adhesion of the decorative sheet 1 when it is attached to a substrate. In addition, the production stability during printing and lamination can be improved. If the breaking elongation is less than 10%, the sheet becomes hard, and there is a concern that the sheet may crack during wrapping processing, resulting in a loss of design. In addition, if the breaking elongation exceeds 450%, the sheet becomes easily stretched, which may reduce the production stability during printing and lamination of a pattern.

[0073] [Measurement of mechanical properties] The mechanical properties (elastic modulus, yield strength, and breaking elongation) of the decorative sheet 1 according to this embodiment are measured by a tensile test in accordance with JIS K7161. The measurement conditions are, for example, temperatures of 0°C, 20°C, and 40°C, a tensile speed of 50 mm / min, a distance between chucks of 70 mm, and a distance between chucks of 40 mm. In addition, the thickness of the test piece is 80 μm, and the width of the test piece is 10 mm.

[0074] <Total sheet thickness> The overall thickness (total thickness) of the decorative sheet 1 according to this embodiment is preferably in the range of 50 μm to 200 μm, more preferably in the range of 120 μm to 200 μm. This makes it possible to form a decorative sheet 1 that has good weather resistance, has the same degree of concealment as a decorative sheet formed using a conventional olefin-based resin, and also has good processability. In this example, the total thickness of the decorative sheet 1 is the sum of the thicknesses of the two layers, the colored raw fabric layer 2 and the transparent resin layer 4. In addition, when the decorative sheet 1 does not include the colored raw fabric layer 2, the thickness of the single layer of the transparent resin layer 4 is the total thickness of the decorative sheet 1.

[0075] As described above, the decorative sheet 1 according to this embodiment is formed by laminating at least the colored raw fabric layer 2, the pattern layer 3, the transparent resin layer 4, and the surface protective layer 5 in this order, the colored raw fabric layer 2 being formed of a colored polyvinyl chloride resin, the transparent resin layer 4 being formed of a transparent polyvinyl chloride resin and containing at least one of a polyester-based plasticizer and a phthalic acid-based plasticizer, and the amount of plasticizer added to the transparent resin layer 4 is within a range of 20 PHR to 30 PHR. This makes it possible to obtain a decorative sheet in which the mechanical properties are well controlled throughout the year (for example, in a temperature environment of 0 to 40°C), and which ensures good processability and productivity, even when formed using polyvinyl chloride resin.

[0076] (Decorative materials) In this embodiment, the decorative material 10 may be formed by bonding the above-mentioned decorative sheet 1 to a substrate 8, which is a substrate for a decorative material.

[0077] (base material) The substrate 8 may be a wood substrate or a metal substrate. The substrate 8 may be, for example, a wood veneer, a wood plywood, a laminated lumber, a particle board, a medium density fiberboard, or a hard fiberboard. The metal substrate may be, for example, a steel plate or an aluminum plate. The substrate 8 may be a resin such as plastic, or a composite material thereof. When the substrate 8 is a resin substrate, for example, polyvinyl chloride resin may be used. The substrate 8 made of polyvinyl chloride resin has high thermal insulation properties and is in high demand as a window frame fixture (sash). The decorative material 10 in which the substrate 8 made of polyvinyl chloride resin is decorated with the decorative sheet 1 can be reused by dissolving both the substrate 8 and the decorative sheet 1, which can improve recyclability. The base material 8 may be made of, for example, a fireproof steel plate or a fireproof material as specified by Notification No. 1400 of the Ministry of Construction.

[0078] (adhesive layer) The adhesive layer 9 is a layer made of an adhesive, and is a layer for bonding the base material 8 and the colored original fabric layer 2 together. The adhesive constituting the adhesive layer 9 may be, for example, a urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, or other adhesive. In particular, in this embodiment, a two-liquid curing urethane-based adhesive made by blending polyester polyol and polyisocyanate is preferred. Furthermore, when inorganic powder such as silica, barium sulfate, or calcium carbonate is added to these materials to form the adhesive layer 9, this is effective in preventing blocking during storage in a roll and improving adhesive strength by the anchoring effect. The thickness of the adhesive layer 9 is preferably about 0.5 μm to 6 μm.

[0079] As shown in Fig. 1, a decorative sheet 1 is laminated on one surface (the upper surface in Fig. 1) of a base material 8. That is, a decorative material 10 according to this embodiment includes a base material 8 that is a base material for a decorative material, and a decorative sheet 1 bonded to the base material 8. By laminating the decorative sheet 1 of this embodiment to a substrate 8, a decorative material can be obtained that has excellent weather resistance even when formed using polyvinyl chloride resin, and further has excellent processability and recyclability. More specifically, the decorative material 10 includes a base material 8 and a decorative sheet 1 laminated on one surface of the base material 8. The configuration of the decorative material 10 is not limited to the example shown in Fig. 1. That is, the decorative material 10 may be configured to include a decorative sheet 1 laminated on the other surface of the base material 8 (the lower surface in Fig. 1) in addition to the one surface of the base material 8.

[0080] (Method of manufacturing decorative sheets and decorative members) An example of a method for producing the decorative sheet 1 according to this embodiment will now be briefly described. A pattern layer 3 is printed on the colored base fabric layer 2 described above. Next, a transparent resin layer 4 is formed by thermal lamination on the colored original fabric layer 2 on which the pattern layer 3 is formed, and at the same time, an embossed portion 7 is formed by providing a concave-convex pattern on the surface of the transparent resin layer 4 opposite to the colored original fabric layer 2 by embossing. Next, a coating liquid for forming a surface protective layer 5 is applied onto the surface of the transparent resin layer 4 on which the uneven pattern (embossed portion 7) has been formed. Finally, the coating liquid is wiped so as to fill the embossed portions 7 constituting the concave-convex pattern, and the coating liquid is cured to form the surface protection layer 5 on the transparent resin layer 4. In this manner, the decorative sheet 1 according to this embodiment is formed. An example of a method for producing the decorative material 10 according to this embodiment will be briefly described below. The decorative sheet 1 and the substrate 8 are bonded together to form the decorative material 10.

[0081] (Effects of this embodiment) The decorative sheet 1 and decorative material 10 according to this embodiment have the following effects. (1) The decorative sheet 1 of this embodiment is formed by laminating at least a colored raw fabric layer 2, a pattern layer 3, a transparent resin layer 4, and a surface protection layer 5 in this order, the colored raw fabric layer 2 being formed of a colored polyvinyl chloride resin, the transparent resin layer 4 being formed of a transparent polyvinyl chloride resin and containing at least one of a polyester-based plasticizer or a phthalic acid-based plasticizer, and the amount of plasticizer added in the transparent resin layer 4 being within the range of 20 PHR or more and 30 PHR or less. With this configuration, even when formed using polyvinyl chloride resin, the mechanical properties of the decorative sheet 1 (in this example, elastic modulus, yield strength, and breaking elongation) are well controlled throughout the year (for example, in a temperature environment of 0 to 40°C), ensuring good processing suitability and productivity. (2) In a tensile test conforming to JIS K7161 under temperature conditions of 0°C, 20°C, and 40°C, the decorative sheet 1 may have an elastic modulus at 2.5% displacement in the range of 70 MPa or more and 1500 MPa or less, a yield strength in the range of 20 MPa or more and 80 MPa or less, and a breaking elongation in the range of 10% or more and 450% or less. This configuration can improve the mechanical properties of the decorative sheet. (3) In the decorative sheet 1, the transparent resin layer 4 may contain at least one of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. According to this configuration, excellent weather resistance can be imparted to the transparent vinyl chloride resin forming the transparent resin layer 4, thereby improving the weather resistance of the decorative sheet. (4) In the decorative sheet 1, the surface protective layer may contain an ultraviolet absorbing agent and a light stabilizer. According to this configuration, the weather resistance of the decorative sheet can be further improved. (5) The decorative sheet 1 may have an embossed portion formed in the surface protective layer, which is the outermost layer. According to this configuration, it is possible to improve the fingerprint resistance while maintaining the matte feel of the surface of the decorative sheet. (6) The decorative material 10 according to this embodiment includes a base material 8 for the decorative material, and a decorative sheet 1 attached to the base material 8. According to this configuration, even when the plate is formed using polyvinyl chloride resin, the mechanical properties are well controlled throughout the year, and good processability and productivity are ensured.

[0082] <Example> The present disclosure will be described in detail below with reference to examples and comparative examples, but the present disclosure is not limited to the following examples.

[0083] Example 1 A printing ink for PVC was gravure printed on a colored polyvinyl chloride resin (hereinafter, PVC: Poly Vinyl Chloride) sheet as a colored base fabric layer to form a pattern layer. After that, a transparent PVC sheet was heat laminated as a transparent resin layer onto the colored base fabric layer with the pattern layer, and a surface protective layer mainly composed of an acrylic resin composition was formed on the transparent resin layer. A weathering agent was added to the surface protective layer to make it a highly weather-resistant sheet. Thereafter, the surface of the colored base layer (colored PVC sheet) opposite the design layer was attached to the PVC substrate using a urethane adhesive to obtain the decorative material according to Example 1. The additives for each layer according to this example are shown below. [Transparent resin layer] Additive: High molecular weight polyester plasticizer (PN-7160, manufactured by ADEKA) ···20PHR Weather resistance agents (ultraviolet absorbers (UVA), light stabilizers (HALS))...No additives [Surface protective layer] Base agent (methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) 90 parts by weight Ultraviolet absorber (Tinuvin 479; manufactured by BASF Japan Ltd.) 9 parts by weight Light stabilizer (Tinuvin 123; manufactured by BASF Japan Ltd.) 1 part by weight Hardener (Takenate D170; Mitsui Chemicals, Inc.) 10 parts by weight Solvent (ethyl acetate) 240 parts by weight ·Amount of application: 3g / m 2

[0084] Example 2 A decorative sheet and a decorative material according to Example 2 were obtained in the same manner as in Example 1 except that a benzotriazole-based ultraviolet absorber and a light stabilizer (HALS) were added to the transparent resin layer. Example 3 A triazine-based ultraviolet absorber was added to the transparent resin layer, and the amount of plasticizer added was 25 PHR. Otherwise, the same procedure as in Example 2 was repeated to obtain a decorative sheet and a decorative material according to Example 3. Example 4 The amount of plasticizer added to the transparent resin layer was 30 PHR. Other than that, the decorative sheet and decorative material according to Example 4 were obtained in the same manner as in Example 3. Example 5 A decorative sheet and a decorative material according to Example 5 were obtained in the same manner as in Example 3, except that dioctyl phthalate (DOP) was added as a plasticizer to the transparent resin layer. Example 6 A decorative sheet and a decorative material according to Example 6 were obtained in the same manner as in Example 3 except that 20 PHR of diisononyl phthalate (DINP) was added as a plasticizer to the transparent resin layer.

[0085] Comparative Example 1 The amount of plasticizer added to the transparent resin layer was 15 PHR. Other than that, the same procedure as in Example 3 was carried out to obtain a decorative sheet and a decorative material according to Comparative Example 1. Comparative Example 2 The amount of plasticizer added to the transparent resin layer was 40 PHR. Other than that, the same procedure as in Example 3 was carried out to obtain a decorative sheet and a decorative material according to Comparative Example 2.

[0086] <Mechanical property measurements> Tensile tests were carried out according to JIS K7161 for the prepared decorative sheets of each of the Examples and Comparative Examples at temperatures of 0°C, 20°C, and 40°C to measure the elastic modulus, yield strength, and breaking elongation at 2.5% displacement. The measurement conditions were a tensile speed of 50mm / min, a distance between chucks of 70mm, a distance between chucks of 40mm, a thickness of the test piece of 80μm, and a width of the test piece of 10mm.

[0087] <Evaluation> The decorative sheets obtained in the above Examples and Comparative Examples were evaluated for productivity, cold impact resistance, processability (wrapping processability), weather resistance, and the presence or absence of bleed-out by the following methods. The evaluation results are shown in Table 1. In Table 1, the "elastic modulus at 2.5% displacement" is simply referred to as "elastic modulus."

[0088] (Productivity) The decorative sheets of each Example and Comparative Example were evaluated for productivity under the conditions of printing on the film. If production was possible under a wide range of production conditions, it was marked as "◯", and if production was difficult, it was marked as "×". In this Example, "◯" was considered to be acceptable. (Cold impact resistance) For each of the decorative sheets of the Examples and Comparative Examples, a test was carried out in accordance with ASTM D 1593-81 in a low temperature (5° C.) environment, in which impact was applied, and the presence or absence of cracks was visually confirmed. 〇: No cracks occurred when the decorative sheet was subjected to impact at low temperatures. ×: When the decorative sheet was subjected to an impact at low temperature, cracks occurred.

[0089] (Processability) The decorative sheets of each of the Examples and Comparative Examples were used to wrap a PVC substrate. The folded surface of the decorative sheet after wrapping was visually inspected for abnormalities such as whitening or cracks, and the suitability for processing and the processing conditions were evaluated. 〇: The decorative sheet does not turn white when stretched during wrapping, and no cracks are found in the decorative sheet at the corners of the wrapping substrate. ×: When the decorative sheet is stretched during wrapping, it turns white, and cracks in the decorative sheet are observed at the corners of the wrapping base material. In this example, a grade of "◯" or higher was considered to be acceptable.

[0090] (Weather resistance test) The appearance of the decorative sheets of each of the Examples and Comparative Examples after the accelerated weathering test was visually evaluated according to the following criteria. The accelerated weathering test was performed using a metal weather tester (KU-R5DCI-A) manufactured by Daipla Wintes Co., Ltd. The decorative sheets were placed in the tester at a black panel temperature of 63°C and an illuminance of 65mW / cm. 2 The test was carried out for 25 cycles (600 hours) with 20 hours of UV irradiation + 4 hours of condensation as one cycle. The illuminance was measured using a UVD-365PD made by Ushio Inc. The evaluation criteria are as follows: ○: No brown discoloration occurred within the test period △: Brown discoloration occurred locally (scattered) during the test period. ×: Brown discoloration occurred throughout the entire surface within the test period. In this example, a grade of "◯" or higher was considered to be acceptable.

[0091] (with or without bleed out) The decorative sheets of each Example and Comparative Example were subjected to an environmental test at a temperature of 50° C. and a humidity of 90% for one week, after which ink was applied and dried, and after drying, the degree of adhesion of the ink was checked with cellophane tape. 〇: Ink did not peel off ×: Ink peeling occurred

[0092] [Table 1]

[0093] As can be seen from Table 1, in the decorative sheets of Examples 1 to 6, the colored base layer is formed of a colored polyvinyl chloride resin, and the transparent resin layer is formed of a polyvinyl chloride resin and contains at least one of a polyester-based plasticizer and a phthalic acid-based plasticizer. Furthermore, a plasticizer is added to the transparent resin layer in a range of 20 PHR to 30 PHR. As a result, as shown in Table 1, the decorative sheets of Examples 1 to 6, in tensile tests conforming to JIS K7161 under temperature conditions of 0°C, 20°C, and 40°C, have an elastic modulus at 2.5% displacement in the range of 70 MPa or more and 1500 MPa or less, a yield strength in the range of 20 MPa or more and 80 MPa or less, and a breaking elongation controlled in the range of 10% or more and 450% or less. For this reason, all of the decorative sheets of Examples 1 to 6 were rated as "good" for productivity and processing suitability, and it was found that even when formed using polyvinyl chloride resin, the mechanical properties (elastic modulus, yield strength, and breaking elongation) were well controlled throughout the year (in a temperature environment of 0 to 40°C), and good mechanical properties (processability and productivity) were ensured. In addition, the cold impact resistance was also rated as "good", and it was found that the mechanical properties were maintained even in a cold environment.

[0094] In addition, the decorative sheets of Examples 2 to 6, which contain weather resistance agents (UVA, HALS) in the transparent resin layer, all passed the weather resistance evaluation ("△" or better), and in particular, Examples 3 to 6, which contained a triazine-based ultraviolet absorber, showed good weather resistance (evaluated as "◯"). Furthermore, no bleeding out was observed in the decorative sheets of Examples 1 to 4 (evaluated as "◯").

[0095] On the other hand, the decorative sheets of Comparative Examples 1 and 2 did not have a configuration in which the mechanical properties (elastic modulus, yield strength, and breaking elongation) were not well controlled to be within the above-mentioned range throughout the year (at a temperature environment of 0 to 40°C) because the amount of plasticizer added in the transparent resin layer was not within the range of 20 PHR or more and 30 PHR or less, and good mechanical properties (processability and productivity) were not guaranteed. Specifically, the decorative sheet of Comparative Example 1 had a small amount of plasticizer added of 15 PHR, so the decorative sheet became excessively hard, especially in a cold environment (0°C), and the mechanical properties were not well controlled. For this reason, the productivity, cold impact resistance, and processability were all unsatisfactory (evaluated as "x"). Furthermore, the decorative sheet of Comparative Example 2 had a large amount of plasticizer added of 40 PHR, so the decorative sheet became excessively soft, especially in a warm environment (40°C), and the mechanical properties were not well controlled. For this reason, the productivity was unsatisfactory (evaluated as "x").

[0096] The decorative sheet and decorative material of the present disclosure are not limited to the above-described embodiments and examples, and various modifications are possible without departing from the characteristics of the invention.

[0097] Furthermore, for example, the present disclosure can have the following configuration. (1) At least a colored base layer, a design layer, a transparent resin layer, and a surface protective layer are laminated in this order, The colored base layer is formed of a colored polyvinyl chloride resin, the transparent resin layer is formed of a transparent polyvinyl chloride resin and contains at least one of a polyester-based plasticizer and a phthalic acid-based plasticizer; The amount of plasticizer added to the transparent resin layer is within a range of 20 PHR to 30 PHR. A decorative sheet characterized by: (2) In tensile tests based on JIS K7161 under temperature conditions of 0℃, 20℃, and 40℃, The elastic modulus at 2.5% displacement is within the range of 70 MPa to 1500 MPa. The yield strength is within the range of 20Mpa to 80Mpa, The breaking elongation is within the range of 10% to 450%. 4. The decorative sheet according to claim 1, (3) The transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. 4. The decorative sheet according to claim 1 or 2, (4) The surface protective layer contains an ultraviolet absorbing agent and a light stabilizer. The decorative sheet according to any one of (1) to (3) above, (5) The surface protective layer, which is the outermost layer, has an embossed portion formed thereon. The decorative sheet according to any one of (1) to (4) above, (6) A base material for a cosmetic material, The decorative sheet according to any one of (1) to (5) above, which is bonded to the substrate for decorative material; A decorative material comprising: [Industrial Applicability]

[0098] The present disclosure relates to a technology suitable for use in building exteriors and semi-exterior buildings, i.e., surface decorative materials such as entrance doors, door frames, window frames, and bay window counters. [Explanation of symbols]

[0099] 1 Decorative sheet 2 Colored original fabric layer 3. Picture layer 4 Transparent resin layer 5 Surface protective layer 7 Embossed section 8 Base material 9 Adhesive layer 10 Cosmetic materials

Claims

1. At least a colored base layer, a design layer, a transparent resin layer, and a surface protective layer are laminated in this order, The colored base layer is formed of a colored polyvinyl chloride resin, the transparent resin layer is formed of a transparent polyvinyl chloride resin and contains at least one of a polyester-based plasticizer and a phthalic acid-based plasticizer; The amount of plasticizer added to the transparent resin layer is within a range of 20 PHR to 30 PHR. A decorative sheet characterized by:

2. In a tensile test in accordance with JIS K7161 under the temperature conditions of 0°C, 20°C, and 40°C, The elastic modulus at 2.5% displacement is in the range of 70 MPa or more and 1500 MPa or less, The yield strength is in the range of 20 MPa to 80 MPa, The breaking elongation is in the range of 10% or more and 450% or less.

2. The decorative sheet according to claim 1.

3. The transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber.

3. The decorative sheet according to claim 2.

4. The surface protective layer contains an ultraviolet absorbing agent and a light stabilizer.

4. The decorative sheet according to claim 3.

5. The surface protective layer, which is the outermost layer, has an embossed portion formed thereon.

5. The decorative sheet according to claim 4.

6. A base material for a cosmetic material, The decorative sheet according to claim 1 , which is bonded to the substrate for decorative material; A decorative material comprising:

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