Laminate sheet and decorative material

Abstract

To provide a laminate sheet which exhibits flameproof performance and can suppress weather resistance deterioration, even if a polyvinyl chloride resin is used.SOLUTION: A laminate sheet 1 has a transparent resin layer 4 containing a polyvinyl chloride resin as a main agent, and a surface protective layer 5 which is formed on one surface of the transparent resin layer 4 and contains a resin composition as a main agent, wherein both the transparent resin layer 4 and the surface protective layer 5 contain an ultraviolet absorber and a flame retardant. The content of the flame retardant of the transparent resin layer 4 is within the range of 7 pts.mass or more and 15 pts.mass or less with respect to 100 pts.mass of the polyvinyl chloride resin, and the content of the flame retardant of the surface protective layer 5 is within the range of 3 pts.mass or more and 6 pts.mass or less with respect to 90 pts.mass of the resin composition. The laminate sheet 1 has excellent flame retardance and weather resistance, which exhibits flameproof performance and can suppress weather resistance deterioration.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a laminated sheet and a decorative material. [Background technology]

[0002] It has been pointed out that polyvinyl chloride resin sheets may emit gases when burned, which may contain dioxins, which are considered to be harmful substances.

[0003] In recent years, the use of polyvinyl chloride resin is being reconsidered as the generation of harmful substances has been reduced due to improvements in incineration facilities and exhaust gas treatment technology.

[0004] 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.

[0005] Furthermore, since polyvinyl chloride resins are self-extinguishing, they are often used in components that require flame retardant performance (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6120207 Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional polyvinyl chloride sheets may discolor due to weathering, making it difficult to use polyvinyl chloride clear films for exterior applications. For this reason, there has been a demand for polyvinyl chloride sheets that can be used as clear curtains for outdoor use or as exterior decorative films for surface protection.

[0008] The present invention has been made in light of the above-mentioned points, and aims to provide a laminated sheet and decorative material that exhibit flame retardant performance while suppressing weather deterioration. [Means for solving the problem]

[0009] A laminate sheet according to one embodiment of the present invention has a resin layer mainly composed of polyvinyl chloride resin, and a surface protective layer formed on one side of the resin layer and mainly composed of a resin composition, wherein the resin layer and the surface protective layer both contain an ultraviolet absorber and a flame retardant, the content of the flame retardant in the resin layer is within a range of 7 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the polyvinyl chloride resin, and the content of the flame retardant in the surface protective layer is within a range of 3 parts by mass or more and 6 parts by mass or less per 90 parts by mass of the resin composition.

[0010] A decorative material according to another aspect of the present invention is characterized by comprising a base material for a decorative material and the laminate sheet of the above aspect bonded to the base material for a decorative material. Effect of the Invention

[0011] According to one aspect of the present invention, it is possible to provide a laminate sheet and a decorative material that exhibit flame retardant performance and are capable of suppressing weather resistance deterioration. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic example of a decorative material according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, a laminate sheet and a decorative material according to one embodiment of the present invention will be described with reference to the drawings.

[0014] 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.

[0015] 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] FIG. 1 is a cross-sectional view that shows a schematic diagram of a decorative material 10 according to one embodiment of the present invention. (Composition of decorative materials) As shown in FIG. 1, the decorative material 10 includes a laminate sheet 1 and a substrate (substrate for decorative material) 8 which is a substrate for a decorative material and is a substrate to which the laminate sheet 1 is attached. In this example, the laminate sheet 1 is laminated on one surface (the upper surface in FIG. 1) of the base material 8. That is, the decorative material 10 includes the base material 8 and the laminate sheet 1 laminated on one surface of the base material 8.

[0017] (Structure of laminated sheet) As shown in FIG. 1, the laminate sheet 1 includes a colored base fabric layer 2, a design layer 3, a transparent resin layer (resin layer) 4, a surface protective layer 5, and an embossed portion . Specifically, in the laminate sheet 1, a design layer 3, a transparent resin layer 4, and a surface protective layer 5 are laminated in this order on one surface side of a colored raw fabric layer 2. In addition, an embossed portion 7 is formed on the surface of the surface protective layer 5, which is the outermost layer of the laminate sheet 1 (the surface opposite to the transparent resin layer 4).

[0018] In the laminated sheet 1 according to the present embodiment, the pattern layer 3 and the colored base fabric layer 2 are not essential components and can be provided as necessary. In other words, the laminated sheet 1 only needs to have a configuration in which at least the transparent resin layer 4 and the surface protective layer 5 are laminated.

[0019] (Colored original fabric layer) The colored raw fabric layer 2 functions as a support for the laminated sheet 1. In this embodiment, the colored raw fabric layer 2 is colored opaquely and has concealing properties. As a result, when the laminated sheet 1 and a predetermined substrate are bonded together to form the decorative material 10, the colored raw fabric layer 2 can conceal color variations and defects on the substrate surface.

[0020] In addition, the material of 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 laminated 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 scraps of the laminated sheet 1 during the production of the decorative material 10 or the used laminated sheet 1 can be melted and extruded with an extruder or the like to be reused as a recycled base material. In addition, PVC is easier to reuse by melting than olefin-based resins.

[0021] That is, by forming the colored raw fabric layer 2 of the laminate sheet 1 according to this embodiment from PVC, it is possible to improve processability and recyclability.

[0022] 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.

[0023] 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) constituting the colored raw fabric layer 2. As the coloring agent, organic or inorganic pigments can be used, but it is preferable to use inorganic pigments. In other words, it is preferable that the colored raw fabric layer 2 contains an inorganic substance as a coloring agent. For example, it is preferable that the colored raw fabric layer 2 contains one or more inorganic substances selected from calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0024] 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.

[0025] (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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] Any pattern can be used as the design, for example, 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 laminated 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 containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0030] The thickness of the design layer 3 is preferably within the range of 1 μm to 10 μm. This is because when the thickness of the design layer 3 is 1 μm or more, printing can be made clear. Also, when the thickness of the design layer 3 is 10 μm or less, printing workability is improved when manufacturing the laminated sheet 1, and manufacturing costs can be reduced.

[0031] 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.

[0032] (Transparent resin layer) The transparent resin layer 4 is a layer for improving the weather resistance of the laminate sheet 1. In the laminate sheet 1 according to this embodiment, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and is suitable for printing, is used as the material for the transparent resin layer 4. That is, in the laminate 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 substrate by melting and extruding it, and is easier to reuse by melting than olefin-based resins.

[0033] In the laminate sheet 1 according to this embodiment, the colored raw fabric layer 2 and the transparent resin layer 4 are formed from PVC, so that the processability and recyclability can be reliably improved.

[0034] The transparent resin layer 4 is preferably transparent enough to see through the pattern layer 3 provided on the surface facing the colored raw fabric layer 2 (the lower surface in FIG. 1). For example, the transparent resin layer 4 is colorless transparent, colored transparent, or translucent. When the pattern layer 3 is not provided below the transparent resin layer 4, it is not necessarily necessary to provide a transparent resin layer (transparent resin layer 4) as the resin layer, and a colored resin layer may be provided instead of the transparent resin layer 4.

[0035] In this embodiment, the transparent resin layer 4 contains a flame retardant and an ultraviolet absorbing agent. That is, in the laminate sheet 1 according to this embodiment, the transparent resin layer 4 is formed from a transparent polyvinyl chloride resin as a main component, and further contains a flame retardant and an ultraviolet absorbing agent. This can impart excellent weather resistance and flame retardancy to the transparent resin layer 4.

[0036] [Flame retardant] By containing a flame retardant, the transparent resin layer 4 can impart excellent flame retardancy to the transparent vinyl chloride resin forming the transparent resin layer 4, thereby improving the flame retardancy of the laminate sheet 1. As the flame retardant contained in the transparent resin layer 4, for example, known flame retardants such as tricresyl phosphate and hindered amine flame retardants can be used.

[0037] The amount of the flame retardant added to the transparent resin layer 4 is preferably within a range of, for example, 7 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the transparent vinyl chloride resin constituting the transparent resin layer 4. This makes it possible to more reliably improve the flame retardancy of the laminate sheet 1.

[0038] [Ultraviolet absorber] The transparent resin layer 4 contains an ultraviolet absorbing agent, which can impart excellent weather resistance to the transparent resin layer 4. Specifically, the transparent resin layer 4 contains at least one ultraviolet absorbing agent selected from a benzotriazole-based ultraviolet absorbing agent and a triazine-based ultraviolet absorbing agent as an ultraviolet absorbing agent.

[0039] The amount of the ultraviolet absorbing agent added to the transparent resin layer 4 may be determined according to the desired weather resistance, but is preferably 0.5 parts by mass or more per 100 parts by mass of the transparent vinyl chloride resin constituting the transparent resin layer 4, for example.

[0040] (Benzotriazole-based UV absorber) Examples of the "benzotriazole-based" ultraviolet absorbers 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-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and the like, as well as mixtures, modified products, polymers and derivatives thereof.

[0041] (Triazine-based UV absorber) Examples of the "triazine-based" ultraviolet absorbers 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.

[0042] 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 further preferably in the range of 60 μm to 80 μm. When the thickness of the transparent resin layer 4 is 50 μm or more, the weather resistance of the laminated sheet 1 can be reliably improved. 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, and the processability (e.g., bending processability) is improved and the manufacturing cost of the laminated sheet 1 can be reduced.

[0043] (Surface protective layer) The surface protective layer 5 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design to the laminate sheet 1. The material constituting the surface protective layer 5 is not particularly limited, and can be appropriately selected from, for example, urethane-based, acrylic-based, acrylic silicone-based, fluorine-based, and epoxy-based resin materials.

[0044] The surface protective layer 5 is mainly made of a resin composition and further contains a flame retardant, an ultraviolet absorbing agent, and a light stabilizer. That is, in the laminate sheet 1 according to the present embodiment, the surface protective layer 5 is formed of a resin composition and further contains a flame retardant and an ultraviolet absorbing agent. This can provide the surface protective layer 5 with excellent weather resistance and flame retardancy.

[0045] The surface protective layer 5 may contain various additives, such as a heat stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, if necessary.

[0046] Hereinafter, an example of the surface protective layer 5 according to this embodiment will be described with reference to a specific example. 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.

[0047] 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 laminated sheet, such as improving the maintenance of surface hardness, improving the stain resistance, and adjusting the surface gloss. 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.

[0048] 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.

[0049] 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, a flame retardant described below, and a weathering agent such as an ultraviolet absorber, onto the outermost surface of the laminate sheet 1. For example, the surface protective layer 5 may be formed by applying a coating liquid containing the above-mentioned acrylic resin composition, a flame retardant, and a weathering agent onto the transparent resin layer 4 having recesses that will become the embossed portions 7, and then by wiping, filling the recesses with the coating liquid.

[0050] 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 material, a two-component curing type which is crosslinked by isocyanate curing is desirable.

[0051] 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.

[0052] 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 may not proceed sufficiently, and the desired performance may not be imparted to the surface protective layer 5, which is not preferable.

[0053] 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.

[0054] [Flame retardant] By containing a flame retardant, the surface protective layer 5 can impart excellent flame retardancy to the resin composition forming the surface protective layer 5, and can improve the flame retardancy of the laminate sheet 1. As with the transparent resin layer 4, examples of the flame retardant contained in the surface protective layer 5 include tricresyl phosphate and hindered amine flame retardants.

[0055] The amount of the flame retardant added to the surface protective layer 5 is, for example, preferably in the range of 3 parts by mass to 6 parts by mass, and more preferably in the range of 3 parts by mass to 5 parts by mass, relative to 90 parts by mass of the main component (resin composition) constituting the surface protective layer 5. This makes it possible to more reliably improve the flame retardancy of the laminate sheet 1.

[0056] [Ultraviolet absorber] The surface protective layer 5 contains an ultraviolet absorbing agent, which can impart excellent weather resistance to the surface protective layer 5. The surface protective layer 5 contains at least one ultraviolet absorbing agent selected from a benzotriazole-based ultraviolet absorbing agent and a triazine-based ultraviolet absorbing agent as an ultraviolet absorbing agent.

[0057] As the ultraviolet absorbent of the surface protective layer 5, a triazine-based ultraviolet absorbent is preferable, and among them, if a hydroxyphenyltriazine-based ultraviolet absorbent is selected, 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 with the skeletons of benzotriazole-based ultraviolet absorbents and benzophenone-based ultraviolet absorbents. In other words, the surface protective layer 5 preferably contains a triazine-based ultraviolet absorbent as the ultraviolet absorbent.

[0058] 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.

[0059] 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."

[0060] In the surface protective layer 5 of this embodiment, the amount of the triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber added is preferably within a range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the main agent (e.g., an acrylic resin composition) forming the surface protective layer 5. By setting the amount of the ultraviolet absorber added to 1 part by mass or more, an effect of improving weather resistance is exhibited, 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 level that does not cause practical problems.

[0061] 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.

[0062] 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 triazine-based (hydroxyphenyltriazine-based) 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".

[0063] In this embodiment, the amount of ultraviolet absorber A added in the surface protective layer 5 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 absorber B. By setting the amount of ultraviolet absorber A added within the above numerical range, even better weather resistance can be imparted.

[0064] [Light stabilizer] The surface protective layer 5 contains a light stabilizer in addition to an ultraviolet absorbing agent as a weather resistance agent, thereby enabling the weather resistance of the laminate sheet 1 to be further improved.

[0065] For example, a radical scavenger can be used as the light stabilizer added to the surface protective layer 5. By using the above-mentioned triazine-based ultraviolet absorber and the radical scavenger in combination, the weather resistance of the laminate sheet 1 can be further improved. Examples of the hindered amine radical scavenger 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, and tetrakis(2,2,6,6-tetramethyl-4-piperidyl). -1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-ditert-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-octylamino-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-(2,2,6,6-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-triazine-6 -yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, reaction product of cyclohexane with N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide and reaction product of 2-aminoethanol, etc., but are not limited thereto.

[0066] In this embodiment, the amount of light stabilizer (e.g., a hindered amine-based radical scavenger) added to the surface protective layer 5 is preferably within a range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition (e.g., an acrylic resin composition) forming the surface protective layer 5. By adding 1 part by mass or more of the light stabilizer, it is possible to obtain the desired weather resistance, and by adding 30 parts by mass or less, it is possible to suppress bleeding out of the weather resistance agent and also to suppress the effect on other physical properties of the surface protective layer 5.

[0067] In the present embodiment, the surface protective layer 5 contains an ultraviolet absorbing agent and a light stabilizer, but the present disclosure is not limited thereto. The surface protective layer 5 may be provided with desired weather resistance according to the application, and may contain at least one of an ultraviolet absorbing agent and a light stabilizer.

[0068] <Amount of application> The coating amount of the surface protective layer 5, i.e., the coating amount of the material of the surface protective layer 5 on the transparent resin layer 4, is 2 g / m 2 More than 12g / m 2 The coating amount is preferably in the range of less than 2 g / m 2If it is less than 12 g / m, good weather resistance cannot be obtained. 2 By setting the coating amount within the above range, it is possible to achieve both good weather resistance and good recyclability. Also, by setting the coating amount within the above range, it is possible to improve productivity and processability (e.g., bending processability).

[0069] (embossed part) As shown in FIG. 1, an embossed portion 7 is provided on the outermost surface of the laminate 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 laminate sheet 1. The embossed portion 7 can be formed into various uneven shapes, such as wood grain duct grooves, stone slab surface embossments (granite cleavage surface, etc.), cloth surface texture, matte finish, sand grain, hairline, and stripe grooves, to impart a given design to the surface of the laminate 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 according to a desired design.

[0070] The embossed portion 7 is formed on the surface (outermost surface) side of the surface protection layer 5, which is the outermost layer of the laminate sheet 1, and forms a concave-convex pattern. In this embodiment, the above-mentioned surface protection layer 5 is embedded in the embossed portion 7 that forms the concave-convex pattern. This point will be described below.

[0071] In the laminate 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 easy to fill the embossed portion 7 with a surface protective layer composition (coating liquid) by wiping.

[0072] 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 .

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] (Laminate of transparent resin layer and surface protective layer) As described above, in this embodiment, the transparent resin layer 4 mainly made of polyvinyl chloride resin and the surface protective layer 5 mainly made of a resin composition formed on one side of the transparent resin layer 4 both contain an ultraviolet absorber and a flame retardant, the content of the flame retardant in the transparent resin layer 4 is within a range of 7 parts by mass to 15 parts by mass to 100 parts by mass of the polyvinyl chloride resin, and the content of the flame retardant in the surface protective layer 5 is within a range of 3 parts by mass to 6 parts by mass to 90 parts by mass of the resin composition. In this embodiment, the laminate of the two layers, the transparent resin layer 4 and the surface protective layer 5, imparts excellent weather resistance and flame retardancy to the laminate sheet 1, and by providing this laminate (the transparent resin layer 4 and the surface protective layer 5), the laminate sheet 1 according to this embodiment is imparted with excellent weather resistance and flame retardancy, and can be expected to withstand long-term outdoor use as a decorative sheet for decorating the surface of a decorative material for exterior use, as well as flame retardancy.

[0078] (Total sheet thickness) The thickness (total thickness) of the entire laminate sheet 1 according to this embodiment is preferably in the range of 50 μm or more and 300 μm or less, and more preferably in the range of 100 μm or more and 200 μm or less.

[0079] Here, when the laminate sheet 1 is formed of a laminate of a transparent resin layer 4 and a surface protective layer 5, the total thickness is the sum of the thicknesses of these two layers, and when the laminate sheet 1 is formed of a laminate of a colored original fabric layer 2, a pattern layer 3, a transparent resin layer 4, and a surface protective layer 5 as shown in Figure 1, the total thickness is the sum of the thicknesses of these four layers. In this way, by setting the overall thickness of the laminate sheet 1 within the range of 50 μm or more and 300 μm or less, a decorative sheet with good productivity and post-processability can be obtained.

[0080] (effect) The laminated sheet 1 according to the present embodiment has a transparent resin layer 4 and a surface protective layer 5 formed on one side of the transparent resin layer 4, the transparent resin layer 4 being mainly composed of polyvinyl chloride resin and further containing an ultraviolet absorber and a flame retardant, the surface protective layer 5 being mainly composed of a resin composition and further containing an ultraviolet absorber and a flame retardant, the content of the flame retardant in the transparent resin layer 4 being within a range of 7 parts by mass to 15 parts by mass to 100 parts by mass of polyvinyl chloride resin, and the content of the flame retardant in the surface protective layer 5 being within a range of 3 parts by mass to 6 parts by mass to 90 parts by mass of the resin composition. As a result, even when the laminated sheet 1 including the transparent resin layer 4 and the surface protective layer 5, which are mainly composed of polyvinyl chloride resin, is formed, it is possible to exhibit flame retardant performance and suppress weathering deterioration, and it is possible to obtain a laminated sheet 1 having weather resistance equivalent to that of a conventional olefin-based exterior sheet.

[0081] (Decorative materials) In this embodiment, the above-mentioned laminate sheet 1 may be attached to a substrate 8, which is a substrate for a decorative material, to form a decorative material 10.

[0082] (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). In addition, the decorative material 10 in which the substrate 8 made of polyvinyl chloride resin is decorated with the laminated sheet 1 can be reused by dissolving both the substrate 8 and the laminated sheet 1, which can improve recyclability.

[0083] From the viewpoint of flame retardancy, the base material 8 is preferably a flame retardant base material made of a flame-retardant steel plate or a flame-retardant material as specified in Notification No. 1400 of the Ministry of Construction.

[0084] As shown in Fig. 1, a laminate 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 laminate sheet 1 bonded to the base material 8.

[0085] By bonding the laminate sheet 1 according to this embodiment to a substrate 8, a decorative material 10 having excellent weather resistance and flame retardancy can be obtained even when formed using a polyvinyl chloride resin.

[0086] 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 such that, in addition to one surface of the base material 8, the laminate sheet 1 is laminated on the other surface of the base material 8 (the lower surface in Fig. 1).

[0087] (Method of manufacturing laminated sheet and decorative material) An example of a method for producing the laminate sheet 1 according to this embodiment will be briefly described below.

[0088] First, the 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.

[0089] 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 laminate sheet 1 according to the present embodiment is formed.

[0090] <Modification> Although the hydroxyphenyltriazine-based ultraviolet absorbers that can be added to the surface protective layer 5 have been described above, 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).

[0091] [ka]

[0092] In 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 containing a carbonyl group; R4 and R5 each independently represent a hydroxyl group, a methyl group, or a hydrogen atom; and R6 to R8 each independently represent a methyl group or a hydrogen atom.

[0093] [ka]

[0094] 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.

[0095] [ka]

[0096] [ka]

[0097] 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.

[0098] 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.

[0099] (Effects of this embodiment) (1) The laminate sheet 1 has a transparent resin layer 4 mainly made of polyvinyl chloride resin, and a surface protective layer 5 mainly made of a resin composition formed on one side of the transparent resin layer 4, the transparent resin layer 4 and the surface protective layer 5 both containing an ultraviolet absorber and a flame retardant, the content of the flame retardant in the transparent resin layer 4 is within a range of 7 parts by mass to 15 parts by mass to 100 parts by mass of the polyvinyl chloride resin, and the content of the flame retardant in the surface protective layer 5 is within a range of 3 parts by mass to 6 parts by mass to 90 parts by mass of the resin composition. Therefore, even when the laminate sheet 1 is formed using a polyvinyl chloride resin, it is possible to provide a laminate sheet having excellent weather resistance and flame retardancy, while exhibiting flame retardant performance and suppressing weather deterioration. (2) The content of the flame retardant in the surface protective layer 5 is within a range of 3 parts by mass to 5 parts by mass with respect to 100 parts by mass of the resin composition, which makes it possible to suppress a decrease in productivity and obtain a laminate sheet having flame retardancy and weather resistance equivalent to that of conventional laminates. (3) The ultraviolet absorber is at least one of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber, which can impart excellent weather resistance to the transparent resin layer 4 and the surface protective layer 5, thereby improving the weather resistance of the laminate sheet 1. (4) The surface protective layer 5 contains a triazine-based ultraviolet absorber and a light stabilizer, so that the weather resistance of the laminate sheet 1 can be further improved. (5) The decorative material 10 includes a substrate 8 and a laminate sheet 1. Therefore, even when formed using a polyvinyl chloride resin, it is possible to provide a decorative material 10 that has excellent weather resistance and flame retardancy. EXAMPLES

[0100] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0101] Example 1 A sheet made of polyvinyl chloride resin (hereinafter referred to as transparent PVC sheet) serving as a transparent resin layer was used as a substrate, and a surface protective layer was formed on one side of this transparent PVC sheet to obtain a laminated sheet.

[0102] The transparent resin layer and the surface protective layer have the following structures. [Transparent resin layer] Material: PVC, thickness: 100μm UV absorber: Triazine UV absorber 0.5 parts by weight per 100 parts by weight of PVC Flame retardant: Tricresyl phosphate 10 parts by weight per 100 parts by weight of PVC

[0103] [Surface protective layer] Base: 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 mass Hardener (Takenate D170; Mitsui Chemicals, Inc.) 10 parts by weight Solvent (ethyl acetate) 240 parts by weight Flame retardant: hindered amine flame retardant 3 parts by mass Coating amount: 6g / m 2 , thickness 6μm

[0104] Example 2 A laminate sheet of Example 2 was obtained in the same manner as in Example 1, except that the amount of the hindered amine flame retardant added as the flame retardant in the surface protective layer was 5 parts by mass. Example 3 A laminate sheet of Example 3 was obtained in the same manner as in Example 1, except that the amount of tricresyl phosphate added as a flame retardant to the transparent resin layer was 15 parts by mass. Example 4 A laminate sheet of Example 4 was obtained in the same manner as in Example 1, except that the amount of tricresyl phosphate added as a flame retardant to the transparent resin layer was 7 parts by mass.

[0105] Example 5 A laminate sheet of Example 5 was obtained in the same manner as in Example 1, except that the amount of the hindered amine flame retardant added as the flame retardant in the surface protective layer was 6 parts by mass. Example 6 The surface protection layer is applied at a rate of 2g / m 2 A laminate sheet of Example 6 was obtained in the same manner as in Example 1, except that the above-mentioned was used. Example 7 The surface protection layer is applied with a coating weight of 12 g / m 2 A laminate sheet of Example 7 was obtained in the same manner as in Example 1, except that the above-mentioned was used.

[0106] Comparative Example 1 A laminate sheet of Comparative Example 1 was obtained in the same manner as in Example 1, except that the amount of the hindered amine flame retardant added as the flame retardant in the surface protective layer was 2 parts by mass. Comparative Example 2 A laminate sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that the amount of tricresyl phosphate added as a flame retardant to the transparent resin layer was 6 parts by mass. Comparative Example 3 In Example 1, a sheet was formed only from a transparent resin layer without providing a surface protective layer.

[0107] 〔evaluation〕 The laminate sheets of the above Examples and Comparative Examples were evaluated for flame retardancy, weather resistance, and productivity by the following methods. The evaluation results are shown in Table 1. (Flame retardant performance) The laminated sheets of each of the Examples and Comparative Examples were subjected to a flame retardancy test in accordance with the 45° Meckel burner method of JIS L1091, standard for flame retardant articles under the Fire Service Act. A flame afterburner time of 3 seconds or less, a glow afterburner time of 5 seconds or less, and a unit cost area of ​​30 cm or less were evaluated as "○" (pass), and any other results were evaluated as "×" (fail).

[0108] (weather resistance) The appearance of each laminate sheet after the accelerated weathering test was evaluated in terms of the amount of hue change ΔE. The accelerated weathering test was performed using a metal weather tester (KU-R5DCI-A) manufactured by Daipla Wintes Co., Ltd., with a black panel temperature of 63°C and an illuminance of 65mW / cm. 2 The test was repeated 21 times (504 hours) with 20 hours of UV irradiation + 4 hours of condensation as one cycle. A colorimeter was used to measure the hue, and the Lab value was measured to calculate the amount of hue change ΔE. The evaluation criteria are as follows:

[0109] ⊚: The color difference before and after the weather resistance test is less than ΔE=2. ◯: The color difference before and after the weather resistance test is △E=2 or more and 4 or less. △: There are some places where the color difference before and after the weather resistance test is △E=4 or more. ×: Overall, the color difference before and after the weather resistance test is ΔE=4 or more. Here, a grade of "△" or higher was considered a pass.

[0110] (Productivity) Each laminate sheet was visually judged for the degree of defect, such as the film formability of the surface state, the presence or absence of fish eyes, the presence or absence of unevenness in thickness, etc. If there were almost no defects and it was comparable to a conventional laminate sheet (current product) made of an olefin-based resin, it was judged as "◎", if there were defects and it was inferior to the current product but did not affect production, it was judged as "○", if production was possible but there were defects that affected production and some ingenuity was required during production, it was judged as "△", and if production was impossible, it was judged as "×". Note that if there were about 1 to 2 defective parts per square meter, it was judged as "○". In this example, "△" or higher was judged to be pass.

[0111] [Table 1]

[0112] As can be seen from Table 1, the laminated sheets of Examples 1 to 7 have a transparent resin layer 4 mainly made of polyvinyl chloride resin and a surface protective layer 5 mainly made of a resin composition formed on one side of the transparent resin layer 4, and both the transparent resin layer 4 and the surface protective layer 5 contain an ultraviolet absorber and a flame retardant, and the content of the flame retardant in the transparent resin layer 4 is in the range of 7 parts by mass to 15 parts by mass to 100 parts by mass of polyvinyl chloride resin, and the content of the flame retardant in the surface protective layer 5 is in the range of 3 parts by mass to 6 parts by mass to 90 parts by mass of the main agent made of the resin composition. As a result, the laminated sheets of Examples 1 to 7 were all passed ("△" or higher) in terms of flame retardant performance, weather resistance, and productivity, and it was confirmed that they had excellent flame retardant performance and could suppress weather deterioration.

[0113] Moreover, it was confirmed from Examples 2 and 6 that the productivity was higher when the amount of the flame retardant added to the surface protective layer 5 was 5 parts by mass or less.

[0114] Furthermore, from Examples 6 and 7, it can be seen that reducing the amount of surface protective layer 5 applied results in a slight decrease in weather resistance, but allows flame retardant performance and productivity to be maintained, and conversely, increasing the amount of surface protective layer 5 applied results in a slight decrease in productivity, but allows flame retardant performance and weather resistance to be maintained.

[0115] On the other hand, Comparative Example 1 and Comparative Example 2 did not satisfy the conditions that the content of the flame retardant in the transparent resin layer is within the range of 7 parts by mass to 15 parts by mass to 100 parts by mass of polyvinyl chloride resin, and the content of the flame retardant in the surface protective layer is within the range of 3 parts by mass to 6 parts by mass to 90 parts by mass of the main agent made of a resin composition, and therefore it was confirmed that sufficient flame retardant performance was not obtained. Also, Comparative Example 3 did not satisfy the condition that the laminate sheet has a transparent resin layer and a surface protective layer, and therefore it was confirmed that sufficient flame retardant performance and weather resistance were not obtained.

[0116] The present invention can have the following configurations, for example. (1) A resin layer containing a polyvinyl chloride resin as a main component and a surface protective layer formed on one surface of the resin layer and containing a resin composition as a main component, the resin layer and the surface protective layer both contain an ultraviolet absorber and a flame retardant, The content of the flame retardant in the resin layer is within a range of 7 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the polyvinyl chloride resin, A laminate sheet, characterized in that the content of the flame retardant in the surface protective layer is within the range of 3 parts by mass or more and 6 parts by mass or less relative to 90 parts by mass of the resin composition. (2) The laminate sheet according to (1) above, characterized in that the content of the flame retardant in the surface protective layer is within the range of 3 parts by mass or more and 5 parts by mass or less with respect to 90 parts by mass of the resin composition. (3) The laminate sheet according to (1) or (2) above, wherein the ultraviolet absorber is at least one of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. (4) The laminate sheet according to any one of (1) to (3) above, wherein the surface protective layer contains a triazine-based ultraviolet absorber as the ultraviolet absorber and a light stabilizer. (5) The laminate sheet according to any one of (1) to (4) above, characterized in that the total thickness of the sheet is 50 μm or more and 300 μm or less. (6) The laminate sheet according to any one of (1) to (5) above, wherein an embossed portion is formed on the surface of the surface protective layer opposite to the resin layer. (7) The laminate sheet according to any one of (1) to (6) above, further comprising a pattern layer on the side of the resin layer opposite to the surface protective layer. (8) The laminate sheet according to any one of (1) to (7) above, characterized in that a colored base layer is provided on the side of the resin layer opposite to the surface protective layer. (9) A base material for a cosmetic material, A decorative material comprising the laminate sheet according to any one of (1) to (8) above bonded to the substrate for decorative material. [Explanation of symbols]

[0117] 1 Laminated sheet 2 Colored original fabric layer 3. Picture layer 4 Transparent resin layer 5 Surface protective layer 7 Embossed section 8 Base material 10 Cosmetic materials

Claims

1. A resin layer containing a polyvinyl chloride resin as a main component and a surface protective layer formed on one surface of the resin layer and containing a resin composition as a main component, the resin layer and the surface protective layer both contain an ultraviolet absorber and a flame retardant, The content of the flame retardant in the resin layer is within a range of 7 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the polyvinyl chloride resin, A laminate sheet, characterized in that the content of the flame retardant in the surface protective layer is within the range of 3 parts by mass or more and 6 parts by mass or less relative to 90 parts by mass of the resin composition.

2. 2. The laminate sheet according to claim 1, wherein the content of the flame retardant in the surface protective layer is within a range of 3 parts by mass to 5 parts by mass with respect to 90 parts by mass of the resin composition.

3. 3. The laminate sheet according to claim 2, wherein the ultraviolet absorbing agent is at least one of a benzotriazole-based ultraviolet absorbing agent and a triazine-based ultraviolet absorbing agent.

4. 4. The laminate sheet according to claim 3, wherein the surface protective layer contains a triazine-based ultraviolet absorber as the ultraviolet absorber and a light stabilizer.

5. 5. The laminate sheet according to claim 4, wherein the total thickness of the sheet is 50 μm or more and 300 μm or less.

6. 6. The laminate sheet according to claim 5, wherein an embossed portion is formed on the surface of the surface protection layer opposite to the resin layer.

7. 7. The laminate sheet according to claim 6, further comprising a design layer on the side of the resin layer opposite to the surface protective layer.

8. 8. The laminate sheet according to claim 7, wherein a colored base fabric layer is provided on the side of the resin layer opposite to the surface protective layer.

9. A base material for a cosmetic material, The laminate sheet according to any one of claims 1 to 8, which is bonded to the substrate for decorative material; A decorative material comprising:

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