Decorative sheet, decorative member, and fitting

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 cosmetic sheet, a cosmetic member, and a fixture.

Background Art

[0002] Conventionally, a vinyl chloride resin-based cosmetic sheet used for decorating interior materials for houses and the like is known (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Although it has been pointed out that polyvinyl chloride resin may contain dioxin, which is a harmful substance in the gas when burned, in recent years, due to the improvement of incineration facilities and exhaust gas treatment technologies, the generation of harmful substances has been suppressed, so the existence of polyvinyl chloride resin is being reexamined. In addition, due to the increasing awareness of zero-energy houses (ZEH) and the like, there is a high demand for highly heat-insulating window frames (resin sashes) using polyvinyl chloride resin, and it is also considered to decorate the base materials thereof. When an olefin-based resin sheet is used as a decorative material for such window frames (resin sashes) and the like, there are problems such as difficulty in recycling.

[0005] On the other hand, polyvinyl chloride resin has excellent processing suitability and the advantage of being easy to recycle. Therefore, by using polyvinyl chloride resin as a decorative material together with a base material such as a vinyl chloride window frame, it is expected to greatly contribute to reducing the environmental load. However, when a polyvinyl chloride resin sheet is used outdoors for a long time, discoloration and the like occur. Also, when it is used by being bonded to a base material such as a window frame, the sheet is often bent and processed. Since the polyvinyl chloride resin sheet is prone to cracking when processed at low temperatures, it is important to design considering this characteristic.

[0006] The present invention has been made in view of the above points, and an object thereof is to provide a decorative sheet, a decorative member, and a fitting having excellent processing suitability.

Means for Solving the Problems

[0007] As a result of intensive research, the present inventors have found that, in a decorative sheet containing polyvinyl chloride resin, by setting the formulation of this decorative sheet, specifically, the degree of polymerization and the contents of a plasticizer and a weathering agent to appropriate values, the above object can be achieved. That is, a decorative sheet according to one aspect of the present invention is a decorative sheet in which at least a pattern layer and a transparent resin layer are laminated in this order, and the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less, and the transparent resin layer is characterized by containing 20 PHR or more and 30 PHR or less of a high molecular weight polyester-based plasticizer. Also, a decorative sheet according to another aspect of the present invention is a decorative sheet in which at least a pattern layer and a transparent resin layer are laminated in this order, and the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated according to JIS K7367-2:1999 of 60 or more and 75 or less, and the transparent resin layer is characterized by containing 20 PHR or more and 30 PHR or less of a high molecular weight polyester-based plasticizer.

[0008] In addition, the decorative member according to another aspect of the present invention is characterized by including the decorative sheet of the above aspect and a base material disposed on the outermost surface of the decorative sheet on the pattern layer side. Furthermore, the fitting according to another aspect of the present invention is characterized by including the decorative sheet of the above aspect and a fitting member disposed on the outermost surface of the decorative sheet on the pattern layer side.

Effects of the Invention

[0009] According to one aspect of the present invention, it is possible to obtain a decorative sheet, a decorative member, and a fitting having excellent processing suitability.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present technology will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thicknesses of the respective layers, etc. are different from the actual ones. As long as it is within the scope of the present disclosure, it is not necessarily required to be laminated in the order shown in the drawings. Also, layers not described in this drawing may be added. Further, the embodiments shown below are examples of configurations for embodying the technical idea of the present disclosure, and the technical idea of the present disclosure is not limited to the materials, shapes, structures, etc. of the constituent parts being the following. The technical idea of the present disclosure can be variously modified within the technical scope defined by the claims described in the claims. In addition, the directions of "left and right" and "up and down" in the following description are merely definitions for convenience of explanation and do not limit the technical idea of the present disclosure. Therefore, for example, if the paper surface is rotated by 90 degrees, "left and right" and "up and down" are read in exchange, and if the paper surface is rotated by 180 degrees, "left" becomes "right" and "right" becomes "left", of course. (First Embodiment) First, the first embodiment will be described.

[0012] (Configuration of Cosmetic Sheet) FIG. 1 is a cross-sectional view schematically showing an example of a cosmetic sheet 1 according to the first embodiment of the present invention. As shown in FIG. 1, the cosmetic sheet 1 includes a colored polyvinyl chloride resin layer (colored base material layer) 2, a pattern layer 4, a transparent polyvinyl chloride resin layer (transparent resin layer) 6, and a surface protective layer 8. An embossed portion 10 is formed on the surface protective layer 8, which is the outermost layer of the cosmetic sheet 1, 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 of the cosmetic sheet 1, is opaque and colored, and has concealability. Thereby, when the cosmetic sheet 1 is adhered to an adherend such as a window frame, the colored polyvinyl chloride resin layer 2 can conceal color variations, defects, etc. on the surface of the adherend. The colored polyvinyl chloride resin layer 2 is formed of a polyvinyl chloride resin. For example, it is formed of a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processing suitability, and further has printing suitability. By forming the cosmetic sheet 1 using the colored polyvinyl chloride resin layer 2, the end material of the cosmetic sheet 1 when the cosmetic sheet 1 is adhered to an adherend, or the used cosmetic sheet 1 can be melted and extruded by an extruder or the like and reused as a recycled base material. Also, since PVC is easier to reuse by melting than olefin-based resins, that is, the cosmetic sheet 1 according to the present embodiment can improve processing suitability and recyclability.

[0014] In addition, the opaque colored polyvinyl chloride resin layer 2 can have its hue appropriately selected as the base color of the pattern layer 4. Also, when making use 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 side of the surface protective layer 8. The colored polyvinyl chloride resin layer 2 can be obtained, for example, by mixing a colorant such as a pigment into the polyvinyl chloride resin or kneading it in. As the colorant, organic and inorganic pigments can be used, but it is preferable to use an inorganic pigment. That is, the colored polyvinyl chloride resin layer 2 preferably contains an inorganic substance as the colorant. For example, the colored polyvinyl chloride resin layer 2 preferably contains any one or more of inorganic substances such as calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0015] In addition, to the colored polyvinyl chloride resin layer 2, one or more additives selected from various additives such as, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, a fungicide, a friction reducer, a light scattering agent, and a gloss modifier may be added as necessary. Here, the case where the colored polyvinyl chloride resin layer 2 made of polyvinyl chloride resin is provided as the colored base material layer has been described, but it is not limited to polyvinyl chloride resin. A colored thermoplastic resin layer made of a thermoplastic resin may be provided as the colored base material layer, but from the perspective of recycling, it is preferable to use polyvinyl chloride resin as the resin constituting the colored base material layer, similar to the transparent polyvinyl chloride resin layer 6.

[0016] (Pattern 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 for imparting design properties to the decorative sheet 1. In addition, the pattern layer 4 is formed using printing ink, paint, or the like. The printing ink, paint, or the like for forming the pattern layer 4 is formed by dissolving or dispersing a colorant such as a dye or pigment in a suitable diluting solvent together with a suitable binder resin. Examples of the pigment include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigments such as mica, and the like.

[0017] The printing ink, paint, or the like for forming the pattern layer 4 is applied using various printing methods such as the gravure printing method or the offset printing method, or various coating methods such as the gravure coating method or the roll coating method. The binder resin contained in the pattern layer 4 is not particularly limited, but it is preferable to use a resin with good adhesion. That is, a resin having heat fusion properties with a polyvinyl chloride resin, for example, a vinyl chloride-vinyl acetate copolymer, a single acrylic resin, or a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin is preferable. As the pattern formed by the pattern layer 4, any pattern can be used. For example, a wood grain pattern, a stone grain pattern, a cloth grain pattern, an abstract pattern, a geometric pattern, characters, symbols, a single-color plain, or a combination thereof can be used. Further, in order to improve the concealment of the decorative sheet 1, a concealment layer may be provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2. The concealment layer is formed using, for example, an opaque printing ink or paint containing a large amount of an opaque pigment such as titanium dioxide or iron oxide.

[0018] The thickness of the pattern 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 pattern layer 4 is 1 μm or more, printing can be made clear. Also, when the thickness of the pattern layer 4 is 10 μm or less, the printing workability when manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed. In addition, in order to impart various functions to the pattern layer 4, for example, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retarders may be added. Further, the pattern layer 4 may have a configuration having, for example, a solid-colored original layer to conceal the color and pattern of the adherend to which the decorative sheet 1 is attached, and a pattern layer for adding a pattern for imparting design properties.

[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 a polyvinyl chloride resin. For example, it is formed of a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processing suitability, and further has printability. As described above, PVC can be used as a recycled base material by melting and extruding it, and it is easier to reuse by melting compared to olefin-based resins. That is, the decorative sheet 1 according to the present embodiment can surely improve the processing suitability and recyclability by using the colored polyvinyl chloride resin layer 2 containing a polyvinyl chloride resin and the transparent polyvinyl chloride resin layer 6.

[0020] In addition, the transparent polyvinyl chloride resin layer 6 preferably has transparency such that the pattern layer 4 provided on, for example, the surface on the side of the colored polyvinyl chloride resin layer 2 (the lower surface in FIG. 1) can be seen through from the surface protection layer 8 side. The transparent polyvinyl chloride resin layer 6 is preferably, for example, any of colorless transparent, colored transparent, and translucent. The resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less. In terms of the K value calculated according to 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 or more and 75 or less.

[0021] The higher the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6, the tougher, more stretchable, less prone to cracking, and more durable the decorative sheet 1 can be. If the average degree of polymerization is too high, the gelation temperature will be high, resulting in the occurrence of fish eyes and the like, making it difficult to form the transparent polyvinyl chloride resin layer 6. Also, the lower the average degree of polymerization, the more prone the decorative sheet 1 is to cracking, and due to the low viscosity, the calendering suitability is poor and the film-forming stability is poor. Therefore, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less. Also, when the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is 800 or more and 1500 or less, the elongation at break of the decorative sheet 1 at 0°C is 10% or more and 400% or less, and the production stability during processing such as wrapping is good. If the elongation at break at 0°C is less than 10%, the decorative sheet 1 is hard, so whitening and cracking may occur. If the elongation at break at 0°C is more than 400%, the decorative sheet 1 is too soft and lacks firmness, making it difficult to handle, with 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 elongation at break of the decorative sheet 1 at 0°C is 10% or more and 400% or less. When the K value is less than 60 or greater than 75, the elongation at break of the decorative sheet 1 at 0°C is less than 10% or greater than 400%. Also, a plasticizer may be added to the transparent polyvinyl chloride resin layer 6. As the plasticizer, a high molecular weight polyester-based resin is preferred, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. Also, in terms of viscosity, the viscosity of the plasticizer measured by a capillary viscometer according to JIS K7367-5:2000 is preferably 500 MPa·s or more and 3000 MPa·s or less.

[0023] As a plasticizer, among polyester resins, high molecular weight polyesters are preferred. Phthalic acid resins (such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more likely to bleed out compared to high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance. When the content of the plasticizer is less than 20 PHR, even if a phthalic acid resin is used, the cold resistance deteriorates. Therefore, when using a high molecular weight polyester resin as the plasticizer, the content of the plasticizer is preferably 20 PHR or more. When the content of the plasticizer is more than 30 PHR, the decorative sheet 1 becomes soft and loses its firmness, making it difficult to handle and resulting in poor productivity during processing. Also, the scratch resistance of the decorative sheet 1 is low.

[0024] Also, when the viscosity of the plasticizer is less than 500 MPa·s, it has a low molecular weight and is likely to bleed out and has poor weather resistance. When the viscosity of the plasticizer is greater than 3000 MPa·s, it is too high in molecular weight, resulting in high viscosity and difficult resin productivity. Also, the cold resistance is poor. When the content of the plasticizer is within the range of 20 PHR or more and 30 PHR or less, the elongation at break of the decorative sheet 1 at 0 °C is 10% or more and 400% or less, and the production stability during processing such as wrapping is good. As described above, when the elongation at break at 0 °C is less than 10%, the decorative sheet 1 is hard, resulting in whitening and cracking. When it is more than 400%, the decorative sheet 1 is soft and lacks firmness, making it difficult to handle and resulting in poor productivity, and also having poor scratch resistance.

[0025] 〔Weathering agent〕 The transparent polyvinyl chloride resin layer 6 may further contain a weathering agent. Thereby, excellent weather resistance can be imparted 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 weathering agent. When using a NOR type HALS with low basicity, the de-HCl reaction of the transparent polyvinyl chloride resin layer 6 can be suppressed, which is effective against current acid rain. Examples of NOR type hindered amine light stabilizers (HALS) applicable to the transparent polyvinyl chloride resin layer 6 include, for example, "ADEKA STAB LA-81" manufactured by ADEKA Corporation, "Tinuvin 123" (bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate) manufactured by BASF Japan Ltd., "Tinuvin XT850FF" manufactured by BASF Japan Ltd., and the like.

[0026] In addition, the transparent polyvinyl chloride resin layer 6 may contain an ultraviolet absorber as a weathering agent, and preferably contains at least one or more of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers, and more preferably contains a cyanoacrylate-based ultraviolet absorber. The addition amount of the ultraviolet absorber in the transparent polyvinyl chloride resin layer 6 may be added according to the desired weather resistance. For example, it is preferable that the ultraviolet absorber is 0.5 parts by mass or more with respect to 100 parts by mass of the transparent vinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6. Thereby, the weather resistance of the decorative sheet 1 can be surely improved.

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

[0028] (Benzotriazole-based ultraviolet 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 ultraviolet absorbers) 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-iso-octyloxyphenyl)-s-triazine, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

[0030] (Cyanoacrylate-based ultraviolet absorbers) Examples of the cyanoacrylate-based 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 or more and 150 μm or less, more preferably in the range of 50 μm or more and 100 μm or less, and even more preferably in the range of 60 μm or more and 80 μm or less. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 can be surely improved, and further, the unevenness and the like of the adherend such as a window frame can be absorbed to improve the construction finish of the decorative sheet 1. Further, when 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, the processing suitability (for example, bendability) is improved, and the manufacturing cost of the decorative sheet 1 can be reduced.

[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 protection layer) The surface protection 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 protection layer 8 is not particularly limited, and for example, it can be appropriately selected and used from resin materials such as urethane-based, acrylic-based, acrylic-silicone-based, fluorine-based, and epoxy-based. The surface protection layer 8 may be blended with various additives such as, for example, 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 necessary, and it is preferable that the surface protection layer 8 is provided with an ultraviolet absorber and a light stabilizer. Note that the surface protection layer 8 does not necessarily have to be provided, but it is preferable to provide it.

[0033] Hereinafter, an example of the surface protection layer 8 according to the present embodiment will be described with specific examples. In the present embodiment, the surface protective layer 8 may mainly contain, for example, an acrylic resin composition containing cyclohexyl (meth) acrylate as a monomer component. In the present embodiment, cyclohexyl (meth) acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By containing 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 desirably in the range of 5% by mass or more and 50% by mass or less among the monomer components of all the acrylic resin compositions, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protective layer 8. By setting the content of cyclohexyl (meth) acrylate to 5% by mass or more, a sufficient deterioration suppressing effect can be obtained. Further, by setting the content of cyclohexyl (meth) acrylate to 50% by mass or less, high weather resistance over time can be imparted without significantly changing the various performances of the surface protective layer 8 of the decorative sheet, such as maintaining and improving surface hardness, improving stain resistance, and adjusting the surface gloss. Here, the above-mentioned "main component" means that the content of the acrylic resin composition constituting the surface protective layer 8 is 50% by mass or more with respect to the mass of the entire surface protective layer 8.

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

[0036] Also, in the present embodiment, the surface protective layer 8 may be formed by applying a coating liquid containing an acrylic resin composition containing the above-mentioned cyclohexyl (meth) acrylate as a monomer component and a weathering agent such as an ultraviolet absorber described later to the outermost surface of the decorative sheet. Although it will be described in detail later, for example, after applying a coating liquid containing the above-mentioned acrylic resin composition and a weathering agent onto the transparent polyvinyl chloride resin layer 6 on which the embossed portion 10 is formed, wiping it may embed the coating liquid into the embossed portion 10 to form the surface protective layer 8. As a method for curing the coating liquid for forming the surface protective layer 8, for example, any of a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type in which curing is performed by irradiating ultraviolet rays, ionizing radiation, etc. can be used. However, considering weather resistance, the two-component curing type or the active energy ray curing type is preferable. If the post-processability after being laminated on various substrates to form a decorative member is considered, the two-component curing type crosslinked by isocyanate curing is desirable.

[0037] As the two-component curing type acrylic resin composition, for example, a composition containing an acrylic resin having two or more functional groups selected from a hydroxyl group, an amino group, and a carboxyl group in one molecule and a polyisocyanate compound having two or more isocyanate groups capable of reacting with the functional group in one molecule is preferable. Particularly preferably, it is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0038] As the acrylic polyol having two or more carboxyl groups in one molecule, in addition to the cyclohexyl (meth) acrylate described above, for example, a (meth) acrylic acid ester copolymer containing hydroxyethyl (meth) acrylate as a monomer component can be used. On the other hand, as the polyisocyanate compound having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, burette types, etc. synthesized from one or more of these compounds by known techniques can be mentioned. In addition, a composition in which one or more selected from these different types of polyisocyanates are mixed can be used. Among them, HDI, or the trimer type, TMP adduct type, burette type of HDI is preferable from the viewpoint of weather resistance. The content of the isocyanate compound with respect to the resin component described above can be arbitrarily set, but it is desirable to set the equivalent ratio of hydroxyl group / isocyanate group to be about 1 / 1 to 1 / 3. In particular, when the equivalent amount of the hydroxyl group is more than the equivalent amount of the isocyanate group, crosslinking does not proceed sufficiently and the desired performance is not added to the surface protection layer 8, which may be unfavorable.

[0039] When the curing method of the coating liquid for forming the surface protection layer 8 is active energy ray curing, as the active energy ray curing type acrylic resin composition, known monomers, oligomers, etc. having a (meth) acryloyl group can be used. In addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth) acrylate may be blended. In order to further improve the weather resistance of the decorative sheet 1, in the present embodiment, an ultraviolet absorber and a light stabilizer are added to the surface protection layer 8 as weathering agents.

[0040] (Ultraviolet absorber) As the ultraviolet absorber, for example, known ones such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), benzophenone-based ones can be used. Among these, if a hydroxyphenyltriazine-based ultraviolet absorber is selected, the triazine skeleton suppresses bleed, and the triazine skeleton is chemically more stable compared to the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, etc., making it possible to maintain long-term ultraviolet absorption performance. That is, 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-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and the like. In the present 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 used as 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 the present embodiment, the addition amount of the above-mentioned triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition (for example, an acrylic resin composition) for forming the surface protective layer 8. By setting the addition amount of the above-mentioned ultraviolet absorber to 1 part by mass or more, the weather resistance improvement effect is exhibited, and by setting it to 30 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a practically acceptable level. In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber added to the surface protective layer 8, its addition amount is preferably in the range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition, more preferably in the range of 5 parts by mass or more and 15 parts by mass or less, and even more preferably in the range of 8 parts by mass or more and 12 parts by mass or less. By setting the addition amount of ultraviolet absorber A to 1 part by mass or more, the weather resistance improvement effect is exhibited, and by setting it to 20 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a practically acceptable level.

[0043] In the present embodiment, further excellent weather resistance performance is imparted by using ultraviolet absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter, referred to as "ultraviolet absorber B" for convenience) in combination as the triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber in the surface protective layer 8. This is because ultraviolet absorber B has a high ultraviolet absorption ability in the short-wavelength region, which is relatively high in energy among ultraviolet rays, and is chemically stable compared to other ultraviolet absorbers that absorb in almost the same wavelength region, so that the wavelength region for absorbing ultraviolet rays becomes wider by the combination. Note that 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is used as ultraviolet absorber B, is generally known as the main component of "ADEKA STAB LA-46: manufactured by ADEKA CORPORATION".

[0044] In the present embodiment, it is preferable that the addition amount of the ultraviolet absorber A in the surface protective layer 8 is in the range of 10 parts by mass or more and 200 parts by mass or less, more preferably in the range of 20 parts by mass or more and 100 parts by mass or less, and even more preferably in the range of 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the ultraviolet absorber B. By setting the addition amount of the ultraviolet absorber A within the above numerical range, more excellent 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 and the radical scavenger in combination, the weather resistance of the cosmetic sheet 1 can be further improved. Examples of the hindered amine-based radical scavenger that can be used in this embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-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 / succinic acid diethyl polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl〕-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(1,2,2,6,(6-Pentamethyl-4-piperidyl)amino)-s-triazin-6-yl)-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate cyclohexane and the reaction product of N-butyl 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine and the reaction product with 2-aminoethanol, etc. can be mentioned, but it is not limited thereto.,

[0046] In this embodiment, the addition amount of the light stabilizer (for example, a hindered amine-based radical scavenger) in the surface protection layer 8 is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition (for example, an acrylic resin composition) forming the surface protection layer 8. By adding 1 part by mass or more of the light stabilizer, desired weather resistance can be obtained, and by setting it to 30 parts by mass or less, bleed-out of the weathering agent can be suppressed, and the influence on other physical properties of the surface protection layer 8 can be suppressed. In addition, although the surface protection layer 8 is described as containing an ultraviolet absorber and a light stabilizer in this embodiment, the present disclosure is not limited thereto. The surface protection layer 8 may be provided with desired weather resistance according to the application, and the surface protection layer 8 may be configured to contain at least one of an ultraviolet absorber and a light stabilizer.

[0047] (Coating amount) The coating amount of the surface protection layer 8, that is, the coating amount of the material of the surface protection layer 8 on the transparent polyvinyl chloride resin layer 6 is 3 g / m 2 or more and 10 g / m 2 less. When the coating amount is less than 3 g / m 2 less, good weather resistance cannot be obtained, and when it is 10 g / m2 If it exceeds the above range, it may inhibit recyclability. Therefore, by setting the coating amount within the above range, it is possible to achieve both good weather resistance and recyclability. In addition, by setting the coating amount within the above range, productivity and processability (e.g., bend processability) can be improved.

[0048] (Embossed part) As shown in FIG. 1, an embossed part 10 is provided on the outermost surface of the decorative sheet 1. By providing the embossed part 10 on the outermost surface, it is possible to improve fingerprint resistance while maintaining, for example, the matte feeling on the surface of the decorative sheet 1. Further, the embossed part 10 can be formed into various uneven shapes such as wood grain board conduit grooves, unevenness on the surface of slate (such as granite split surface), fabric surface texture, satin finish, sandblasted finish, hairline, and multi-line grooves, so as to impart a given design property to the surface of the decorative sheet 1. The embossed part 10 can be formed into various uneven shapes according to, for example, the design of the pattern layer 4 or the desired design property. The embossed part 10 is formed on the surface (outermost surface) side of the surface protection layer 8 which is the outermost layer of the decorative sheet 1, and constitutes an uneven pattern. In the present embodiment, the above-described surface protection layer 8 is embedded in the embossed part 10 that constitutes this uneven pattern. Hereinafter, this point will be described.

[0049] In the decorative sheet 1 according to the present embodiment, the embossed part 10 is provided in the transparent polyvinyl chloride resin layer 6. That is, the transparent polyvinyl chloride resin layer 6 is a layer in which the embossed part 10 is formed. The shape of the uneven pattern provided on the surface of the transparent polyvinyl chloride resin layer 6 is not particularly limited, but the shape of the embossed part 10 that constitutes the uneven pattern is preferably such that the opening diameter increases from the pattern layer 4 side of the transparent polyvinyl chloride resin layer 6 toward the surface protection layer 8. With such a shape, when the surface protection layer composition (coating liquid) is embedded in the embossed part 10 by wiping, the embedding becomes easy.

[0050] Also, the side surface forming the embossed portion 10 is preferably an inclined surface. If the side surface forming the embossed portion 10 is an inclined surface, when embedding the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, the embedding becomes easier. Also, all of the side surfaces forming the embossed portion 10 may be covered with the surface protective layer 8. Also, the depth of the embossed portion 10 is preferably in the range of 1 μm or more and 50 μm or less with respect to the thickness direction of the transparent polyvinyl chloride resin layer 6. If the depth of the embossed portion 10 is within the above numerical range, when embedding the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, the embedding becomes easier, and peeling of the surface protective layer can be prevented.

[0051] Also, the width of the embossed portion 10 in the cross section shown in FIG. 1 is preferably in the range of 1 μm or more and 20 μm or less. If the width of the embossed portion 10 is within the above numerical range, when embedding the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, the embedding becomes easier, and peeling of the surface protective layer embedded in the embossed portion 10 can be prevented.

[0052] Also, although the embossed portion 10 is preferably entirely filled (packed) with the surface protective layer composition (coating liquid), the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is preferably 10% or more. If the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is 10% or more, the weather resistance in the embossed portion 10 can be improved. That is, if the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is 10% or more, for example, the occurrence of whitening and breakage in the conduit portion can be reduced. Also, as described above, although the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is preferably 100%, it is more preferably 80% or less, and even more preferably 60% or less. If the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 is 80% or less, a sufficient tactile sensation can be obtained in the embossed portion 10.

[0053] Further, by making the filling rate of the surface protective layer 8 with respect to the volume of the embossed portion 10 100%, the surface of the surface protective layer 8 filled in the embossed portion 10 and the surface of the transparent polyvinyl chloride resin layer 6 in the region without the embossed portion 10 may be flush, so to speak. Note that the embossed portion 10 does not necessarily have to be provided, but it is preferably provided.

[0054] (Total thickness of the decorative sheet) The total thickness of the decorative sheet 1, that 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, and the thickness of the surface protective layer 8 is preferably in the range of 100 μm or more and 300 μm or less, and more preferably in the range of 120 μm or more and 200 μm or less. If the total thickness of the decorative sheet 1 is less than 100 μm, the concealability and scratch resistance will decrease. Further, when processing the decorative sheet 1, the sheet will be flimsy and the productivity will decrease. If the total thickness of the decorative sheet 1 is more than 300 μm, the processability such as bending will decrease. As a result, for example, a decorative sheet 1 having concealability equivalent to that of a conventional decorative sheet formed using an olefin-based resin and having good processability can be formed. Here, the total thickness of the decorative sheet 1 means, in the case of the decorative sheet 1 shown in FIG. 1, 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, and the thickness of the surface protective layer 8, that is, the sum of the thicknesses of all the layers constituting the decorative sheet 1. For example, in the decorative sheet 1 shown in FIG. 1, when a concealment layer is provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2, it means the total thickness of the decorative sheet 1 obtained by adding 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 further the thickness of the concealment layer, that is, 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] (Modification example) In the decorative sheet 1, a gloss adjustment layer (not shown) may be provided on the surface protection layer 8, and the gloss adjustment layer may be synchronized with the pattern of the pattern layer 4. Also, in the decorative sheet 1, the pattern of the pattern layer 4 and the embossed portion 10 may be synchronized. The decorative sheet 1 includes a colored polyvinyl chloride resin layer 2 as a colored base material layer, but the colored polyvinyl chloride resin layer (colored base material layer) 2 is not necessarily provided. That is, the decorative sheet 1 may have a single-layer specification. When the decorative sheet 1 has a single-layer specification, it is preferable to provide a concealment layer (not shown) on the surface opposite to the transparent polyvinyl chloride resin layer 6 of the pattern layer 4.

[0056] (Decorative member) The decorative sheet 1 shown in FIG. 1 may be bonded to the base material 20 as shown in FIG. 2 to form a decorative member 100.

[0057] (Base material) As the base material 20, a wooden base material or a metal base material can be used. As the wooden base material, for example, a wood veneer, a plywood, a laminated wood, a particle board, a medium density fiber board, or a hard fiber board can be adopted. As the metal base material, a steel plate, an aluminum plate, etc. can be adopted. Also, the base material 20 may be a resin such as plastic or a composite material thereof. When the base material 20 is a resin base material, for example, a vinyl chloride resin can be adopted. The base material 20 made of vinyl chloride resin has high heat insulation properties and the demand as a window frame fitting (sash) is increasing. Also, the decorative member 100 decorated with the decorative sheet 1 on the base material 20 made of vinyl chloride resin can dissolve both the base material 20 and the decorative sheet 1 and be reused, and the recyclability can be made better.

[0058] Also, the base material 20 may be composed of, for example, a non-combustible steel plate or a non-combustible material specified in the Ministry of Construction Notification No. 1400. Also, the base material 20 may have a structure subjected to bending processing or a three-dimensional structure. By bonding the decorative sheet 1 according to the present embodiment to the base material 20, even when the base material 20 is formed using a polyvinyl chloride resin, a decorative member excellent in processability and recyclability can be obtained. Note that the configuration of the decorative member 100 is not limited to the example shown in FIG. 2. That is, the configuration of the decorative member 100 may include a decorative sheet 1 laminated on the other surface (the lower surface in FIG. 1) of the base material 20 in addition to one surface of the base material 20.

[0059] When laminating the decorative sheet 1 on the base material 20, an adhesive layer 12 may be provided by laminating through an appropriately selected adhesive as needed, or direct lamination may be performed without using an adhesive or the like. The adhesive may be selected according to the material of the base material 20, and may be a two-component curing type or hot melt type adhesive. As a method of laminating and bonding the decorative sheet 1 to the base material 20, it is possible to use a method of pressing flat by contacting a metal plate or a rotary pressure continuous lamination method. In particular, when using a continuous lamination method using an endless metal belt, there are no warps or undulations on the surface, and furthermore, the adhesion between layers is good, and a high-quality decorative member 100 that is densely cured and integrated can be continuously manufactured at high speed.

[0060] Applying it to a fitting member such as a window frame, particularly an exterior fitting member, as the base material 20 is effective. That is, due to the increasing awareness of zero-energy houses (ZEH) and the like, there is a high demand for fittings such as highly heat-insulating window frames using polyvinyl chloride resin for exterior fittings. Since the decorative sheet 1 is formed using polyvinyl chloride, it is particularly attached to fitting members such as window frames using polyvinyl chloride resin, and by making the base material 20 and the decorative sheet 1 into a single material, a fitting having higher recyclability than the case of using an olefin-based resin sheet or the like, particularly an exterior fitting, can be obtained. In addition, it is also possible to apply a fitting member made of another material, such as an aluminum material, as the base material 20. In this case, although the recyclability is somewhat reduced compared to the case of using a single material, by laminating the decorative sheet 1 using polyvinyl chloride resin, a fitting with high processability can be obtained.

[0061] (Method for manufacturing a decorative sheet and a decorative member) Hereinafter, an example of the method for manufacturing the decorative sheet 1 according to the present embodiment will be briefly described. For example, a pattern layer 4 is printed on a colored polyvinyl chloride resin layer 2 made of a colored polyvinyl chloride resin sheet. Next, a transparent polyvinyl chloride resin layer 6 is formed on the colored polyvinyl chloride resin layer 2 on which the pattern layer 4 is formed by thermal lamination. At the same time, an embossed portion 10 is formed by providing an uneven 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 uneven pattern (embossed portion 10) is formed. Finally, the coating liquid is wiped so as to be embedded in the embossed portion 10 constituting the uneven pattern, and the coating liquid is cured to form the surface protection layer 8 on the transparent polyvinyl chloride resin layer 6. In this way, the decorative sheet 1 according to the present 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 the base material 20 is attached. Thus, a decorative member 100 in which the decorative sheet 1 and the base material 20 are bonded together via an adhesive layer 12 is formed. Note that 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 according to the design and the like without departing from the technical idea of the present invention even in forms other than this embodiment.

[0063] (Effect) (1) The cosmetic sheet 1 according to the first embodiment of the present invention is formed by laminating at least a pattern layer 4 and a transparent polyvinyl chloride resin layer 6 in this order. The resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less. Further, the transparent polyvinyl chloride resin layer 6 contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less. Therefore, even when forming a sheet made of transparent polyvinyl chloride resin, it is possible to ensure the film-forming stability, and to obtain good wrapping processability of the cosmetic sheet 1 and a good bending state during the wrapping process of the cosmetic sheet 1. Also, the cosmetic sheet 1 is formed by laminating at least a pattern layer 4 and a transparent polyvinyl chloride resin layer 6 in this order. The resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having a K value calculated according to JIS K7367-2:1999 of 60 or more and 75 or less. Further, the transparent polyvinyl chloride resin layer 6 contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less. Therefore, also in this case, even when forming a sheet made of transparent polyvinyl chloride resin, it is possible to ensure the film-forming stability, and to obtain good wrapping processability of the cosmetic sheet 1 and a good bending state during the wrapping process of the cosmetic sheet 1.

[0064] (2) Since the elongation at break of the cosmetic sheet 1 at 0 °C is 10% or more and 400% or less, it has appropriate softness, so it is possible to suppress whitening and cracking during wrapping, and to suppress 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 satisfies a viscosity measured by a capillary viscometer according to JIS K7367-5:2000 of 500 MPa·s or more and 3000 MPa·s or less. Therefore, it is possible to ensure good weather resistance, and by setting the viscosity to 500 MPa·s or more and 3000 MPa·s or less, the elongation at break of the cosmetic sheet 1 at 0 °C can be easily adjusted within the range of 10% or more and 400% or less. (4) By using NOR-type HALS as the HALS added to the transparent polyvinyl chloride resin layer 6, the dehydrochlorination reaction can be suppressed.

[0065] (5) By forming the decorative member 100 with the base material 20 and the decorative sheet 1 laminated on the base material 20, even when the decorative sheet 1 is formed using polyvinyl chloride resin, a decorative member 100 excellent in processing suitability can be provided. (6) Since the decorative sheet 1 is laminated on the fitting member as the base material 20 to form a fitting, even when the decorative sheet 1 is formed using polyvinyl chloride resin, a fitting excellent in processing suitability can be provided. In particular, by laminating the decorative sheet 1 on the exterior fitting member (base material 20) made of a vinyl chloride-based material, both the decorative sheet 1 and the fitting member are made of a vinyl chloride-based material, so that the recyclability can be further enhanced. (Example 1)

[0066] Hereinafter, the first embodiment of the present invention will be described in detail with reference to examples and comparative examples. Note that 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 base material layer). Gravure printing was performed on one surface of the colored polyvinyl chloride resin sheet using printing ink for vinyl chloride to form a pattern layer. Then, a transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was thermally laminated on the colored polyvinyl chloride resin sheet including the pattern layer. Then, as the surface protective layer, a resin composition mainly composed of an acrylic resin composition was laminated on the transparent polyvinyl chloride sheet. Thereby, the decorative sheet of Example 1-1 was obtained. The elongation at break of the obtained decorative sheet at 0°C was 40%. 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-based Viscosity: 510 Additive: 20 PHR Ultraviolet absorber: Cyanoacrylate-based ultraviolet absorber 0.5 parts by mass HALS: NOR type 0.5 parts by mass (manufactured by ADEKA Corporation, Adeka Stab LA81)

[0070] (Pattern layer) Binder resin: Mixture of vinyl chloride resin-vinyl acetate resin copolymer resin and acrylic resin

[0071] (Surface protection layer) Main agent: Methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) 90 parts by mass Ultraviolet absorber: Tinuvin 479 manufactured by BASF Japan Ltd. 9 parts by mass Light stabilizer: Tinuvin 123 manufactured by BASF Japan Ltd. 1 part by mass Hardening agent: Takenate D170 manufactured by Mitsui Chemicals, Inc. 10 parts by mass Solvent: Ethyl acetate 240 parts by mass Coating amount 3 g / m 2

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

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

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

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

[0076] (Comparative Example 1-1) In a transparent polyvinyl chloride resin sheet, 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) having a degree of polymerization of 690 and a K value of 58.6 was used. The elongation at break of the obtained decorative sheet at 0°C was 30%. (Comparative Example 1-2) In a transparent polyvinyl chloride resin sheet, 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) having a degree of polymerization of 1740 and a K value of 77.4 was used. The elongation at break of the obtained decorative sheet at 0°C was 520%.

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

[0078] 〔Evaluation〕 For each of the cosmetic sheets of the examples and comparative examples, evaluations were conducted on the film-forming stability, wrapping process suitability, state of the bent portion during wrapping, and light resistance of the transparent polyvinyl chloride resin sheet. The evaluation criteria are as follows.

[0079] (Film-forming stability of transparent polyvinyl chloride resin sheet) The film-forming stability when forming a polyvinyl chloride resin sheet was evaluated. 〇 (Pass): No fish eyes or the like occur, the calendering suitability is good, and the sheet can be formed stably. × (Fail): Fish eyes or the like occur. Or the calendering suitability is poor, and the sheet cannot be formed stably.

[0080] (Wrapping process suitability) The ease of handling during wrapping of the cosmetic sheet was evaluated. ◎ (Pass): Possible under a wide range of production conditions 〇 (Pass): Possible with limited production conditions × (Fail): Difficult to produce (lacking flexibility and difficult to handle, or prone to tearing and cracking

[0081] (State of the bent portion during wrapping) The state of the bent portion during wrapping of the cosmetic sheet was evaluated. ◎ (Pass): No whitening or cracking occurs in the bent portion during processing at 0°C. 〇 (Pass): Slight whitening occurs in the bent portion during processing at 0°C, but it is at an acceptable level. Also, no cracking occurs. × (Fail): Whitening and cracking occur in the bent portion during processing at 0°C.

[0082] (Weather resistance) A metal weather tester (manufactured by Daipra Wintersteiger Co., Ltd., KU-R5DCI-A) was used to conduct an accelerated weather resistance test for 504 h under the following test conditions. Test conditions: BPT (black panel temperature): 63°C, illuminance 65 mW / cm 2Using "UV irradiation for 20 hours + condensation for 4 hours" as one cycle, 21 cycles were carried out. The color difference ΔE before and after the weathering acceleration test was evaluated. ◎ (Pass): ΔE < 2.0 〇 (Pass): 2.0 ≤ ΔE ≤ 4.0 × (Fail): ΔE > 4.0 Those with "〇" or above were considered qualified.

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

[0084]

Table 1

[0085] As shown in Table 1, for Examples 1-1 to 1-9, the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) is a polyvinyl chloride resin having an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less, or a polyvinyl chloride resin having a K value calculated according to JIS K7367-2:1999 of 60 or more and 75 or less, and contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less. It was confirmed that the elongation at break at 0 °C is 10% or more and 400% or less, and all of the film-forming stability of the transparent polyvinyl chloride resin sheet, the wrapping process suitability of the decorative sheet, and the bending part state during the wrapping process of the decorative sheet are good.

[0086] In addition, although the cosmetic sheets of Examples 1-1 to 1-6 had good weather resistance, it was confirmed that better weather resistance was obtained when a cyanoacrylate-based ultraviolet absorber was used (Example 1-3) compared to when a benzophenone-based ultraviolet absorber was used (Example 1-4). Further, in Example 1-7 where 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 ultraviolet absorber was used as the ultraviolet absorber, in Example 1-8 where an NH type was used as the HALS for the transparent polyvinyl chloride resin sheet, and in Example 1-9 where the transparent polyvinyl chloride resin sheet did not contain an ultraviolet absorber, it was confirmed that the weather resistance was not sufficient.

[0087] Also, in Example 1-1, in Comparative Example 1-1 where 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, since the elongation at break viscosity at 0°C was low, it was confirmed that the film-forming stability of the transparent polyvinyl chloride resin sheet decreased. Conversely, in Example 1-1, in Comparative Example 1-2 where 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, it was easier to stretch and less likely to crack, but the elongation at break at 0°C increased and it became soft and lacked firmness. Therefore, it was confirmed that the film-forming stability of the transparent polyvinyl chloride resin sheet was poor, and the wrapping process suitability of the cosmetic sheet was also poor, and the state of the bent portion during wrapping was also poor.

[0088] Furthermore, in Example 1-5, in Comparative Example 3 where the addition amount of the plasticizer added to the transparent polyvinyl chloride resin sheet exceeded 30 PHR, since the elongation at break at 0°C exceeded 400% and it was soft and lacked firmness, it was confirmed that the wrapping process suitability and the state of the bent portion during wrapping were poor. Also, in Example 1-1, in Comparative Example 1-4 where the addition amount of the plasticizer added to the transparent polyvinyl chloride resin sheet did not reach 20 PHR, since the elongation at break at 0°C was less than 10% and it was hard, it was confirmed that the wrapping process suitability and the state of the bent portion during wrapping were poor.

[0089] (Second Embodiment) Next, a second embodiment of the present invention will be described. The cosmetic sheet of the second embodiment is the same as the cosmetic sheet in the first embodiment, except that the configuration of the transparent polyvinyl chloride resin layer 6 is different. Therefore, the same reference numerals are given to the same parts, and detailed descriptions thereof are 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 cosmetic sheet 1. The transparent polyvinyl chloride resin layer 6a is formed of a polyvinyl chloride resin. For example, it is formed of a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processing suitability, and further has printing suitability. As described above, PVC can be used as a recycled base material by melting and extruding it, and it is easier to reuse by melting compared to olefin resins. That is, the cosmetic sheet 1 according to the second embodiment can surely improve the processing suitability and recyclability by using the colored polyvinyl chloride resin layer 2 containing a polyvinyl chloride resin and the transparent polyvinyl chloride resin layer 6a.

[0091] Note that the transparent polyvinyl chloride resin layer 6a preferably has such transparency that the pattern layer 4 provided on the surface on the side of the colored polyvinyl chloride resin layer 2 (the lower surface in FIG. 1) can be seen through from the surface protection layer 8 side. The transparent polyvinyl chloride resin layer 6a is preferably any of colorless transparent, colored transparent, and translucent, for example. 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 a low basicity, preferably a base dissociation constant pkb of 5 or more and 12 or less, and more preferably a base dissociation constant pkb of 8 or more and 10 or less. If the basicity is low and the base dissociation constant pkb is 5 or more, the transparent polyvinyl chloride resin layer 6a is caused by a base. 脱HClThe reaction can be suppressed, and it is effective against current acid rain. On the other hand, the greater the basicity, the lower the weather resistance, so the base dissociation constant pkb is preferably 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, more preferably 0.1% or more and 1% or less based on the resin solid content. Also, 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 according to JIS K6720-2 of 800 or more and 1500 or less. Or the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having a K value calculated according to 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 tougher, more stretchable, less likely to crack, and the more durable the decorative sheet 1 can be. If the average degree of polymerization is too high, the gelation temperature will be high, resulting in fish eyes and the like, making it difficult to form the transparent polyvinyl chloride resin layer 6a. Also, the lower the average degree of polymerization, the more likely the decorative sheet 1 is to crack, and due to the low viscosity, the calendering suitability is poor and the film-forming stability is poor. Therefore, the resin constituting the transparent polyvinyl chloride resin layer 6a is preferably a polyvinyl chloride resin having an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less.

[0094] Also, 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. Here, for the decorative sheet (polyvinyl chloride (PVC) sheet) formed using polyvinyl chloride resin, due to the absorption of ultraviolet light near 320 nm, the C-C bond in the PVC main chain breaks, and the embrittlement of the sheet and the dehydrochlorination reaction start. Also, near 360 nm, the C-Cl bond in PVC breaks, and a polyene with a C=C double bond is generated, resulting in a phenomenon where the sheet turns brown (referred to as brown spots) that can be observed. 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 setting the transmittance of ultraviolet light at a wavelength of 320 nm to 0.05%T or less, the embrittlement and dehydrochlorination reaction of the decorative sheet can be suppressed. Also, by setting the transmittance of ultraviolet light at a wavelength of 360 nm to 0.4%T or less, the generation of polyene with a C=C double bond can be suppressed, and the occurrence of discoloration (brown spots) can be suppressed. That is, in the transparent polyvinyl chloride resin layer 6a, by controlling the transmittance of ultraviolet light at wavelengths of 320 nm and 360 nm to be the above upper limit values, the weather resistance of the decorative sheet 1 can be improved. Therefore, for example, as a decorative sheet for decorating the surface of decorative materials for exterior and semi-exterior applications, a decorative sheet 1 with excellent weather resistance that can withstand long-term outdoor use can be obtained. A plasticizer may be added to the transparent polyvinyl chloride resin layer 6a. As the plasticizer, a high molecular weight polyester resin is preferred, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. Also, in terms of viscosity, the viscosity of the plasticizer measured by a capillary viscometer in accordance with JIS K7367-5:2000 is preferably 500 MPa·s or more and 3000 MPa·s or less.

[0095] As a plasticizer, a high molecular weight polyester is preferred among polyester resins. Phthalic acid resins (such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more likely to bleed out compared to high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance. When the content of the plasticizer is less than 20 PHR, the cold resistance deteriorates even when using a phthalic acid resin. Therefore, when using a high molecular weight polyester resin as the plasticizer, the content of the plasticizer is preferably 20 PHR or more. When the content of the plasticizer is more than 30 PHR, the decorative sheet 1 becomes too soft and loses its firmness, making it difficult to handle and resulting in poor productivity during processing. Also, the scratch resistance of the decorative sheet 1 is low.

[0096] Also, when the viscosity of the plasticizer is less than 500 MPa·s, it has a low molecular weight and is likely to bleed out and has poor weather resistance. When the viscosity of the plasticizer is more than 3000 MPa·s, it is too high in molecular weight, has a high viscosity, and makes resin production difficult. Also, the cold resistance is poor.

[0097] 〔Weathering agent〕 The transparent polyvinyl chloride resin layer 6a may further contain a weathering agent. Thereby, excellent weather resistance can be imparted to the transparent polyvinyl chloride resin layer 6a.

[0098] In order to favorably control the above-described ultraviolet transmittance, the transparent polyvinyl chloride resin layer 6a preferably contains an ultraviolet absorber. That is, in the decorative sheet 1 according to the second embodiment, the transparent polyvinyl chloride resin layer 6a is preferably formed of a transparent polyvinyl chloride resin and contains an ultraviolet absorber. Thereby, the ultraviolet transmittance of the transparent polyvinyl chloride resin layer 6a can be favorably controlled as described above, and excellent weather resistance can be imparted to the decorative sheet 1. More specifically, the transparent polyvinyl chloride resin layer 6a preferably contains at least one ultraviolet absorber selected from benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers as the ultraviolet absorber. Thereby, the ultraviolet absorption ability of the transparent polyvinyl chloride resin layer 6a is improved over a wide range of wavelengths of 320 nm and 360 nm, the ultraviolet transmittance is well controlled, excellent weather resistance is imparted to the transparent polyvinyl chloride resin layer 6a, and the weather resistance of the decorative sheet 1 can be improved.

[0099] Some benzophenone-based ultraviolet absorbers can absorb in the wavelength range of 320 to 340 nm. In addition, benzotriazole-based ultraviolet absorbers can absorb in the wavelength ranges of 300 to 320 nm and 340 to 360 nm. Further, triazine-based ultraviolet absorbers absorb in the wavelength range covering 270 to 360 nm, and cyanoacrylate-based ultraviolet absorbers have a maximum absorption at around 310 nm and are preferably used for PVC. The content of the ultraviolet absorber in the transparent polyvinyl chloride resin layer 6a may be added according to the desired weather resistance. For example, it preferably exceeds 0.3 parts by mass and is within the range of 1.0 part by mass or less with respect to 100 parts by mass of the transparent vinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6a, and more preferably within the range of 0.5 part by mass or more and 0.8 part by mass or less. Thereby, the weather resistance of the decorative sheet 1 can be surely improved.

[0100] (Benzophenone-based ultraviolet absorber) As the benzophenone-based ultraviolet absorber, for example, octabenzone and its modified products, polymers, and derivatives can be used. Further, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), etc. can be mentioned. Known products include, for example, "ADEKA STAB (registered trademark) LA-1413 manufactured by ADEKA CORPORATION", "Chimassorb 81 manufactured by BASF Japan Ltd.", etc.

[0101] (Benzotriazole-based ultraviolet absorber) Examples of the "benzotriazole-based" ultraviolet absorber 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, etc., as well as mixtures, modified products, polymers, and derivatives thereof.

[0102] (Triazine-based ultraviolet 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 bleed, and the triazine skeleton is chemically stable compared to the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, etc., so that it is possible to maintain long-term ultraviolet absorption performance.

[0103] Examples of the triazine-based ultraviolet absorber used for 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- Examples include [hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

[0104] (Cyanoacrylate-based ultraviolet 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 BASF Japan Ltd.'s cyanoacrylate-based ultraviolet absorbers "Uvinul (registered trademark) 3035 (product number)" (molecular weight 277), "Uvinul 3039" (molecular weight 361), "Uvinul 3030FF" (molecular weight 1060), etc.

[0105] The thickness of the transparent polyvinyl chloride resin layer 6a is preferably in the range of 50 μm or more and 150 μm or less, more preferably in the range of 50 μm or more and 100 μm or less, and even more preferably in the range of 60 μm or more and 80 μm or less. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 can be surely improved, and further, unevenness of adherends such as window frames can be absorbed to improve the construction finish of the decorative sheet 1. Also, when 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, the processing suitability (for example, wrapping processability) is improved, and the manufacturing cost of the decorative sheet 1 can be reduced.

[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 cosmetic sheet 1 according to the second embodiment of the present invention is formed by laminating at least a pattern layer 4 and a transparent polyvinyl chloride resin layer 6a in this order. The resin constituting the transparent polyvinyl chloride resin layer 6a has an average degree of polymerization calculated according to JIS K6720-2 of 800 or more and 1500 or less, or a K value calculated according to JIS K7367-2:1999 of 60 or more and 75 or less. It is a polyvinyl chloride resin that satisfies at least one of the above conditions. Further, 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. Therefore, even when forming a film of a transparent polyvinyl chloride resin sheet, it is possible to ensure the film forming stability, and to obtain good wrapping process suitability of the cosmetic sheet 1 and a good bending state during the wrapping process of the cosmetic sheet 1.

[0108] (2) The viscosity of the plasticizer added to the transparent polyvinyl chloride resin layer 6a satisfies a viscosity measured by a capillary viscometer according to JIS K7367-5:2000 of 500 MPa·s or more and 3000 MPa·s or less, so that good weather resistance can be ensured. (3) By including a light stabilizer and an ultraviolet absorber (UVA) in the transparent polyvinyl chloride resin layer 6a, the weather resistance of the cosmetic sheet can be improved. In particular, by using a NOR type HALS as the light stabilizer added to the transparent polyvinyl chloride resin layer 6, the dehydrochlorination reaction can be suppressed. Further, by using a NOR type HALS with a lower basicity, the dehydrochlorination reaction can be suppressed even more compared to those with a higher basicity. In particular, by using a NOR type HALS with a base dissociation constant pkb of 5 or more and 12 or less, while ensuring weather resistance, the reaction by the base 脱HCl can be suppressed, which is effective. (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 a polyvinyl chloride resin, a decorative sheet excellent in weather resistance can be provided, and for example, a decorative sheet 1 having excellent weather resistance that can withstand long-term use even outdoors can be obtained. That is, a decorative sheet 1 excellent not only in processability but also in weather resistance can be obtained.

[0109] (5) By forming the decorative member 100 with the base material 20 and the decorative sheet 1 adhered to the base material 20, even when the decorative sheet 1 is formed using a polyvinyl chloride resin, a decorative member 100 excellent in processability can be provided. (6) Since the decorative sheet 1 is adhered to the fitting member as the base material 20 to form a fitting, even when the decorative sheet 1 is formed using a polyvinyl chloride resin, a fitting excellent in processability can be provided. In particular, by adhering the decorative sheet 1 to the exterior fitting member (base material 20) made of a vinyl chloride-based material, both the decorative sheet 1 and the fitting member are formed of a vinyl chloride-based material, so that recyclability can be further enhanced. (Example 2)

[0110] Hereinafter, the second embodiment of the present invention will be described in detail by showing examples and comparative examples. Note that 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 base material layer). Gravure printing was performed on one surface of the colored polyvinyl chloride resin sheet using printing ink for vinyl chloride to form a pattern layer. Thereafter, a transparent polyvinyl chloride resin sheet as a transparent polyvinyl chloride resin layer (transparent resin layer) was thermally laminated on the colored polyvinyl chloride resin sheet including the pattern layer. Thereafter, a resin composition mainly composed of an acrylic resin composition was laminated on 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 Additive: 20 PHR HALS: NOR type pkb = 10 0.2% (manufactured by ADEKA Corporation, Adeka Stub LA81) UV absorber: Triazine-based 0.5 parts by mass

[0114] (Pattern layer) Binder resin: Mixture of vinyl chloride resin-vinyl acetate resin copolymer resin and acrylic resin

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

[0116] (Example 2-2) In the decorative sheet of Example 2-1, a decorative sheet of Example 2-2 was obtained in the same procedure as in Example 1, except that 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) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Example 2-3 was obtained in the same procedure as in Example 2-1, except that the addition amount of HALS in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 1%.

[0117] (Example 2-4) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Example 2-4 was obtained in the same procedure as in Example 2-1, except that the addition amount of HALS 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. (Example 2-5) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Example 2-5 was obtained in the same procedure as in Example 2-1, except that the addition amount of HALS in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3% and the addition amount of the plasticizer was 28 PHR.

[0118] (Example 2-6) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Example 2-6 was obtained in the same procedure as in Example 2-1, except that the addition amount of HALS in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3% and the addition amount of the ultraviolet absorber was 0.8 parts by mass. (Example 2-7) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Example 2-7 was obtained in the same procedure as in Example 2-1, except that the addition amount of HALS in 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) In the cosmetic sheet of Example 2-1, in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer), an NH-type HALS with a base dissociation constant of pkb = 4 was used as the HALS, and a cosmetic sheet of Comparative Example 2-1 was obtained in the same procedure as in Example 2-1 except that the addition amount of this HALS was 0.3%. (Comparative Example 2-2) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Comparative Example 2-2 was obtained in the same manner as in Example 2-1 except that the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) did not contain HALS, 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) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Comparative Example 2-3 was obtained in the same procedure as in Example 2-1 except that 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) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Comparative Example 2-4 was obtained in the same procedure as in Example 2-1 except that 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) In the cosmetic sheet of Example 2-1, a cosmetic sheet of Comparative Example 2-5 was obtained in the same procedure as in Example 2-1 except that the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb = 8, the addition amount of the HALS was 0.3%, the addition amount of the plasticizer was 35 PHR, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber. (Comparative Example 2-6) In the cosmetic sheet of Example 2-1, except that the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) is pkb = 8, the addition amount of the HALS is 0.3%, and the addition amount of the ultraviolet absorber is 0.1 part by mass, a cosmetic sheet of Comparative Example 2-6 was obtained by the same procedure as in Example 2-1. (Comparative Example 2-7) In the cosmetic sheet of Example 2-1, except that the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) is pkb = 8, the addition amount of the HALS is 0.3%, and no ultraviolet absorber was added, a cosmetic sheet of Comparative Example 2-7 was obtained by the same procedure as in Example 2-1. (Comparative Example 2-8) In the cosmetic sheet of Example 2-1, except that the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) is pkb = 9, the addition amount of the HALS is 0.3%, the addition amount of the plasticizer is 15 PHR, and the ultraviolet absorber is a cyanoacrylate-based ultraviolet absorber, a cosmetic sheet of Comparative Example 2-8 was obtained by the same procedure as in Example 2-1.

[0121] 〔Evaluation〕 For each of the cosmetic sheets of the examples and comparative examples, the ultraviolet transmittance (320 nm) and the ultraviolet transmittance (360 nm) were measured. In addition, for each cosmetic sheet, evaluations were made on the weather resistance, the film-forming stability of the transparent polyvinyl chloride resin sheet, and the wrapping process suitability. The evaluation criteria are as follows.

[0122] (Weather resistance) Using a metal weather tester (manufactured by Dipla Wintersteiger Co., Ltd., KU-R5DCI-A), a 504 h accelerated weather resistance test was conducted under the following test conditions. Test conditions: BPT (black panel temperature): 63 °C, illuminance 65 mW / cm 2With "UV irradiation for 20 hours + condensation for 4 hours" as one cycle, 21 cycles (504 hours) were carried out. The color difference ΔE before and after the weathering acceleration test was evaluated. The evaluation criteria are as follows. ◎ (Pass): ΔE < 2.0 〇 (Pass): 2.0 ≤ ΔE < 4.0 × (Fail): ΔE ≥ 4.0 (Film-forming stability of transparent polyvinyl chloride resin sheet) The film-forming stability when forming a polyvinyl chloride resin sheet was evaluated. 〇 (Pass): No fish eyes or the like occur, the calendering suitability is good, and the sheet can be stably formed. × (Fail): Fish eyes or the like occur. Or the calendering suitability is poor and the sheet cannot be stably formed.

[0123] (Lapping process suitability) The ease of handling during lapping of the decorative sheet was evaluated. ◎ (Pass): Possible under a wide range of production conditions 〇 (Pass): Possible with limited production conditions × (Fail): Difficult to produce (lacking flexibility and difficult to handle, or easily torn or cracked, or whitening or cracking occurs at the bent part)

[0124] The above measurement results and the evaluation results of 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 resin constituting the transparent polyvinyl chloride resin sheet (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 or more and 1500 or less, or a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less. It contains a high molecular weight polyester-based plasticizer of 20 PHR or more and 30 PHR or less, has 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. All of the decorative sheets of Examples 2-1 to 2-7 have a weather resistance evaluation of "◎" (qualified), and also have excellent weather resistance when formed using polyvinyl chloride resin (PVC), and it was confirmed that they can withstand long-term use in exterior and semi-exterior applications.

[0128] In addition, it was confirmed that the decorative sheets of Examples 2-1 to 2-7 are both good in the film-forming stability of the transparent polyvinyl chloride resin sheet and the wrapping process suitability of the decorative sheet. Also, it was confirmed that good characteristics can be obtained even when a cyanoacrylate-based ultraviolet absorber is used as the ultraviolet absorber (Example 2-7) as in the case of using a triazine-based ultraviolet absorber. Among the decorative sheets of Examples 2-1 to 2-7, the decorative sheet of Example 2-5, which has a larger addition amount of plasticizer than other decorative sheets, was confirmed to be within the qualified range although the wrapping process suitability is somewhat difficult to handle.

[0129] On the one hand, in Example 2-1, the cosmetic sheet of Comparative Example 2-1 with 0.3% addition of NH-type HALS, and in Example 2-4, the cosmetic sheet of Comparative Example 2-2 without addition of HALS had good film-forming stability of the transparent polyvinyl chloride resin sheet and good suitability for wrapping processing of the cosmetic sheet, but sufficient weather resistance could not be obtained. Further, the cosmetic sheets of Comparative Examples 2-3 and 2-4 outside the range of average degree of polymerization of 800 or more and 1500 or less and outside the range of K value of 60 or more and 75 or less could obtain good weather resistance, but the film-forming stability of the transparent polyvinyl chloride resin sheet was unqualified. The cosmetic sheet of Comparative Example 2-4 with an average degree of polymerization exceeding 1500 and a K value exceeding 75 was also unqualified in terms of suitability for wrapping processing of the cosmetic sheet. In addition, the cosmetic sheets of Comparative Example 2-5 with a plasticizer addition amount exceeding 30 PHR and Comparative Example 2-8 with a plasticizer addition amount less than 20 PHR were unqualified in terms of suitability for wrapping processing of the cosmetic sheet. Furthermore, the cosmetic sheet of Comparative Example 2-6 with an ultraviolet transmittance at a wavelength of 320 nm exceeding 0.05% T and an ultraviolet transmittance at a wavelength of 360 nm exceeding 0.4% T, and the cosmetic sheet of Comparative Example 2-7 containing no ultraviolet absorber could not obtain sufficient weather resistance.

[0130] Incidentally, the present invention can be configured as follows, for example. (1) A cosmetic sheet in which at least a pattern layer and a transparent resin layer are laminated in this order, wherein the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated according to 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. (2) A cosmetic sheet in which at least a pattern layer and a transparent resin layer are laminated in this order, wherein the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated according to 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 in an amount 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 plasticizer has a viscosity measured by a capillary viscometer in accordance with JIS K7367-5:2000 of 500 MPa·s or more and 3000 MPa·s or less. (5) The decorative sheet according to any one of (1) to (4) above, characterized in that the transparent resin layer contains a NOR type hindered amine light stabilizer (HALS). (6) The decorative sheet according to (5) above, characterized in that 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 or more of a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, and a cyanoacrylate type ultraviolet absorber. (8) The decorative sheet according to any one of (1) to (7) above, characterized in that 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, characterized in that a surface protective layer is provided on the outermost surface on the transparent resin layer side. (10) The decorative sheet according to any one of (1) to (9) above, characterized in that a colored base material layer is provided on the side of the pattern layer opposite to the transparent resin layer. (11) The decorative sheet according to any one of (1) to (10) above, and A decorative member, comprising a base material disposed on the outermost surface of the decorative sheet on the pattern layer side. (12) A decorative sheet according to any one of (1) to (10) above, and A fixture, comprising a fixture member disposed on the outermost surface of the decorative sheet on the pattern layer side. (13) The fixture according to (12) above, wherein the fixture member is an exterior fixture member made of a vinyl chloride-based material.

Description of reference numerals

[0131] 1 Decorative sheet 2 Colored polyvinyl chloride resin layer 4 Pattern layer 6, 6a Transparent polyvinyl chloride resin layer 8 Surface protection layer 10 Embossed portion 20 Base material 100 Decorative member

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 decorative sheet is characterized in that the transparent resin layer contains a high molecular weight polyester plasticizer in an amount 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 in an amount of 20 PHR or more and 30 PHR or less.

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

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

5. 3. The decorative sheet according to claim 1, wherein the transparent resin layer contains a NOR type hindered amine light stabilizer (HALS).

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

7. 3. The decorative sheet according to claim 1, wherein 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. 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.

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

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

11. 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.

12. The decorative sheet according to claim 1 or 2, A fitting component is disposed on the outermost surface of the decorative sheet, the surface being the pattern layer side.

13. The fixture according to claim 12, characterized in that the fixture component is an exterior fixture component made of a polyvinyl chloride material.

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