Decorative sheets, decorative materials and fittings

Abstract

To provide a decorative sheet, a decorative member, and a fitting, having superior workability and formed using a polyvinyl chloride resin.SOLUTION: A decorative sheet 1 comprises at least a pattern layer 4 and a transparent polyvinyl chloride resin layer 6 stacked in this order, wherein the resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having an average degree of polymerization of 800 or more and 1500 or less as calculated in accordance with JIS K6720-2, and the transparent polyvinyl chloride resin layer 6 contains a high-molecular-weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less. This structure can achieve the decorative sheet 1 with superior workability.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet, a decorative member, and a fitting. [Background technology]

[0002] BACKGROUND ART Conventionally, decorative sheets made of vinyl chloride resin are known for use in decorating interior materials for housing and the like (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] It has been pointed out that polyvinyl chloride resin may contain dioxins, which are considered to be harmful substances, in the gases it emits when burned. However, in recent years, improvements in incineration equipment and exhaust gas treatment technology have helped to reduce the generation of harmful substances, and the existence of polyvinyl chloride resin is being reconsidered. Furthermore, with the growing awareness of zero-energy homes (ZEH), there is a high demand for highly insulated window frames (resin sashes) made of polyvinyl chloride resin, and the application of decoration to these base materials is also being considered. However, when olefin resin sheets are used as decorative materials for such window frames (resin sashes), there are problems such as the difficulty of recycling.

[0005] In contrast, polyvinyl chloride resin has the advantages of being highly adaptable to processing and easy to recycle, and so its use as a decorative material in combination with substrates such as vinyl chloride window frames is expected to contribute significantly to reducing the environmental impact. However, when polyvinyl chloride resin sheets are used outdoors for long periods of time, they can discolor, and when they are attached to substrates such as window frames, the sheets are often bent during processing, and polyvinyl chloride resin sheets have the characteristic of being prone to cracking when processed at low temperatures, so it is important to take this into consideration when designing.

[0006] The present invention has been made in view of the above-mentioned points, and has as its object to provide a decorative sheet, a decorative member, and a fitting that are excellent in processability. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have discovered that the above-mentioned objectives can be achieved in decorative sheets containing polyvinyl chloride resin by setting the composition of the decorative sheet, specifically the degree of polymerization and the content of plasticizer and weathering agent, to appropriate values. In other words, a decorative sheet according to one embodiment of the present invention is a decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in that order, wherein the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less, and the transparent resin layer contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less. In addition, a decorative sheet according to another aspect of the present invention is a decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, wherein the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less, and the transparent resin layer contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less.

[0008] In addition, a decorative member according to another aspect of the present invention is characterized by comprising the decorative sheet of the above aspect and a substrate arranged on the outermost surface of the decorative sheet on the side of the pattern layer. Furthermore, a fixture according to another aspect of the present invention is characterized by comprising the decorative sheet of the above aspect and a fixture component arranged on the outermost surface of the decorative sheet on the side of the pattern layer. [Effects of the Invention]

[0009] According to one aspect of the present invention, decorative sheets, decorative members, and fittings having excellent processability can be obtained. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a decorative sheet according to one embodiment of the present invention. [Figure 2] FIG. 10 is a cross-sectional view schematically illustrating an example of a decorative member according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present technology will be described with reference to the drawings. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., differ from the actual ones. The layers do not necessarily have to be stacked in the order shown in the drawings, as long as they are within the scope of the present disclosure. Layers not shown in the drawings may also be added. Furthermore, the embodiments shown below are illustrative of configurations that embody the technical ideas of the present disclosure, and the materials, shapes, structures, etc. of the components of the present disclosure are not limited to those described below. The technical ideas of the present disclosure may be modified in various ways within the technical scope defined by the claims. Furthermore, the directions of "left and right" and "up and down" in the following explanation are merely definitions for the convenience of explanation and do not limit the technical idea 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." (First embodiment) First, the first embodiment will be described.

[0012] (Composition of decorative sheet) FIG. 1 is a cross-sectional view that schematically shows an example of a decorative sheet 1 according to a first embodiment of the present invention. As shown in Figure 1, the decorative sheet 1 comprises a colored polyvinyl chloride resin layer (colored substrate layer) 2, a design layer 4, a transparent polyvinyl chloride resin layer (transparent resin layer) 6, and a surface protective layer 8. The surface protective layer 8, which is the outermost layer of the decorative sheet 1, has an embossed portion 10 formed from the surface side to the transparent polyvinyl chloride resin layer 6.

[0013] (Colored polyvinyl chloride resin layer) The colored polyvinyl chloride resin layer 2 functions as a support for the decorative sheet 1, and is colored opaquely to provide hiding properties, which allows the colored polyvinyl chloride resin layer 2 to conceal color variations and defects on the surface of the adherend when the decorative sheet 1 is attached to the adherend, such as a window frame. The colored polyvinyl chloride resin layer 2 is formed from polyvinyl chloride resin, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good formability and processability, and is also suitable for printing. By forming the decorative sheet 1 using the colored polyvinyl chloride resin layer 2, scraps of the decorative sheet 1 that are generated when the decorative sheet 1 is attached to an adherend, or used decorative sheet 1, can be melted and extruded using an extruder or the like and reused as recycled substrates. Furthermore, since PVC is easier to recycle by melting than olefin-based resins, the decorative sheet 1 according to this embodiment can have improved processability and recyclability.

[0014] Furthermore, the hue of the opaque colored polyvinyl chloride resin layer 2 can be appropriately selected as the base color of the pattern layer 4. Furthermore, when taking advantage of the texture of the surface of the adherend, the colored polyvinyl chloride resin layer 2 preferably has a transparency that allows the surface of the adherend to be seen through when viewed from the surface protective layer 8 side. The colored polyvinyl chloride resin layer 2 can be obtained, for example, by mixing or kneading a colorant such as a pigment into polyvinyl chloride resin. While organic or inorganic pigments can be used as colorants, inorganic pigments are preferred. In other words, the colored polyvinyl chloride resin layer 2 preferably contains an inorganic substance as a colorant. For example, the colored polyvinyl chloride resin layer 2 preferably contains one or more inorganic substances selected from the group consisting of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0015] Furthermore, the colored polyvinyl chloride resin layer 2 may contain, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters. Although the colored polyvinyl chloride resin layer 2 made of polyvinyl chloride resin is described here as the colored substrate layer, it is not limited to polyvinyl chloride resin. A colored thermoplastic resin layer made of a thermoplastic resin may be provided as the colored substrate layer, but from the viewpoint of recycling, it is preferable to use a polyvinyl chloride resin as the resin constituting the colored substrate layer, similar to the transparent polyvinyl chloride resin layer 6.

[0016] (Picture layer) The pattern layer 4 is laminated on one surface (the upper surface in FIG. 1) of the colored polyvinyl chloride resin layer 2, and is a layer for adding a pattern to impart design properties to the decorative sheet 1. The design layer 4 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the design layer 4 is formed, for example, by dissolving or dispersing a colorant such as a dye or pigment together with an appropriate binder resin in an appropriate diluent solvent. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

[0017] The printing ink or paint that forms the design layer 4 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. The binder resin contained in the design layer 4 is not particularly limited, but it is preferable to use a resin with good adhesiveness. That is, a resin that has thermal fusion properties with polyvinyl chloride resin, such as a vinyl chloride-vinyl acetate copolymer, an acrylic resin alone, or a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin, is preferable. Any pattern can be used as the pattern formed by the pattern layer 4, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, letters, symbols, solid colors, or combinations thereof. In order to improve the hiding power of the decorative sheet 1, a hiding layer may be provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2. The hiding layer is formed using, for example, an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0018] The thickness of the design layer 4 is preferably in the range of 1 μm or more and 10 μm or less. This is because when the thickness of the design layer 4 is 1 μm or more, it is possible to make the printing clear. On the other hand, when the thickness of the design layer 4 is 10 μm or less, it is possible to improve the printing workability when producing the decorative sheet 1 and to reduce production costs. In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the design layer 4 to impart various functions. In addition, the pattern layer 4 may be configured to have, for example, a solid colored base layer to conceal the color and pattern of the substrate to which the decorative sheet 1 is attached, and a pattern layer to add a pattern to impart design features.

[0019] (Transparent polyvinyl chloride resin layer) The transparent polyvinyl chloride resin layer 6 is a layer for improving the weather resistance of the decorative sheet 1. The transparent polyvinyl chloride resin layer 6 is formed of polyvinyl chloride resin, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, and has good moldability and processability, and is also suitable for printing. As mentioned 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. In other words, the decorative sheet 1 according to this embodiment can reliably improve processability and recyclability by using the colored polyvinyl chloride resin layer 2 and transparent polyvinyl chloride resin layer 6, both of which contain polyvinyl chloride resin.

[0020] The transparent polyvinyl chloride resin layer 6 preferably has a transparency sufficient to allow the pattern layer 4 provided on the surface on the colored polyvinyl chloride resin layer 2 side (the lower surface in FIG. 1) to be seen through when viewed from the surface protection layer 8 side. The transparent polyvinyl chloride resin layer 6 is preferably, for example, colorless and transparent, colored and transparent, or translucent. The resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500. In terms of the K value calculated in accordance with JIS K7367-2:1999, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having a K value of 60 to 75.

[0021] The higher the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6, the stronger, more elongated, and less susceptible to cracking the decorative sheet 1, and the more durable it is. If the average degree of polymerization is too high, the gelation temperature increases, resulting in fisheyes and other defects, making film formation of the transparent polyvinyl chloride resin layer 6 difficult. Furthermore, the lower the average degree of polymerization, the more susceptible the decorative sheet 1 is to cracking, and the lower the viscosity, the poorer the calendering suitability and the poorer the film formation stability. Therefore, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin with an average degree of polymerization of 800 to 1500, as calculated in accordance with JIS K6720-2. Furthermore, when the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is 800 to 1500, the decorative sheet 1 has a breaking elongation of 10% to 400% at 0°C, ensuring stable production during processes such as wrapping. If the breaking elongation at 0°C is less than 10%, the decorative sheet 1 is too hard, potentially causing whitening and cracking. If the breaking elongation at 0°C is greater than 400%, the decorative sheet 1 will be soft and have no stiffness, making it difficult to handle, resulting in poor productivity and poor scratch resistance.

[0022] Similarly, when the K value of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is within the range of 60 or more and 75 or less, the breaking elongation of the decorative sheet 1 at 0°C is 10% or more and 400% or less, and when the K value is less than 60 or greater than 75, the breaking elongation of the decorative sheet 1 at 0°C is less than 10% or greater than 400%. A plasticizer may be added to the transparent polyvinyl chloride resin layer 6. A high-molecular-weight polyester resin is preferred as the plasticizer, and the content of the plasticizer is preferably 20 PHR to 30 PHR. In terms of viscosity, the viscosity of the plasticizer measured with a capillary viscometer in accordance with JIS K7367-5:2000 is preferably 500 MPa s to 3000 MPa s.

[0023] Among polyester resins, high molecular weight polyesters are preferred as plasticizers. Phthalic acid resins (dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more prone to bleed-out than high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance. If the plasticizer content is less than 20 PHR, cold resistance will be poor even if a phthalic acid resin is used, so if a high molecular weight polyester resin is used as the plasticizer, the plasticizer content is preferably 20 PHR or more. If the plasticizer content is more than 30 PHR, the decorative sheet 1 will become soft and lose its stiffness, making it difficult to handle and reducing productivity during processing. In addition, the decorative sheet 1 will have poor scratch resistance.

[0024] Furthermore, if the viscosity of the plasticizer is less than 500 MPa·s, it has a low molecular weight, is prone to bleeding, and has poor weather resistance. If the viscosity of the plasticizer is more than 3000 MPa·s, it is too high a molecular weight, making resin production difficult. It also has poor cold resistance. When the plasticizer content is within the range of 20 PHR or more and 30 PHR or less, the breaking elongation of the decorative sheet 1 at 0°C is 10% or more and 400% or less, resulting in good production stability during processing such as wrapping. As mentioned above, if the breaking elongation at 0°C is less than 10%, the decorative sheet 1 will be hard and will whiten and crack, and if it is more than 400%, the decorative sheet 1 will be soft and have no stiffness, making it difficult to handle, resulting in poor productivity and poor scratch resistance.

[0025] [Weatherproofing agent] The transparent polyvinyl chloride resin layer 6 may further contain a weather resistance agent, which can impart excellent weather resistance to the transparent polyvinyl chloride resin layer 6. The transparent polyvinyl chloride resin layer 6 may contain a NOR-type hindered amine light stabilizer (HALS) as a weather resistance agent. Using a NOR-type HALS with low basicity can suppress the dehydrochlorination reaction of the transparent polyvinyl chloride resin layer 6, making it effective against recent acid rain. Examples of NOR-type hindered amine light stabilizers (HALS) that can be used in the transparent polyvinyl chloride resin layer 6 include "ADEKA STAB LA-81" manufactured by ADEKA Corporation, "TINUVIN 123" (decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester) manufactured by BASF Japan Ltd., and "TINUVIN XT850FF" manufactured by BASF Japan Ltd.

[0026] Furthermore, the transparent polyvinyl chloride resin layer 6 may contain an ultraviolet absorber as a weather resistance agent, and preferably contains at least one of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber, and more preferably contains a cyanoacrylate-based ultraviolet absorber. The amount of UV absorber added to the transparent polyvinyl chloride resin layer 6 may be determined according to the desired weather resistance, but it is preferable that the amount of UV absorber be 0.5 parts by mass or more per 100 parts by mass of the transparent vinyl chloride resin that constitutes the transparent polyvinyl chloride resin layer 6. This ensures that the weather resistance of the decorative sheet 1 is improved.

[0027] (Benzophenone-based UV absorber) Examples of "benzophenone-based" ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), and mixtures, modified products, polymers, and derivatives thereof.

[0028] (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-(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.

[0029] (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.

[0030] (Cyanoacrylate UV absorber) Examples of "cyanoacrylate" ultraviolet absorbers include ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and the like. The thickness of the transparent polyvinyl chloride resin layer 6 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. A thickness of 50 μm or more reliably improves the weather resistance of the decorative sheet 1 and can also absorb irregularities in the adherend, such as window frames, to improve the application finish of the decorative sheet 1. Furthermore, if the thickness of the transparent polyvinyl chloride resin layer 6 is 150 μm or less, the transparent polyvinyl chloride resin layer 6 is not formed thicker than necessary, improving processability (e.g., bending processability) and reducing the manufacturing cost of the decorative sheet 1.

[0031] [Heat stabilizer] The transparent polyvinyl chloride resin layer 6 preferably contains a metal salt of a higher fatty acid as a heat stabilizer.

[0032] (Surface protective layer) The surface protective layer 8 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 1. The material constituting the surface protective layer 8 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. The surface protective layer 8 may contain various additives such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as needed, and preferably contains an ultraviolet absorber and a light stabilizer. The surface protective layer 8 is not necessarily provided, but is preferably provided.

[0033] An example of the surface protection layer 8 according to this embodiment will be described below by giving a specific example. In this embodiment, the surface protection layer 8 may be mainly composed of an acrylic resin composition containing cyclohexyl(meth)acrylate as a monomer component. In this embodiment, cyclohexyl(meth)acrylate refers to cyclohexyl acrylate or cyclohexyl methacrylate. By including cyclohexyl(meth)acrylate as a monomer component, the affinity for water can be reduced, and deterioration due to hydrolysis or the like can be suppressed.

[0034] 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, i.e., among the monomer components of the acrylic resin composition that is the main component of the surface protective layer 8. By setting the cyclohexyl (meth)acrylate content to 5% by mass or more, a sufficient deterioration suppression effect can be obtained. Furthermore, by setting the cyclohexyl (meth)acrylate content to 50% by mass or less, it is possible to impart high weather resistance over time without significantly changing the various performance properties of the surface protective layer 8 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 that constitutes the surface protective layer 8 is 50% by mass or more relative to the total mass of the surface protective layer 8.

[0035] In addition to cyclohexyl(meth)acrylate, examples of monomer components of the acrylic resin composition that can be used for the surface protective layer 8 according to this embodiment include cyclohexylmethyl(meth)acrylate, cyclohexylethyl(meth)acrylate, cyclohexylpropyl(meth)acrylate, cyclohexylbutyl(meth)acrylate, dimethylcyclohexane mono(meth)acrylate, dimethylcyclohexane di(meth)acrylate, trimethylcyclohexane mono(meth)acrylate, trimethylcyclohexane di(meth)acrylate, trimethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane mono(meth)acrylate, tetramethylcyclohexane di(meth)acrylate, tetramethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane tetra(meth)acrylate, dicyclohexylmethyl(meth)acrylate, dicyclohexylmethyl(meth)acrylate, phenoxycyclohexylmethyl(meth)acrylate, and methoxycyclohexylmethyl(meth)acrylate. Among these, those containing isomers may be each isomer alone and / or a mixture of each isomer.

[0036] Furthermore, in this embodiment, the surface protective layer 8 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, which will be described later, to the outermost surface of the decorative sheet. As will be described in detail later, for example, the surface protective layer 8 may be formed by applying a coating liquid containing the above-mentioned acrylic resin composition and a weathering agent to the transparent polyvinyl chloride resin layer 6 on which the embossed portions 10 have been formed, and then wiping the surface to embed the coating liquid in the embossed portions 10. The curing method for the coating liquid for forming the surface protection layer 8 can be, for example, a one-component curing type, a two-component curing type that uses a curing agent, or an active energy ray curing type that is cured by irradiating with ultraviolet light or ionizing radiation, etc. However, 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 bonded to various substrates to form a decorative component, the two-component curing type that is crosslinked by isocyanate curing is desirable.

[0037] A preferred example of a two-component curing acrylic resin composition is 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. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0038] Examples of acrylic polyols having two or more hydroxyl groups per molecule include (meth)acrylic acid ester copolymers containing, in addition to the aforementioned cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate as a monomer component. Examples of polyisocyanate compounds having two or more isocyanate groups per molecule include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer, TMP adduct, and biuret types synthesized from one or more compounds selected from these compounds using known techniques. Compositions containing a mixture of one or more of these different types of polyisocyanates can also be used. Among these, HDI, or HDI trimer, TMP adduct, and biuret types are preferred from the standpoint of weather resistance. The content of the isocyanate compound relative to the resin component can be set arbitrarily, but it is desirable to set it so that the equivalent ratio of hydroxyl groups to isocyanate groups is about 1:1 to 1:3. In particular, if the equivalent weight of hydroxyl groups is greater than the equivalent weight of isocyanate groups, crosslinking may not proceed sufficiently, and the desired performance may not be imparted to surface protective layer 8, which is not preferable.

[0039] When the coating liquid for forming the surface protection layer 8 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. In order to further improve the weather resistance of the decorative sheet 1, in this embodiment, an ultraviolet absorber and a light stabilizer are added to the surface protective layer 8 as weather resistance agents.

[0040] (ultraviolet absorber) As the ultraviolet absorber, for example, known ones such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), and benzophenone-based ones can be used. Among these, if a hydroxyphenyltriazine-based ultraviolet absorber is selected, the triazine skeleton suppresses bleeding, and the triazine skeleton is more chemically stable than the skeletons of benzotriazole-based and benzophenone-based ultraviolet absorbers, making it possible to maintain ultraviolet absorption performance for a long period of time. In other words, it is preferable that the surface protective layer 8 contains a triazine-based ultraviolet absorber as the ultraviolet absorber.

[0041] 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-ethylhexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl) -3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and the like. In this embodiment, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter referred to as "ultraviolet absorber A" for convenience) may be contained in the surface protective layer 8. 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."

[0042] In the surface protective layer 8 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 relative to 100 parts by mass of the resin composition (e.g., an acrylic resin composition) that forms the surface protective layer 8. By adding the ultraviolet absorber in an amount of 1 part by mass or more, an effect of improving weather resistance is exhibited, and by adding the ultraviolet absorber in an amount of 30 parts by mass or less, the effects on physical properties of the surface protective layer 8 other than weather resistance can be suppressed to a level that does not pose a practical problem. In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber to be added to the surface protective layer 8, the amount added is preferably in the range of 1 to 20 parts by mass, more preferably in the range of 5 to 15 parts by mass, and even more preferably in the range of 8 to 12 parts by mass, relative to 100 parts by mass of the acrylic resin composition. By adding the ultraviolet absorber A in an amount of 1 part by mass or more, an effect of improving weather resistance is exerted, and by adding it in an amount of 20 parts by mass or less, the effects on physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a level that does not cause practical problems.

[0043] Furthermore, in this embodiment, the surface protective layer 8 includes a triazine-based (hydroxyphenyltriazine-based) UV absorber. The combination of UV absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter referred to as "UV absorber B") provides even better weather resistance. This is because UV absorber B has a high UV absorption capacity in the relatively high-energy short-wavelength region of UV and is chemically more stable than other UV absorbers that absorb in roughly the same wavelength region. Therefore, the combined use of these two UV absorbers broadens the UV absorption wavelength range. UV absorber B, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, is commonly known as the main component of "ADK STAB LA-46 (manufactured by ADEKA Corporation)."

[0044] In this embodiment, the amount of ultraviolet absorber A added to the surface protective layer 8 is preferably in the range of 10 to 200 parts by mass, more preferably in the range of 20 to 100 parts by mass, and even more preferably in the range of 40 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.

[0045] (light stabilizer) As the light stabilizer added to the surface protective layer 8, for example, a radical scavenger can be used. By using the above-mentioned triazine-based ultraviolet absorber in combination with this radical scavenger, the weather resistance performance of the decorative sheet 1 can be further improved. Examples of hindered amine-based 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-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, 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-mono Fluorino-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-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-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, the reaction product of cyclohexane with N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide and 2-aminoethanol, but are not limited thereto.

[0046] In this embodiment, the amount of light stabilizer (e.g., a hindered amine-based radical scavenger) added to surface protective layer 8 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 resin composition (e.g., an acrylic resin composition) that forms surface protective layer 8. 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 bleed-out of the weather resistance agent and also to suppress the effect on other physical properties of surface protective layer 8. In the present embodiment, the surface protective layer 8 contains an ultraviolet absorber and a light stabilizer, but the present disclosure is not limited to this. The surface protective layer 8 may be configured to contain at least one of an ultraviolet absorber and a light stabilizer, as long as it has the desired weather resistance depending on the application.

[0047] (Amount of application) The coating amount of the surface protective layer 8, i.e., the coating amount of the material of the surface protective layer 8 on the transparent polyvinyl chloride resin layer 6, was 3 g / m 2 More than 10g / m 2 The coating amount is preferably in the range of less than 3 g / m 2 If it is less than 10 g / m, good weather resistance cannot be obtained.2 Since a coating amount above this range may impair recyclability, by setting the coating amount within this range, it is possible to achieve both good weather resistance and recyclability. Furthermore, by setting the coating amount within this range, it is possible to improve productivity and processability (for example, bending processability).

[0048] (embossed part) As shown in FIG. 1 , an embossed portion 10 is provided on the outermost surface of the decorative sheet 1. By providing the embossed portion 10 on the outermost surface, it is possible to improve fingerprint resistance while maintaining the matte feel of the surface of the decorative sheet 1. Furthermore, the embossed portion 10 can be formed into various uneven shapes, such as wood grain vascular grooves, stone slab surface unevenness (granite cleavage planes, etc.), cloth surface texture, matte finish, sand grain, hairline, and linear grooves, thereby imparting a given design to the surface of the decorative sheet 1. The embossed portion 10 can be formed into various uneven shapes, for example, depending on the design of the picture layer 4 or the desired design. The embossed portions 10 are formed on the surface (outermost surface) side of the surface protection layer 8, which is the outermost layer of the decorative sheet 1, and form a concave-convex pattern. In this embodiment, the above-mentioned surface protection layer 8 is embedded in the embossed portions 10 that form this concave-convex pattern. This point will be explained below.

[0049] In the decorative sheet 1 according to this embodiment, the embossed portions 10 are provided in the transparent polyvinyl chloride resin layer 6. That is, the transparent polyvinyl chloride resin layer 6 is the layer on which the embossed portions 10 are formed. The shape of the uneven pattern provided on the surface of the transparent polyvinyl chloride resin layer 6 is not particularly limited, but it is preferable that the shape of the embossed portions 10 constituting the uneven pattern is such that the opening diameter increases from the design layer 4 side of the transparent polyvinyl chloride resin layer 6 toward the surface protective layer 8. With such a shape, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portions 10 by wiping.

[0050] Furthermore, the side surface on which the embossed portion 10 is formed is preferably an inclined surface. If the side surface on which the embossed portion 10 is formed is an inclined surface, it becomes easier to fill the embossed portion 10 with the surface protection layer composition (coating liquid) by wiping. In addition, the entire side surface forming the embossed portion 10 may be covered with the surface protection layer 8. The depth of the embossed portion 10 is preferably within a range of 1 μm to 50 μm in the thickness direction of the transparent polyvinyl chloride resin layer 6. When the depth of the embossed portion 10 is within the above range, the surface protective layer composition (coating liquid) can be easily embedded into the embossed portion 10 by wiping, and peeling of the surface protective layer can be prevented.

[0051] The width of the embossed portion 10 in the cross section shown in Fig. 1 is preferably in the range of 1 µm to 20 µm. If the width of the embossed portion 10 is in the above-mentioned range, the surface protective layer composition (coating liquid) can be easily embedded in the embossed portion 10 by wiping, and the surface protective layer embedded in the embossed portion 10 can be prevented from peeling off.

[0052] Furthermore, it is preferable that the embossed portion 10 is completely filled (packed) with the surface protective layer composition (coating liquid), and a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 is preferably 10% or more. A filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 10% or more can improve the weather resistance of the embossed portion 10. In other words, a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 10% or more can reduce the occurrence of whitening or breakage in the conduit portion, for example. Furthermore, as described above, a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 100% is preferable, but a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 80% or less is more preferable, and a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 60% or less is even more preferable. A filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 80% or less can provide a satisfactory tactile feel in the embossed portion 10.

[0053] Furthermore, by setting the filling rate of the surface protection layer 8 to 100% of the volume of the embossed portion 10, the surface of the surface protection layer 8 filled in the embossed portion 10 and the surface of the transparent polyvinyl chloride resin layer 6 in the area not having the embossed portion 10 can be made flush, so to speak. The embossed portion 10 is not necessarily provided, but is preferably provided.

[0054] (Total thickness of decorative sheet) The total thickness of the decorative sheet 1, i.e., the sum of the thicknesses of the colored polyvinyl chloride resin layer 2, the design layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8, is preferably in the range of 100 μm to 300 μm, more preferably 120 μm to 200 μm. If the total thickness of the decorative sheet 1 is thinner than 100 μm, the hiding power and scratch resistance are reduced, and further, the decorative sheet 1 loses rigidity during processing, resulting in reduced productivity. If the total thickness of the decorative sheet 1 is thicker than 300 μm, the processability, such as bending, is reduced. This allows for the formation of a decorative sheet 1 that has the same level of hiding power as decorative sheets formed using conventional olefin-based resins and good processability. Note that the total thickness of the decorative sheet 1 here refers, in the case of the decorative sheet 1 shown in FIG. 1, to the sum of the thicknesses of the colored polyvinyl chloride resin layer 2, the design layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8, i.e., the sum of the thicknesses of all layers that make up the decorative sheet 1. For example, in the decorative sheet 1 shown in Figure 1, if a concealing layer is provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2, the thickness refers to the total thickness of the decorative sheet 1, which is the sum of the thickness of the colored polyvinyl chloride resin layer 2, the thickness of the pattern layer 4, the thickness of the transparent polyvinyl chloride resin layer 6, the thickness of the surface protective layer 8, and the thickness of the concealing layer; in other words, it refers to the total thickness of the decorative sheet 1 formed including a laminate in which the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8 are laminated in this order.

[0055] (Variation) In the decorative sheet 1, a gloss-adjusting layer (not shown) may be provided on the surface protective layer 8, and the gloss-adjusting layer and the pattern of the pattern layer 4 may be made to match each other. In addition, in the decorative sheet 1, the pattern of the pattern layer 4 and the embossed portions 10 may be synchronized. Furthermore, although the decorative sheet 1 has a colored polyvinyl chloride resin layer 2 as a colored substrate layer, the colored polyvinyl chloride resin layer (colored substrate layer) 2 does not necessarily have to be provided, that is, the decorative sheet 1 may be a single-layer specification. If the decorative sheet 1 is a single-layer specification, it is preferable to provide a concealing layer (not shown) on the surface of the design layer 4 opposite the transparent polyvinyl chloride resin layer 6.

[0056] (decorative materials) The decorative sheet 1 shown in FIG. 1 may be attached to a substrate 20 as shown in FIG. 2 to form a decorative member 100.

[0057] (base material) The substrate 20 can be a wood substrate or a metal substrate. Examples of wood substrates that can be used include wood veneers, wood plywood, laminated lumber, particle board, medium-density fiberboard, and hard fiberboard. Examples of metal substrates that can be used include steel and aluminum plates. The substrate 20 can also be made of a resin such as plastic, or a composite material thereof. When the substrate 20 is a resin substrate, for example, vinyl chloride resin can be used. Vinyl chloride resin substrates 20 have high insulating properties and are increasingly in demand as window frame fixtures (sashes). Furthermore, a decorative member 100 in which a vinyl chloride resin substrate 20 is decorated with a decorative sheet 1 can be reused by dissolving both the substrate 20 and the decorative sheet 1, thereby improving recyclability.

[0058] The substrate 20 may be made of, for example, a non-combustible steel plate or a non-combustible material as specified in Ministry of Construction Notification No. 1400. The substrate 20 may have a bent structure or a three-dimensional structure. By laminating the decorative sheet 1 according to this embodiment to the substrate 20, a decorative member with excellent processability and recyclability can be obtained, even when the substrate 20 is formed using polyvinyl chloride resin. The configuration of the decorative member 100 is not limited to the example shown in Fig. 2. That is, the decorative member 100 may be configured to include a decorative sheet 1 laminated on one surface of the base material 20, as well as on the other surface of the base material 20 (the lower surface in Fig. 1).

[0059] When laminating the decorative sheet 1 to the substrate 20, an adhesive layer 12 may be provided by laminating the sheet via an adhesive selected as necessary, or the sheet may be laminated directly without an adhesive or the like. The adhesive may be selected depending on the material of the base material 20, and may be a two-component curing or hot melt adhesive. Methods for laminating and adhering the decorative sheet 1 to the substrate 20 include a method of pressing with a metal plate in contact with the substrate using flat pressure, and a continuous lamination method using a circular pressure method. In particular, the continuous lamination method using an endless metal belt allows for the high-quality decorative member 100 to be produced continuously at high speed without warping or waviness on the surface, with good adhesion between the layers and densely cured and integrated.

[0060] The substrate 20 is effective when applied to window frames and other fittings, particularly exterior fittings. In other words, with the growing awareness of zero-energy homes (ZEH), there is a high demand for highly insulated window frames and other fittings made from polyvinyl chloride resin for exterior fittings. Because the decorative sheet 1 is made from polyvinyl chloride, by attaching it to fittings, particularly window frames made from polyvinyl chloride resin, and forming the substrate 20 and the decorative sheet 1 into a mono-material, fittings, particularly exterior fittings, that are highly recyclable compared to those made from olefin-based resin sheets, etc., can be obtained. It is also possible to use building materials made of other materials, such as aluminum, as the base material 20. In this case, recyclability will be somewhat reduced compared to when it is made into a mono-material, but by laminating a decorative sheet 1 made of polyvinyl chloride resin, it is possible to obtain building materials that are highly suitable for processing.

[0061] (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. For example, the design layer 4 is printed on the colored polyvinyl chloride resin layer 2 made of a colored polyvinyl chloride resin sheet. Next, a transparent polyvinyl chloride resin layer 6 is formed by thermal lamination on the colored polyvinyl chloride resin layer 2 on which the pattern layer 4 has been formed, and at the same time, an embossed portion 10 is formed by providing a concave-convex pattern on the surface of the transparent polyvinyl chloride resin layer 6 opposite to the colored polyvinyl chloride resin layer 2 by embossing. Next, a coating liquid for forming a surface protection layer 8 is applied to the surface of the transparent polyvinyl chloride resin layer 6 on which the concave-convex pattern (embossed portion 10) has been formed. Finally, the coating liquid is wiped so as to fill the embossed portions 10 that form the uneven pattern, and the coating liquid is cured to form a surface protection layer 8 on the transparent polyvinyl chloride resin layer 6. In this way, the decorative sheet 1 according to this embodiment is formed.

[0062] An adhesive is applied to the surface of the decorative sheet 1 formed in this manner on the side of the colored polyvinyl chloride resin layer 2, and a substrate 20 is attached to form a decorative member 100 in which the decorative sheet 1 and the substrate 20 are bonded together via the adhesive layer 12. The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even in forms other than this embodiment, as long as they do not deviate from the technical idea of the present invention.

[0063] (effect) (1) The decorative sheet 1 according to the first embodiment of the present invention is formed by laminating at least a design layer 4 and a transparent polyvinyl chloride resin layer 6 in this order, and the resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500, and the transparent polyvinyl chloride resin layer 6 further contains a high-molecular-weight polyester-based plasticizer of 20 to 30 PHR. Therefore, even when forming a film from a transparent polyvinyl chloride resin sheet, film formation stability can be ensured, and good wrapping suitability of the decorative sheet 1 and good bending condition of the decorative sheet 1 during wrapping can be obtained. Furthermore, the decorative sheet 1 is composed of at least a design layer 4 and a transparent polyvinyl chloride resin layer 6 laminated in this order, and the resin that constitutes the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 to 75, and the transparent polyvinyl chloride resin layer 6 further contains a high-molecular-weight polyester-based plasticizer of 20 to 30 PHR. Therefore, even in this case, even when a transparent polyvinyl chloride resin sheet is formed into a film, film formation stability can be ensured, and good wrapping suitability of the decorative sheet 1 and good bending condition of the decorative sheet 1 during wrapping can be obtained.

[0064] (2) The decorative sheet 1 has a breaking elongation of 10% or more and 400% or less at 0°C, so it has moderate softness, which prevents whitening and cracking during wrapping, and prevents a decrease in productivity and a decrease in scratch resistance. (3) The viscosity of the plasticizer added to the transparent polyvinyl chloride resin layer 6, measured using a capillary viscometer in accordance with JIS K7367-5:2000, satisfies the range of 500 MPa·s to 3000 MPa·s, thereby ensuring good weather resistance. At the same time, by adjusting the viscosity to 500 MPa·s to 3000 MPa·s, the breaking elongation of the decorative sheet 1 at 0°C can be easily adjusted to a range of 10% to 400%. (4) By using NOR type HALS as the HALS to be added to the transparent polyvinyl chloride resin layer 6, the dehydrogenation reaction can be suppressed.

[0065] (5) By forming the decorative member 100 from a base material 20 and a decorative sheet 1 bonded to this base material 20, a decorative member 100 with excellent processability can be provided even if the decorative sheet 1 is formed using polyvinyl chloride resin. (6) Because the fittings are formed by laminating the decorative sheet 1 to the fitting material as the base material 20, fittings with excellent processability can be provided even when the decorative sheet 1 is formed using polyvinyl chloride resin. In particular, by laminating the decorative sheet 1 to an exterior fitting material (base material 20) made of a vinyl chloride-based material, both the decorative sheet 1 and the fitting material are made into a mono-material made of a vinyl chloride-based material, which further enhances recyclability. Example 1

[0066] The first embodiment of 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.

[0067] (Example 1-1) A colored polyvinyl chloride resin sheet was used as the colored polyvinyl chloride resin layer (colored substrate layer). A design layer was formed on one side of the colored polyvinyl chloride resin sheet by gravure printing using a printing ink for vinyl chloride. Then, a transparent polyvinyl chloride resin sheet as a transparent polyvinyl chloride resin layer (transparent resin layer) was thermally laminated onto the colored polyvinyl chloride resin sheet including the design layer. Then, a resin composition mainly composed of an acrylic resin composition was laminated onto the transparent polyvinyl chloride sheet as a surface protective layer. This resulted in the decorative sheet of Example 1-1. The resulting decorative sheet had a breaking elongation of 40% at 0°C. The composition of each layer is as follows:

[0068] (Colored polyvinyl chloride resin sheet) Material: Polyvinyl chloride resin (PVC) Thickness: 80 μm

[0069] (Transparent polyvinyl chloride resin sheet) Material: Polyvinyl chloride resin (PVC) Degree of polymerization: 820 K value: 62.1 Thickness: 80 μm Plasticizer: High molecular weight polyester Viscosity: 510 Additives: 20PHR UV absorber: 0.5 parts by mass of cyanoacrylate UV absorber HALS: NOR type 0.5 parts by mass (ADEKA STAB LA81, manufactured by ADEKA Corporation)

[0070] (Picture layer) Binder resin: A mixture of vinyl chloride resin-vinyl acetate resin copolymer and acrylic resin

[0071] (Surface protective layer) Main ingredient: methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) 90 parts by weight UV absorber: Tinuvin 479 (manufactured by BASF Japan Ltd.) 9 parts by mass Light stabilizer: Tinuvin 123 (BASF Japan Ltd.) 1 part by mass Hardener: Takenate D170 manufactured by Mitsui Chemicals, Inc. 10 parts by mass Solvent: 240 parts by weight of ethyl acetate Coating amount 3g / m 2

[0072] (Example 1-2) The decorative sheet of Example 1-2 was obtained in the same manner as in Example 1-1, except that a transparent polyvinyl chloride resin (PVC) with a degree of polymerization of 1440 and a K value of 73.6 was used and the amount of plasticizer added was 28 PHR. The resulting decorative sheet had a breaking elongation of 320% at 0°C. (Examples 1-3) The decorative sheet of Example 1-3 was obtained in the same manner as Example 1-1, except that a high molecular weight polyester plasticizer with a viscosity of 2500 was used as the plasticizer in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 110% at 0°C.

[0073] (Examples 1-4) A decorative sheet of Example 1-4 was obtained in the same manner as in Example 1-3, except that a benzophenone-based ultraviolet absorber was used as the ultraviolet absorber in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 120% at 0°C. (Examples 1-5) The decorative sheet of Example 1-5 was obtained in the same manner as Example 1-1, except that the transparent polyvinyl chloride resin sheet used was a polyvinyl chloride resin (PVC) with a degree of polymerization of 1020 and a K value of 66.5, the plasticizer used was a high molecular weight polyester plasticizer with a viscosity of 1200, and the additive amount of this plasticizer was 24 PHR. The resulting decorative sheet had a breaking elongation of 260% at 0°C.

[0074] (Examples 1 to 6) The decorative sheet of Example 1-6 was obtained in the same manner as in Example 1-5, except that the transparent polyvinyl chloride resin sheet used was a polyvinyl chloride resin (PVC) with a degree of polymerization of 1320 and a K value of 71.7, and the plasticizer used was a high molecular weight polyester-based plasticizer with a viscosity of 2000. The resulting decorative sheet had a breaking elongation of 300% at 0°C. (Examples 1-7) A decorative sheet of Example 1-7 was obtained in the same manner as in Example 1-1, except that a phthalic acid-based plasticizer with a viscosity of 400 was used as the plasticizer in the transparent polyvinyl chloride resin sheet, and a benzophenone-based ultraviolet absorber was used as the ultraviolet absorber. The breaking elongation was 170%.

[0075] (Examples 1-8) A decorative sheet of Example 1-8 was obtained in the same manner as in Example 1-1, except that NH-type HALS was used as the HALS in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 40% at 0°C. (Examples 1-9) The decorative sheet of Example 1-9 was obtained in the same manner as in Example 1-5, except that no ultraviolet absorber was added to the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 250% at 0°C.

[0076] (Comparative Example 1-1) A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1-1, except that a polyvinyl chloride resin (PVC) with a degree of polymerization of 690 and a K value of 58.6 was used in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 30% at 0°C. (Comparative Example 1-2) A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1-1, except that a polyvinyl chloride resin (PVC) with a degree of polymerization of 1740 and a K value of 77.4 was used in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 520% at 0°C.

[0077] (Comparative Examples 1-3) A decorative sheet of Comparative Example 3 was obtained in the same manner as in Examples 1-5, except that the amount of plasticizer added to the transparent polyvinyl chloride resin sheet was 35 PHR. The resulting decorative sheet had a breaking elongation of 460% at 0°C. (Comparative Examples 1-4) A decorative sheet of Comparative Example 4 was obtained in the same manner as in Examples 1-3, except that the amount of plasticizer added to the transparent polyvinyl chloride resin sheet was 15 PHR. The resulting decorative sheet had a breaking elongation of 5% at 0°C.

[0078] 〔evaluation〕 The decorative sheets of the Examples and Comparative Examples were evaluated for film formation stability of the transparent polyvinyl chloride resin sheet, suitability for wrapping, state of bent portions during wrapping, and light resistance. The evaluation criteria were as follows:

[0079] (Film formation stability of transparent polyvinyl chloride resin sheets) The film-forming stability during film-forming of a polyvinyl chloride resin sheet was evaluated. ◯ (Pass): No fish eyes or the like occur, the calendering suitability is good, and sheets can be stably produced. × (fail): Fish eyes or the like are observed, or the calendering suitability is poor, and a sheet cannot be stably produced.

[0080] (suitable for wrapping processing) The ease of handling when wrapping the decorative sheet was evaluated. ◎ (Pass): Possible under a wide range of production conditions 〇 (Pass): Possible under limited production conditions × (failed): Difficult to produce (weak and difficult to handle, or easily cut or cracked)

[0081] (Bent part condition during wrapping process) The state of the bent portion during wrapping of the decorative sheet was evaluated. ◎ (Pass): No whitening or cracking occurs at the bent part when processed at 0°C. Good (pass): When processed at 0°C, slight whitening occurs at the bent portion, but this is within the acceptable level. No cracks occur. × (fail): Whitening and cracking occurred at the bent part during processing at 0°C.

[0082] (weather resistance) Metal weather testing machine (DAIPLA Wintes Co., Ltd., KU-R5DCI-A) A 504-hour accelerated weather resistance test was carried out under the following test conditions. Test conditions: BPT (black panel temperature): 63°C, illuminance: 65mW / cm 2A total of 21 cycles of "20 hours of UV exposure + 4 hours of condensation" were performed. The color difference ΔE before and after the accelerated weathering test was evaluated. ◎(Pass):ΔE<2.0 〇(Pass):ΔE=2.0 or more and 4.0 or less ×(Fail):ΔE>4.0 A score of "○" or above was considered a pass.

[0083] The evaluation results for each of the above evaluation items are shown in Table 1.

[0084] [Table 1]

[0085] As shown in Table 1, Examples 1-1 to 1-9, in which the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) satisfies at least one of the following conditions: a polyvinyl chloride resin having an average degree of polymerization of 800 or more and 1500 or less as calculated in accordance with JIS K6720-2, or a polyvinyl chloride resin having a K value of 60 or more and 75 or less as calculated in accordance with JIS K7367-2:1999, and which contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less, had a breaking elongation at 0°C of 10% or more and 400% or less, and it was confirmed that the film formation stability of the transparent polyvinyl chloride resin sheet, the wrapping processability of the decorative sheet, and the condition of the bent part during wrapping of the decorative sheet were all good.

[0086] Furthermore, although the decorative sheets of Examples 1-1 to 1-6 also had good weather resistance, it was confirmed that better weather resistance was obtained when a cyanoacrylate-based UV absorber was used (Example 1-3) than when a benzophenone-based UV absorber was used (Example 1-4). Furthermore, it was confirmed that insufficient weather resistance was achieved in Example 1-7, in which a phthalic acid-based plasticizer with a viscosity of 400 MPa·s was used as the plasticizer for the transparent polyvinyl chloride resin sheet and a benzophenone-based UV absorber was also used, Example 1-8, in which an NH-type HALS was used for the transparent polyvinyl chloride resin sheet, and Example 1-9, in which the transparent polyvinyl chloride resin sheet did not contain a UV absorber.

[0087] Furthermore, in Example 1-1, Comparative Example 1-1, in which the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) was a polyvinyl chloride resin with an average degree of polymerization of less than 800, had a low breaking elongation viscosity at 0°C, and it was confirmed that the film-forming stability of the transparent polyvinyl chloride resin sheet was reduced. Conversely, in Example 1-1, Comparative Example 1-2, in which the resin constituting the polyvinyl chloride resin sheet with an average degree of polymerization of 1500 or more was a polyvinyl chloride resin sheet with an average degree of polymerization higher than 1500, was easy to stretch and less likely to break, but the breaking elongation at 0°C was large and the transparent polyvinyl chloride resin sheet was soft and had no stiffness, and therefore the film-forming stability of the transparent polyvinyl chloride resin sheet was poor. It was also confirmed that the decorative sheet's suitability for wrapping processing was poor and the state of bent parts during wrapping processing was poor.

[0088] Furthermore, in Examples 1-5, Comparative Example 3, in which the amount of plasticizer added to the transparent polyvinyl chloride resin sheet exceeded 30 PHR, had a breaking elongation of over 400% at 0°C, and was soft and had no stiffness, so it was confirmed that the suitability for wrapping processing and the condition of the bent part during wrapping processing were poor. In addition, in Example 1-1, in Comparative Example 1-4, in which the amount of plasticizer added to the transparent polyvinyl chloride resin sheet was less than 20 PHR, the breaking elongation at 0°C was less than 10%, and it was confirmed that the sheet was hard, and therefore its suitability for wrapping processing and the condition of the bent part during wrapping processing were poor.

[0089] (Second embodiment) Next, a second embodiment of the present invention will be described. The decorative sheet of the second embodiment is the same as the decorative sheet of the first embodiment except for the configuration of the transparent polyvinyl chloride resin layer 6, so the same parts are given the same reference numerals and detailed description thereof will be omitted.

[0090] (Transparent polyvinyl chloride resin layer) The transparent polyvinyl chloride resin layer (transparent resin layer) 6a in the second embodiment is a layer for improving the weather resistance of the decorative sheet 1. The transparent polyvinyl chloride resin layer 6a is formed of polyvinyl chloride resin, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, and has good moldability and processability, and is also suitable for printing. As mentioned 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. In other words, the decorative sheet 1 according to the second embodiment can reliably improve processability and recyclability by using a colored polyvinyl chloride resin layer 2 and a transparent polyvinyl chloride resin layer 6a containing polyvinyl chloride resin.

[0091] The transparent polyvinyl chloride resin layer 6a preferably has a transparency sufficient to allow the pattern layer 4 provided on the surface on the colored polyvinyl chloride resin layer 2 side (the lower surface in FIG. 1) to be seen through when viewed from the surface protection layer 8 side. The transparent polyvinyl chloride resin layer 6a is preferably, for example, colorless and transparent, colored and transparent, or translucent. The resin constituting the transparent polyvinyl chloride resin layer 6a is preferably a polyvinyl chloride resin containing a NOR-type hindered amine light stabilizer (HALS). The hindered amine light stabilizer preferably has low basicity, and preferably has a base dissociation constant pkb of 5 or more and 12 or less, more preferably 8 or more and 10 or less. If the hindered amine light stabilizer has low basicity and a base dissociation constant pkb of 5 or more, the transparent polyvinyl chloride resin layer 6a can be easily decomposed by the base. 脱HClIt can suppress the reaction and is effective against today's acid rain. On the other hand, the higher the basicity, the lower the weather resistance, so it is preferable that the base dissociation constant pkb is 12 or less.

[0092] The content of the hindered amine light stabilizer in the transparent polyvinyl chloride resin layer 6a is preferably 0.05% or more and 5% or less, and more preferably 0.1% or more and 1% or less, based on the resin solid content. The polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6a is preferably a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less. Alternatively, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less.

[0093] The higher the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6a, the stronger, more stretchable, less likely to crack, and more durable the decorative sheet 1 will be. If the average degree of polymerization is too high, the gelation temperature will be high, resulting in fish eyes and other problems, making it difficult to form the transparent polyvinyl chloride resin layer 6a. Furthermore, the lower the average degree of polymerization, the more likely the decorative sheet 1 will crack, and the lower the viscosity will result in poor calendering suitability and poor film formation stability. Therefore, it is preferable that the resin constituting the transparent polyvinyl chloride resin layer 6a be a polyvinyl chloride resin with an average degree of polymerization of 800 or more and 1500 or less, calculated in accordance with JIS K6720-2.

[0094] Furthermore, the transparent polyvinyl chloride resin layer 6a preferably has an ultraviolet transmittance of 0.05% T or less at a wavelength of 320 nm and 0.4% T or less at a wavelength of 360 nm. In decorative sheets (polyvinyl chloride (PVC) sheets) made from polyvinyl chloride resin, the C-C bonds in the PVC main chain are broken by absorbing ultraviolet light around 320 nm, causing the sheet to become embrittled and initiate a dehydrochlorination reaction. At around 360 nm, the C-Cl bonds in PVC are broken, producing polyenes with C=C double bonds, resulting in the sheet turning brown (a phenomenon known as brown spots). In this embodiment, the ultraviolet transmittance of the transparent polyvinyl chloride resin layer 6a is 0.05%T or less at a wavelength of 320 nm and 0.4%T or less at a wavelength of 360 nm. By keeping the ultraviolet transmittance at a wavelength of 320 nm to 0.05%T or less, embrittlement and dehydrochlorination of the decorative sheet can be suppressed. Furthermore, by keeping the ultraviolet transmittance at a wavelength of 360 nm to 0.4%T or less, the formation of polyenes with C=C double bonds can be suppressed, thereby suppressing the occurrence of discoloration (brown spots). In other words, by controlling the ultraviolet transmittance at wavelengths of 320 nm and 360 nm in the transparent polyvinyl chloride resin layer 6a to the above-mentioned upper limit values, the weather resistance of the decorative sheet 1 can be improved. Therefore, a decorative sheet 1 can be obtained that has excellent weather resistance and can withstand long-term outdoor use, for example, as a decorative sheet for decorating the surface of decorative materials for exterior and semi-exterior applications. A plasticizer may be added to the transparent polyvinyl chloride resin layer 6a. A high-molecular-weight polyester resin is preferred as the plasticizer, and the content of the plasticizer is preferably 20 PHR to 30 PHR. Furthermore, the viscosity of the plasticizer, measured using a capillary viscometer in accordance with JIS K7367-5:2000, is preferably 500 MPa·s to 3000 MPa·s.

[0095] Among polyester resins, high molecular weight polyesters are preferred as plasticizers. Phthalic acid resins (dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more prone to bleed-out than high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance. If the plasticizer content is less than 20 PHR, cold resistance will be poor even if a phthalic acid resin is used, so if a high molecular weight polyester resin is used as the plasticizer, the plasticizer content is preferably 20 PHR or more. If the plasticizer content is more than 30 PHR, the decorative sheet 1 will become soft and lose its stiffness, making it difficult to handle and reducing productivity during processing. In addition, the decorative sheet 1 will have poor scratch resistance.

[0096] Furthermore, if the viscosity of the plasticizer is less than 500 MPa·s, it has a low molecular weight, is prone to bleeding, and has poor weather resistance. If the viscosity of the plasticizer is more than 3000 MPa·s, it is too high a molecular weight, making resin production difficult. It also has poor cold resistance.

[0097] [Weatherproofing agent] The transparent polyvinyl chloride resin layer 6a may further contain a weather resistance agent, which can impart excellent weather resistance to the transparent polyvinyl chloride resin layer 6a.

[0098] The transparent polyvinyl chloride resin layer 6a preferably contains an ultraviolet absorber to effectively control the ultraviolet transmittance described above. That is, in the decorative sheet 1 according to the second embodiment, the transparent polyvinyl chloride resin layer 6a is preferably formed from a transparent polyvinyl chloride resin and contains an ultraviolet absorber. This allows the ultraviolet transmittance of the transparent polyvinyl chloride resin layer 6a to be effectively controlled as described above, and provides the decorative sheet 1 with excellent weather resistance. More specifically, the transparent polyvinyl chloride resin layer 6a preferably contains at least one ultraviolet absorber selected from the group consisting of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. This improves the ultraviolet absorption ability of the transparent polyvinyl chloride resin layer 6a over a wide range of wavelengths, from 320 nm to 360 nm, and effectively controls the ultraviolet transmittance, imparting excellent weather resistance to the transparent polyvinyl chloride resin layer 6a and improving the weather resistance of the decorative sheet 1.

[0099] Some benzophenone-based UV absorbers can absorb light in the wavelength range of 320 to 340 nm. Benzotriazole-based UV absorbers can absorb light in the wavelength ranges of 300 to 320 nm and 340 to 360 nm. Triazine-based UV absorbers absorb light in the wavelength range of 270 to 360 nm, and cyanoacrylate-based UV absorbers have a maximum absorption around 310 nm and are suitable for use with PVC. The content of the ultraviolet absorber in the transparent polyvinyl chloride resin layer 6a may be adjusted depending on the desired weather resistance, but for example, it is preferably in the range of more than 0.3 parts by mass and not more than 1.0 part by mass, and more preferably in the range of 0.5 parts by mass to 0.8 parts by mass, per 100 parts by mass of the transparent vinyl chloride resin that constitutes the transparent polyvinyl chloride resin layer 6a. This ensures improved weather resistance of the decorative sheet 1.

[0100] (Benzophenone-based UV absorber) Benzophenone-based UV absorbers include, for example, octabenzone and its modified products, polymers, and derivatives. Other examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone). Examples of known UV absorbers include "ADEKA STAB (registered trademark) LA-1413 manufactured by ADEKA Corporation" and "CHIMASORBO 81 manufactured by BASF Japan Ltd."

[0101] (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-(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.

[0102] (Triazine-based UV absorber) As the triazine-based ultraviolet absorber, for example, a hydroxyphenyltriazine-based one is used. By using a hydroxyphenyltriazine-based ultraviolet absorber, the triazine skeleton suppresses bleeding, and the triazine skeleton is more chemically stable than the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, making it possible to maintain ultraviolet absorption performance for a long period of time.

[0103] Examples of the triazine-based ultraviolet absorber used in the transparent polyvinyl chloride resin layer 6a 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 the like, as well as mixtures, modified products, polymers, and derivatives thereof.

[0104] (Cyanoacrylate UV absorber) Examples of cyanoacrylate-based ultraviolet absorbers include ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, etc. Known products include cyanoacrylate-based ultraviolet absorbers "Uvinal (registered trademark) 3035 (product number)" (molecular weight 277), "Uvinal 3039" (molecular weight 361), and "Uvinal 3030FF" (molecular weight 1060) manufactured by BASF Japan Ltd.

[0105] The thickness of the transparent polyvinyl chloride resin layer 6a 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. A thickness of 50 μm or more reliably improves the weather resistance of the decorative sheet 1 and can absorb unevenness in the adherend, such as a window frame, to improve the finished appearance of the decorative sheet 1. Furthermore, if the thickness of the transparent polyvinyl chloride resin layer 6a is 150 μm or less, the transparent polyvinyl chloride resin layer 6a is not formed thicker than necessary, improving processability (e.g., wrapping processability) and reducing the manufacturing cost of the decorative sheet 1.

[0106] [Heat stabilizer] The transparent polyvinyl chloride resin layer 6a preferably contains a metal salt of a higher fatty acid as a heat stabilizer.

[0107] (effect) (1) The decorative sheet 1 according to the second embodiment of the present invention is composed of at least a design layer 4 and a transparent polyvinyl chloride resin layer 6a laminated in this order, and the resin constituting the transparent polyvinyl chloride resin layer 6a is a polyvinyl chloride resin that satisfies at least one of the following conditions: an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500, or a K value calculated in accordance with JIS K7367-2:1999 of 60 to 75, and further the transparent polyvinyl chloride resin layer 6 contains 20 to 30 PHR of a high-molecular-weight polyester plasticizer. Therefore, even when a transparent polyvinyl chloride resin sheet is formed into a film, film formation stability can be ensured, and good wrapping suitability of the decorative sheet 1 and good bending condition of the decorative sheet 1 during wrapping can be obtained.

[0108] (2) The viscosity of the plasticizer added to the transparent polyvinyl chloride resin layer 6a, as measured by a capillary viscometer in accordance with JIS K7367-5:2000, satisfies the range of 500 MPa·s or more and 3000 MPa·s or less, thereby ensuring good weather resistance. (3) By including a light stabilizer and an ultraviolet absorber (UVA) in the transparent polyvinyl chloride resin layer 6a, the weather resistance of the decorative sheet can be improved. In particular, by using NOR-type HALS as a light stabilizer added to the transparent polyvinyl chloride resin layer 6, the dehydrochlorination reaction can be suppressed. Furthermore, by using a NOR-type HALS with a low basicity, the dehydrochlorination reaction can be suppressed even more than with a high basicity. In particular, by using a NOR-type HALS with a base dissociation constant pkb of 5 to 12, the dehydrochlorination reaction caused by bases can be suppressed while ensuring weather resistance. 脱HCl It is effective in suppressing reactions. (4) The transparent polyvinyl chloride resin layer 6a has an ultraviolet transmittance of 0.05%T or less at a wavelength of 320 nm and 0.4%T or less at a wavelength of 360 nm. Therefore, even when formed using polyvinyl chloride resin, a decorative sheet with excellent weather resistance can be provided, and a decorative sheet 1 with excellent weather resistance that can withstand long periods of use, for example, outdoors, can be obtained. In other words, a decorative sheet 1 with excellent weather resistance as well as processability can be obtained.

[0109] (5) By forming the decorative member 100 from a base material 20 and a decorative sheet 1 bonded to this base material 20, a decorative member 100 with excellent processability can be provided even if the decorative sheet 1 is formed using polyvinyl chloride resin. (6) Because the fittings are formed by laminating the decorative sheet 1 to the fitting material as the base material 20, fittings with excellent processability can be provided even when the decorative sheet 1 is formed using polyvinyl chloride resin. In particular, by laminating the decorative sheet 1 to an exterior fitting material (base material 20) made of a vinyl chloride-based material, both the decorative sheet 1 and the fitting material are made into a mono-material made of a vinyl chloride-based material, which further enhances recyclability. Example 2

[0110] The second embodiment of 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.

[0111] Example 2-1 A colored polyvinyl chloride resin sheet was used as the colored polyvinyl chloride resin layer (colored substrate layer). A design layer was formed on one side of the colored polyvinyl chloride resin sheet by gravure printing using a printing ink for vinyl chloride. Then, a transparent polyvinyl chloride resin sheet as a transparent polyvinyl chloride resin layer (transparent resin layer) was thermally laminated onto the colored polyvinyl chloride resin sheet including the design layer. Then, a resin composition mainly composed of an acrylic resin composition was laminated onto the transparent polyvinyl chloride sheet as a surface protective layer. The composition of each layer is as follows:

[0112] (Colored polyvinyl chloride resin sheet) Material: Polyvinyl chloride resin (PVC) Thickness: 80 μm

[0113] (Transparent polyvinyl chloride resin sheet) Material: Polyvinyl chloride resin (PVC) Degree of polymerization: 820 K value: 62.1 Thickness: 80 μm Plasticizer: High molecular weight polyester Additives: 20PHR HALS:NOR type pkb=10 0.2% (ADEKA STAB LA81 manufactured by ADEKA Corporation) UV absorber: Triazine type 0.5 parts by mass

[0114] (Picture layer) Binder resin: A mixture of vinyl chloride resin-vinyl acetate resin copolymer and acrylic resin

[0115] (Surface protective layer) Main ingredient: methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) 90 parts by weight UV absorber: Tinuvin 479 (manufactured by BASF Japan Ltd.) 9 parts by mass Light stabilizer: Tinuvin 123 (BASF Japan Ltd.) 1 part by mass Hardener: Takenate D170 manufactured by Mitsui Chemicals, Inc. 10 parts by mass Solvent: 240 parts by weight of ethyl acetate Coating amount 3g / m 2

[0116] (Example 2-2) The decorative sheet of Example 2-2 was obtained in the same manner as in Example 1, except that in the decorative sheet of Example 2-1, the base dissociation constant of HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8. (Example 2-3) A decorative sheet of Example 2-3 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added to the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 1%.

[0117] (Examples 2-4) The decorative sheet of Example 2-4 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3%, the degree of polymerization of the transparent polyvinyl chloride resin sheet was 1440, and the K value was 73.6. (Examples 2-5) The decorative sheet of Example 2-5 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3% and the amount of plasticizer added was 28 PHR.

[0118] (Examples 2-6) The decorative sheet of Example 2-6 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3% and the amount of ultraviolet absorber added was 0.8 parts by mass. (Examples 2-7) The decorative sheet of Example 2-7 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added to the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3%, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber.

[0119] (Comparative Example 2-1) The decorative sheet of Comparative Example 2-1 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, a transparent polyvinyl chloride resin sheet was used as the transparent polyvinyl chloride resin layer (transparent resin layer), and NH-type HALS with a base dissociation constant pkb=4 was used as the HALS, and the amount of this HALS added was 0.3%. (Comparative Example 2-2) The decorative sheet of Comparative Example 2-2 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) did not contain HALS, and the degree of polymerization of the transparent polyvinyl chloride resin sheet was 1440 and the K value was 73.6.

[0120] (Comparative Example 2-3) The decorative sheet of Comparative Example 2-3 was obtained using the same procedure as in Example 2-1, except that in the decorative sheet of Example 2-1, the degree of polymerization of the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 690 and the K value was 58.6. (Comparative Example 2-4) The decorative sheet of Comparative Example 2-4 was obtained using the same procedure as in Example 2-1, except that in the decorative sheet of Example 2-1, the degree of polymerization of the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 1740 and the K value was 77.4. (Comparative Example 2-5) The decorative sheet of Comparative Example 2-5 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of HALS contained in the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, the amount of HALS added was 0.3%, the amount of plasticizer added was 35 PHR, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber. (Comparative Example 2-6) The decorative sheet of Comparative Example 2-6 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of HALS contained in the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, the amount of HALS added was 0.3%, and the amount of ultraviolet absorber added was 0.1 parts by mass. (Comparative Example 2-7) The decorative sheet of Comparative Example 2-7 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of HALS contained in the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, the amount of HALS added was 0.3%, and no ultraviolet absorber was added. (Comparative Example 2-8) The decorative sheet of Comparative Example 2-8 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=9, the amount of HALS added was 0.3%, the amount of plasticizer added was 15 PHR, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber.

[0121] 〔evaluation〕 The decorative sheets of the Examples and Comparative Examples were measured for UV transmittance (320 nm) and UV transmittance (360 nm). Each decorative sheet was also evaluated for weather resistance, film-forming stability of the transparent polyvinyl chloride resin sheet, and suitability for wrapping processing. The evaluation criteria were as follows:

[0122] (weather resistance) A 504-hour accelerated weather resistance test was conducted under the following test conditions using a metal weather testing machine (KU-R5DCI-A, manufactured by Daipla Wintes Co., Ltd.). Test conditions: BPT (black panel temperature): 63°C, illuminance: 65mW / cm 2The test was repeated 21 times (504 hours), with 20 hours of UV exposure and 4 hours of condensation being considered as one cycle. The color difference ΔE before and after the accelerated weathering test was evaluated. The evaluation criteria were as follows: ◎(Pass):ΔE<2.0 〇 (Pass): ΔE = 2.0 or more and less than 4.0 ×(Fail):ΔE≧4.0 (Film formation stability of transparent polyvinyl chloride resin sheets) The film-forming stability during film-forming of a polyvinyl chloride resin sheet was evaluated. ◯ (Pass): No fish eyes or the like occur, the calendering suitability is good, and sheets can be stably produced. × (fail): Fish eyes or the like are observed, or the calendering suitability is poor, and a sheet cannot be stably produced.

[0123] (suitable for wrapping processing) The ease of handling when wrapping the decorative sheet was evaluated. ◎ (Pass): Possible under a wide range of production conditions 〇 (Pass): Possible under limited production conditions × (Fail): Difficult to produce (weak and difficult to handle, or prone to breaking or cracking, or whitening or cracking occurs at the bent part)

[0124] The above measurement results and the evaluation results for each evaluation item are shown in Tables 2 and 3.

[0125] [Table 2]

[0126] [Table 3]

[0127] As shown in Tables 2 and 3, the decorative sheets of Examples 2-1 to 2-7, in which the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) satisfies at least one of the following criteria: a polyvinyl chloride resin having an average degree of polymerization of 800 to 1500 as calculated in accordance with JIS K6720-2, or a polyvinyl chloride resin having a K value of 60 to 75 as calculated in accordance with JIS K7367-2:1999; containing 20 to 30 PHR of a high-molecular-weight polyester plasticizer; and having an ultraviolet transmittance of 0.05%T or less at a wavelength of 320 nm and an ultraviolet transmittance of 0.4%T or less at a wavelength of 360 nm, were all rated as "Excellent" (passed) for weather resistance, demonstrating that even when formed using polyvinyl chloride resin (PVC), they have excellent weather resistance and can withstand long-term use in exterior and semi-exterior applications.

[0128] Furthermore, it was confirmed that the decorative sheets of Examples 2-1 to 2-7 had good film-forming stability for the transparent polyvinyl chloride resin sheet and good wrapping processability for the decorative sheets. It was also confirmed that, even when a cyanoacrylate-based UV absorber was used as the UV absorber (Example 2-7), good properties could be obtained, similar to when a triazine-based UV absorber was used. Furthermore, of the decorative sheets of Examples 2-1 to 2-7, the decorative sheet of Example 2-5, which contained a higher amount of plasticizer than the other decorative sheets, was confirmed to have acceptable wrapping processability, although it was somewhat difficult to handle.

[0129] On the other hand, the decorative sheet of Comparative Example 2-1 in Example 2-1, in which 0.3% NH-type HALS was added, and the decorative sheet of Comparative Example 2-2 in Example 2-4, in which no HALS was added, had good film-forming stability of the transparent polyvinyl chloride resin sheet and good wrapping processability of the decorative sheet, but were unable to obtain sufficient weather resistance. Furthermore, the decorative sheets of Comparative Examples 2-3 and 2-4, in which the average degree of polymerization was outside the range of 800 to 1500 and the K value was outside the range of 60 to 75, were able to obtain good weather resistance, but the film-forming stability of the transparent polyvinyl chloride resin sheet was unacceptable, and the decorative sheet of Comparative Example 2-4, in which the average degree of polymerization exceeded 1500 and the K value exceeded 75, also failed to obtain satisfactory wrapping processability of the decorative sheet. The decorative sheet of Comparative Example 2-5, in which the amount of plasticizer added exceeded 30 PHR, and the decorative sheet of Comparative Example 2-8, in which the amount of plasticizer added was less than 20 PHR, failed in terms of wrapping suitability. Furthermore, the decorative sheet of Comparative Example 2-6, in which the UV transmittance at a wavelength of 320 nm exceeded 0.05%T and the UV transmittance at a wavelength of 360 nm exceeded 0.4%T, and the decorative sheet of Comparative Example 2-7, which did not contain an UV absorber, were unable to achieve sufficient weather resistance.

[0130] The present invention can have the following configurations, for example. (1) A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less, The decorative sheet is characterized in that the transparent resin layer contains a high molecular weight polyester plasticizer of 20 PHR or more and 30 PHR or less. (2) A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less; The decorative sheet is characterized in that the transparent resin layer contains a high molecular weight polyester plasticizer of 20 PHR or more and 30 PHR or less. (3) The decorative sheet according to (1) or (2) above, characterized in that the elongation at break at 0°C is 10% or more and 400% or less. (4) The decorative sheet according to any one of (1) to (3) above, characterized in that the viscosity of the plasticizer measured using a capillary viscometer in accordance with JIS K7367-5:2000 is 500 MPa·s or more and 3000 MPa·s or less. (5) The decorative sheet according to any one of (1) to (4) above, wherein the transparent resin layer contains a NOR-type hindered amine light stabilizer (HALS). (6) The decorative sheet according to (5) above, wherein the hindered amine light stabilizer has a base dissociation constant pkb of 5 or more and 12 or less. (7) The decorative sheet according to any one of (1) to (6) above, characterized in that the transparent resin layer contains at least one of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. (8) The decorative sheet according to any one of (1) to (7) above, wherein the transparent resin layer contains a metal salt of a higher fatty acid as a heat stabilizer. (9) The decorative sheet according to any one of (1) to (8) above, further comprising a surface protection layer on the outermost surface on the side of the transparent resin layer. (10) A decorative sheet according to any one of (1) to (9) above, characterized in that a colored substrate layer is provided on the side of the design layer opposite the transparent resin layer. (11) The decorative sheet according to any one of (1) to (10) above, A decorative member comprising: a substrate disposed on the outermost surface of the decorative sheet on the side of the pattern layer. (12) The decorative sheet according to any one of (1) to (10) above, A fitting comprising a fitting component arranged on the outermost surface of the decorative sheet on the side of the pattern layer. (13) The fixture described in (12) above is characterized in that the fixture component is an exterior fixture component made of a vinyl chloride material. [Explanation of symbols]

[0131] 1 decorative sheet 2. Colored polyvinyl chloride resin layer 4. Picture layer 6, 6a Transparent polyvinyl chloride resin layer 8 Surface protective layer 10 Embossed section 20 Base material 100 Decorative materials

Claims

1. A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less, the transparent resin layer contains a high-molecular-weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less; the transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber; The decorative sheet is characterized in that the transparent resin layer contains a NOR-type hindered amine light stabilizer (HALS).

2. A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less, the transparent resin layer contains a high-molecular-weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less; the transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber; The decorative sheet is characterized in that the transparent resin layer contains a NOR-type hindered amine light stabilizer (HALS).

3. 3. The decorative sheet according to claim 1, wherein the elongation at break at 0° C. is 10% or more and 400% or less.

4. 3. The decorative sheet according to claim 1, wherein the viscosity of the plasticizer measured with a capillary viscometer in accordance with JIS K7367-5:2000 is 500 MPa·s or more and 3000 MPa·s or less.

5. 3. The decorative sheet according to claim 1, wherein the hindered amine light stabilizer has a base dissociation constant pkb of 5 or more and 12 or less.

6. 3. The decorative sheet according to claim 1, wherein the transparent resin layer contains at least one of a triazine-based ultraviolet absorber and a cyanoacrylate-based ultraviolet absorber.

7. 3. The decorative sheet according to claim 1, wherein the transparent resin layer contains a metal salt of a higher fatty acid as a heat stabilizer.

8. 3. The decorative sheet according to claim 1, further comprising a surface protection layer on the outermost surface of the transparent resin layer side.

9. 3. The decorative sheet according to claim 1, further comprising a colored substrate layer on the side of said design layer opposite said transparent resin layer.

10. 3. The decorative sheet according to claim 1, wherein the design layer contains a mixture of a vinyl chloride resin-vinyl acetate resin copolymer resin and an acrylic resin as a binder resin.

11. 3. The decorative sheet according to claim 1, wherein the transparent resin layer does not contain a barium-zinc-based heat stabilizer or a magnesium-zinc-based heat stabilizer.

12. The decorative sheet according to claim 1 or 2; A decorative member comprising: a substrate disposed on the outermost surface of the decorative sheet on the side of the pattern layer.

13. The decorative sheet according to claim 1 or claim 2; A fitting comprising a fitting component arranged on the outermost surface of the decorative sheet on the side of the pattern layer.

14. 14. The fixture according to claim 13, wherein the fixture component is an exterior fixture component made of a vinyl chloride material.

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