Decorative sheet and decorative member

Abstract

To provide a decorative sheet and a decorative member excellent in fingerprint resistance.SOLUTION: In a decorative sheet 1 having a surface protective layer 8 on the outermost surface layer, the surface protective layer 8 is formed containing a silicon resin, and a contact angle of oleic acid on a surface of the surface protective layer 8 is 20° or more. With the surface protection layer 8 having such a structure, fingerprint resistance can be imparted to the surface protection layer 8, that is, the fingerprint resistance can be imparted to the decorative sheet 1. Since fingerprint resistance can be imparted without providing an uneven part 10, fingerprint resistance of the decorative sheet 1 can be improved without providing the uneven portion 10 or being restricted by the uneven shape of the uneven part 10.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a decorative sheet and a decorative member.

Background Art

[0002] Decorative sheets are used on the surfaces of entrance doors, frames, fittings, furniture, etc., and are touched by many people's hands. When touched by hand, sebum adheres to the surface of the decorative sheet, fingerprints become prominent, and the gloss may change, impairing the appearance of the decorative sheet. In particular, fingerprints are likely to be prominent on decorative sheets with dark patterns or low gloss. As a countermeasure, there has been proposed a method of imparting fingerprint resistance to a decorative sheet by providing a specific uneven shape on the surface of the decorative sheet (see, 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] In the method of providing an uneven shape on the surface of a decorative sheet, although fingerprint resistance can be imparted, it is necessary to provide an uneven shape, and there are also restrictions on the shape. The present invention has been made in view of the above points, and an object thereof is to provide a decorative sheet and a decorative member having excellent fingerprint resistance without being restricted by an uneven shape.

Means for Solving the Problems

[0005] A decorative sheet according to one aspect of the present invention has a surface protective layer on the outermost layer, the surface protective layer contains a silicone resin, and the contact angle of oleic acid on the surface of the surface protective layer is 20° or more. In addition, the cosmetic member according to another aspect of the present invention is characterized by including the cosmetic sheet of the above aspect and a base material disposed on the outermost surface of the cosmetic sheet on the side opposite to the surface protective layer.

Effects of the Invention

[0006] According to one aspect of the present invention, a cosmetic sheet and a cosmetic member excellent in fingerprint resistance can be obtained.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0008] 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.

[0009] 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.

[0010] (First Embodiment) First, the first embodiment of the present invention will be described. The cosmetic sheet 1 according to the first embodiment is a cosmetic sheet mainly composed of a vinyl chloride resin.

[0011] (Configuration of Cosmetic Sheet) FIG. 1 is a cross-sectional view schematically showing an example of the 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 protection layer 8 in this order. Concavo-convex portions 10 are formed on the surface protection layer 8, which is the outermost layer of the cosmetic sheet 1, from the surface side to the transparent polyvinyl chloride resin layer 6.

[0012] (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 bonded 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.

[0013] The colored polyvinyl chloride resin layer 2 is formed of, for example, a flexible, thermoplastic polyvinyl chloride (PVC) resin film having good moldability and processability and further having printability. In addition, the colored polyvinyl chloride resin layer 2 colored opaque can appropriately select a hue as the base color of the pattern layer 4. Further, when making use of the texture of the surface of the adherend, the colored polyvinyl chloride resin layer 2 preferably has a transparency such that the surface of the adherend can be seen through from the surface protection layer 8 side.

[0014] The colored polyvinyl chloride resin layer 2 can be obtained, for example, by mixing a colorant such as a pigment with the polyvinyl chloride resin or kneading it. 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 one or more inorganic substances such as calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0015] In addition, if necessary, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss modifiers may be added to the colored polyvinyl chloride resin layer 2. Here, the case where the colored polyvinyl chloride resin layer 2 is provided as the colored base material layer has been described, but it is not limited to the polyvinyl chloride resin.

[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.

[0017] 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, for example, by dissolving or dispersing a colorant such as a dye or a 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, and pearl pigments such as mica.

[0018] 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 fusibility 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, etc. is preferable.

[0019] 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, letters, symbols, a single solid color, etc., or a combination thereof can be used. Further, in order to improve the concealability 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, for example, using an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide and iron oxide.

[0020] 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.

[0021] Further, various functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retardants may be added to the pattern layer 4 in order to impart various functions. Also, the pattern layer 4 may have a configuration having a solid-coated colored polyvinyl chloride layer for concealing the color and pattern of the adherend to which the decorative sheet 1 is adhered, and a pattern layer for adding a pattern for imparting design properties.

[0022] (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, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and further has good printability.

[0023] The transparent polyvinyl chloride resin layer 6 preferably has such transparency that the pattern layer 4 provided on the surface (the lower surface in FIG. 1) on the side of the colored polyvinyl chloride resin layer 2 can be seen through from the surface protection layer 8 side. The transparent polyvinyl chloride resin layer 6 is preferably any one of colorless transparent, colored transparent, and translucent.

[0024] 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.

[0025] 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 likely to crack, 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 fish eyes and the like, making it difficult to form the transparent polyvinyl chloride resin layer 6 into a film. 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, having poor productivity, and also having poor scratch resistance.

[0026] 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%.

[0027] Also, a plasticizer may be added to the transparent polyvinyl chloride resin layer 6. As the plasticizer, a high molecular weight polyester resin is preferable, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. 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.

[0028] Among polyester resins, high molecular weight polyesters are preferred as the plasticizer. 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.

[0029] 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 soft and loses its firmness, making it difficult to handle and reducing productivity during processing. Also, the scratch resistance of the decorative sheet 1 is low.

[0030] 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 and has a high viscosity, making resin productivity difficult. Also, the cold resistance is poor.

[0031] When the plasticizer content is within the range of 20 PHR or more and 30 PHR or less, the elongation at break of the cosmetic 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, if the elongation at break at 0 °C is less than 10%, the cosmetic sheet 1 is hard, so whitening and cracking occur. If it is more than 400%, the cosmetic sheet 1 is soft and lacks firmness, so it is difficult to handle, the productivity is poor, and the scratch resistance is also poor.

[0032] 〔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.

[0033] The transparent polyvinyl chloride resin layer 6 may contain a NOR type hindered amine light stabilizer (HALS) as a weathering agent. Since the NOR type HALS has low basicity, it can suppress the de-HCL reaction of the transparent polyvinyl chloride resin layer 6 and is effective against recent acid rain. Examples of the NOR type hindered amine light stabilizer (HALS) applicable to the transparent polyvinyl chloride resin layer 6 include "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.

[0034] Further, 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 a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber, and more preferably contains a cyanoacrylate-based ultraviolet absorber. The amount of the ultraviolet absorber added to 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.

[0035] (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.

[0036] (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, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

[0037] (Triazine-based ultraviolet absorber) Examples of the triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

[0038] (Cyanoacrylate-based ultraviolet absorber) 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.

[0039] 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 the unevenness 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.

[0040] [Heat stabilizer] The transparent polyvinyl chloride resin layer 6 preferably contains a metal salt of a higher fatty acid as a heat stabilizer.

[0041] (Surface protection layer) The surface protective layer 8 is a layer provided on the decorative sheet 1 to impart functions such as weather resistance, scratch resistance, stain resistance, and design. The material constituting the surface protective 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.

[0042] In the surface protective layer 8, an ultraviolet absorber and a light stabilizer are added as weathering agents to further improve the weather resistance of the decorative sheet 1. Further, various additives such as a heat stabilizer, an anti-blocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss regulator may be blended in the surface protective layer 8 as necessary. Hereinafter, an example of the surface protective layer 8 according to the present embodiment will be described with specific examples.

[0043] 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.

[0044] 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 suppression 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.

[0045] As the 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, etc. can be mentioned. Among these, those containing isomers may be each isomer alone and / or a mixture of each isomer.

[0046] Also, in the present embodiment, the surface protection layer 8 may be formed by coating a coating liquid containing an acrylic resin composition containing the above-described cyclohexyl (meth) acrylate as a monomer component and a weathering agent such as an ultraviolet absorber described later on the outermost surface of the decorative sheet. Although it will be described in detail later, for example, after coating a coating liquid containing the above-described acrylic resin composition and a weathering agent on the transparent polyvinyl chloride resin layer 6 having the uneven portions 10, the coating liquid may be wiped to embed the coating liquid in the uneven portions 10 to form the surface protection layer 8.

[0047] As a method for curing the coating liquid for forming the surface protection 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 cured 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 bonded to various base materials to form a decorative member is considered, the two-component curing type crosslinked by isocyanate curing is desirable.

[0048] 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.

[0049] 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. Further, 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 protective layer 8, which may not be preferable.

[0050] When the curing method of the coating liquid for forming the surface protective 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, and in addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth) acrylate may be blended.

[0051] In order to improve the fingerprint resistance of the cosmetic sheet 1, a silicone resin is added to the surface protective layer 8. As the silicone resin, an amino-modified silicone resin is preferable. Further, it is formed such that the contact angle of oleic acid on the surface of the surface protective layer 8 is 20° or more. By adjusting the addition amount of the silicone resin added to the surface protective layer 8, the contact angle of oleic acid can be adjusted. Further, when the surface protective layer 8 is provided with uneven portions, the contact angle of oleic acid can also be adjusted by adjusting the shape of the uneven portions.

[0052] (Ultraviolet absorber) As the ultraviolet absorber, for example, known ones such as benzotriazole-based, triazine-based (for example, hydroxyphenyltriazine-based), and benzophenone-based can be used. Among these, if a hydroxyphenyltriazine-based ultraviolet absorber is selected, the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically stable compared to the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers. etc., it becomes possible to maintain the ultraviolet absorption performance over a long period. That is, it is preferable that the surface protective layer 8 contains a triazine-based ultraviolet absorber as the ultraviolet absorber.

[0053] Examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and the like. In this embodiment, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter, 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."

[0054] In the surface protection 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 protection layer 8. By setting the addition amount of the above-mentioned ultraviolet absorber to 1 part by mass or more, the effect of improving weather resistance is exhibited, and by setting it to 30 parts by mass or less, the influence on physical properties other than the weather resistance of the surface protection layer 8 can be suppressed to a practically acceptable level.

[0055] In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber added to the surface protection 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 effect of improving weather resistance is exhibited, and by setting it to 20 parts by mass or less, the influence on physical properties other than the weather resistance of the surface protection layer 8 can be suppressed to a practically acceptable level.

[0056] In the present embodiment, by using ultraviolet absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter, conveniently referred to as "ultraviolet absorber B") in combination as the triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber in the surface protection layer 8, even more excellent weather resistance performance is imparted. 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 almost the same wavelength region, so that the wavelength region for absorbing ultraviolet rays becomes wider when used in 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".

[0057] In this 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 with respect to 100 parts by mass of the mass of the ultraviolet absorber B, 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. By setting the addition amount of the ultraviolet absorber A within the above numerical range, it is possible to impart more excellent weather resistance.

[0058] (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 performance 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-piperidino-ol / 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 - triazine - 6 - yl〕 - 1,5,8,12 - tetraazadodecane, 1,5,8,12 - tetrakis〔2,4 - bis(N - butyl - N - (1,2,2,6,6 - pentamethyl - 4 - piperidyl)amino) - s - triazine - 6 - yl〕 - 1,5,8 - 12 - tetraazadodecane, 1,6,11 - tris〔2,4 - bis(N - butyl - N - (2,2,6,6 - tetramethyl - 4 - piperidyl)amino) - s - triazine - 6 - yl〕aminoundecane, 1,6,11 - tris〔2,4 - bis(N - butyl - N - (1,2,2,6,6 - pentamethyl - 4 - piperidyl)amino) - s - triazine - 6 - yl〕aminoundecane, bis(1,2,2,6,6 - pentamethyl - 4 - piperidyl)[[3,5 - bis(1,1 - dimethylethyl) - 4 - hydroxyphenyl]methyl]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 with 2 - aminoethanol and the like can be mentioned, but it is not limited thereto.

[0059] In this embodiment, the addition amount of the light stabilizer (for example, a hindered amine - type radical scavenger) in the surface protective 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 protective 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, bleeding out of the weathering agent can be suppressed, and in addition, the influence on other physical properties of the surface protective layer 8 can be suppressed.

[0060] In addition, in this embodiment, the surface protection layer 8 is assumed to contain an ultraviolet absorber and a light stabilizer, but the present disclosure is not limited thereto. The surface protection layer 8 may be provided with desired weather resistance according to its use, and the surface protection layer 8 may be configured to contain at least one of an ultraviolet absorber and a light stabilizer.

[0061] (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 is preferable. If the coating amount is less than 3 g / m 2 less, good weather resistance cannot be obtained, and if it is 10 g / m 2 or more, there is a risk of inhibiting recyclability. By setting the coating amount within this range, it is possible to achieve both good weather resistance and recyclability. In addition, by setting the coating amount within this range, productivity and processability (for example, bend processability) can be improved.

[0062] (Uneven portion) As shown in FIG. 1, uneven portions 10 are provided on the outermost surface of the decorative sheet 1. By providing the uneven portions 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 uneven portions 10 can be formed into various uneven shapes such as wood grain conduit grooves, unevenness on the surface of a stone slab (such as a granite split surface), fabric surface texture, satin finish, sandblasted finish, hairline, and multi-line grooves, thereby imparting a given design property to the surface of the decorative sheet 1. The uneven portions 10 can be formed into various uneven shapes according to, for example, the design of the pattern layer 4 or the desired design property.

[0063] The uneven portions 10 are formed on the surface (outermost surface) side of the surface protection layer 8 that is the outermost layer of the decorative sheet 1 and constitute an uneven pattern. In this embodiment, the surface protection layer 8 described above is embedded in the uneven portions 10 that constitute this uneven pattern. Hereinafter, this point will be described.

[0064] In the cosmetic sheet 1 according to the present embodiment, the uneven portion 10 is provided in the transparent polyvinyl chloride resin layer 6. That is, the transparent polyvinyl chloride resin layer 6 is the layer in which the uneven portion 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 uneven portion 10 constituting 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 protective layer 8. With such a shape, when the surface protective layer composition (coating liquid) is embedded in the uneven portion 10 by wiping, the embedding becomes easy.

[0065] Further, the side surface forming the uneven portion 10 is preferably an inclined surface. If the side surface forming the uneven portion 10 is an inclined surface, when the surface protective layer composition (coating liquid) is embedded in the uneven portion 10 by wiping, the embedding becomes easy. Also, all of the side surfaces forming the uneven portion 10 may be covered with the surface protective layer 8.

[0066] Further, the depth of the uneven 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 uneven portion 10 is within the above numerical range, when the surface protective layer composition (coating liquid) is embedded in the uneven portion 10 by wiping, the embedding becomes easy, and peeling of the surface protective layer can be prevented.

[0067] Also, the width of the uneven 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 uneven portion 10 is within the above numerical range, when the surface protective layer composition (coating liquid) is embedded in the uneven portion 10 by wiping, the embedding becomes easy, and peeling of the surface protective layer embedded in the uneven portion 10 can be prevented.

[0068] Further, although it is preferable that the uneven portions 10 are 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 uneven portions 10 is preferably 10% or more. If the filling rate of the surface protective layer 8 with respect to the volume of the uneven portions 10 is 10% or more, the weather resistance in the uneven portions 10 can be improved. That is, if the filling rate of the surface protective layer 8 with respect to the volume of the uneven portions 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 uneven portions 10 is preferably 100%, it is more preferably 80% or less, and even more preferably 60% or less with respect to the volume of the uneven portions 10. If the filling rate of the surface protective layer 8 with respect to the volume of the uneven portions 10 is 80% or less, a sufficient tactile sensation can be obtained in the uneven portions 10.

[0069] Also, by setting the filling rate of the surface protective layer 8 with respect to the volume of the uneven portions 10 to 100%, the surface of the surface protective layer 8 filled in the uneven portions 10 and the surface of the transparent polyvinyl chloride resin layer 6 in the region without the uneven portions 10 may be flush, so to speak. Note that the uneven portions 10 are not necessarily provided. Instead, a matte adjustment layer may be provided.

[0070] (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 pattern layer 4, the transparent polyvinyl chloride resin layer 6, and 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. Moreover, when processing the decorative sheet 1, the sheet will lack stiffness 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. Thereby, for example, a decorative sheet 1 having concealability equivalent to that of a conventional decorative sheet formed using an olefin-based resin and good processability can be formed. Here, the total thickness of the decorative sheet 1 refers to, 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 pattern layer 4, the transparent polyvinyl chloride resin layer 6, and 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 refers to the thickness of the entire decorative sheet 1 obtained by adding the thickness of the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, the surface protective layer 8, and further the thickness of the concealment layer, that is, the thickness of the entire 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.

[0071] (Modification example) In the decorative sheet 1, the pattern of the pattern layer 4 and the uneven portion 10 may be synchronized.

[0072] Further, although the decorative sheet 1 includes the colored polyvinyl chloride resin layer 2, the colored polyvinyl chloride resin layer 2 does not necessarily have to be provided. That is, the decorative sheet 1 may be of a single-layer specification. When the decorative sheet 1 is of 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.

[0073] (Decorative member) As shown in Fig. 1, the decorative sheet 1 shown in Fig. 1 may be bonded to the base material 20 via the adhesive layer 12 to form the decorative member 50.

[0074] (Base material) As the base material 20, a wood base material or a metal base material can be used. As the wood 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. Further, 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. Further, the decorative member 50 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 can be reused, and the recyclability can be made better.

[0075] 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. Further, the base material 20 may have a structure subjected to bending processing or a three-dimensional structure. Note that the configuration of the decorative member 50 is not limited to the example shown in Fig. 1. That is, the configuration of the decorative member 50 may be a configuration including the 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.

[0076] When laminating the decorative sheet 1 on the base material 20, the adhesive layer 12 may be provided by laminating through an appropriately selected adhesive as necessary, or may be directly laminated 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 a hot melt type adhesive.

[0077] As a method of laminating and adhering 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 laminating method. In particular, when using a continuous laminating 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 50 that is densely cured and integrated can be continuously manufactured at high speed.

[0078] (Method for manufacturing decorative sheet and decorative member) Hereinafter, an example of a 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.

[0079] Next, a transparent polyvinyl chloride resin layer 6 is formed by thermal lamination on the colored polyvinyl chloride resin layer 2 on which the pattern layer 4 is formed. At the same time, an uneven pattern is provided on the surface of the transparent polyvinyl chloride resin layer 6 on the side opposite to the colored polyvinyl chloride resin layer 2 by embossing to form uneven portions 10.

[0080] 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 (uneven portions 10) is formed. Finally, this coating liquid is wiped so as to be embedded in the uneven portions 10, and the coating liquid is cured to form a surface protection layer 8 on the transparent polyvinyl chloride resin layer 6. In this way, the decorative sheet 1 according to the present embodiment is formed.

[0081] An adhesive is applied to the surface of the decorative sheet 1 formed in this way on the side of the colored polyvinyl chloride resin layer 2, and the base material 20 is attached. Thus, a decorative member 50 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 as long as they do not depart from the technical idea of the present invention even in forms other than this embodiment.

[0082] (Effect) (1) In the cosmetic sheet 1 according to the first embodiment, a silicon resin is added to the surface protective layer 8 so that the contact angle of oleic acid on the surface of the surface protective layer 8 is 20° or more. Therefore, fingerprint resistance can be imparted to the cosmetic sheet 1. Further, as a method of imparting fingerprint resistance, it is also conceivable to provide the uneven portions 10 in the surface protective layer 8. However, since fingerprint resistance can be imparted without providing the uneven portions 10, the cosmetic sheet 1 having a desired surface shape can be obtained without providing the uneven portions 10 or being restricted by the shape or the like of the uneven portions 10.

[0083] (2) By bonding the cosmetic sheet 1 to an exterior fitting member (base material 20), fingerprint resistance can be easily imparted to the fitting member.

[0084] (Modification) In the above embodiment, the case where a transparent polyvinyl chloride resin layer is used as the transparent resin layer has been described. However, an acrylic resin layer may be used as the transparent resin layer instead of the transparent polyvinyl chloride resin layer.

[0085] (Second Embodiment) Next, a second embodiment of the present invention will be described. The cosmetic sheet 100 according to the second embodiment is a cosmetic sheet mainly composed of an olefin resin.

[0086] (Configuration of Cosmetic Sheet) FIG. 2 is a cross-sectional view schematically showing an example of the cosmetic sheet 100 according to the second embodiment of the present invention. As shown in FIG. 2, the cosmetic sheet 100 includes a colored thermoplastic resin layer (colored base material layer) 51, a pattern layer 52, an anchor layer 53, a transparent adhesive resin layer 54, a transparent thermoplastic resin layer (transparent resin layer) 55, and a surface protective layer 56 in this order. Further, a primer layer 57 is provided on the surface of the colored thermoplastic resin layer 51 opposite to the pattern layer 52. Concavo-convex portions 110 are formed in the surface protective layer 56, which is the outermost layer of the cosmetic sheet 100, from the surface side to the transparent thermoplastic resin layer 55.

[0087] (Colored thermoplastic resin layer) The colored thermoplastic resin layer 51 has a function as a support of the decorative sheet 100, is colored opaquely and has concealability. Thereby, when the decorative sheet 100 is bonded to an adherend such as a window frame, the colored thermoplastic resin layer 51 can conceal color variations, defects, etc. on the surface of the adherend. As the colored thermoplastic resin layer 51, for example, a polyolefin-based thermoplastic resin can be used.

[0088] As the polyolefin-based resin, a polypropylene-based resin, that is, a homopolymer or copolymer having propylene as a main component can be used. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, etc. can be used alone or in appropriate combination, or a resin obtained by further appropriately blending atactic polypropylene with them can be used. Further, a copolymer containing an olefin-based monomer other than propylene may be used. For example, a copolymer having a polypropylene crystal part and containing 15 mol% or more of one or more comonomers of α-olefins having 2 to 20 carbon atoms other than propylene, preferably ethylene, butene-1, 4-methylpentene-1, hexene-1 or octene-1 can be exemplified. Further, modifiers such as low-density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, styrene-butadiene copolymer or its hydrogenated product, which are usually used for softening polypropylene-based resins, can be appropriately added.

[0089] Furthermore, to the colored thermoplastic resin layer 51, if necessary, for example, one or more additives selected from various additives such as 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.

[0090] (Pattern layer) The pattern layer 52 is provided as needed to impart design properties due to the pattern to the decorative sheet 100. When the pattern layer 52 can be substituted by the coloring of the colored thermoplastic resin layer 51, it can be omitted. The pattern layer 52 is formed using a printing ink or paint obtained by dissolving or dispersing a colorant such as a dye or pigment in a suitable diluting solvent together with a suitable binder resin. The printing ink or paint is applied by various printing methods such as a gravure printing method or an offset printing method, or various coating methods such as a gravure coating method or a roll coating method. As the binder resin, for example, a urethane resin, an acrylic resin, a vinyl chloride acetate resin, a polyimide resin, nitrocellulose, or the like, or a mixture thereof can be used, and a urethane resin is particularly preferable. As the pattern, 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 of two or more of these can be used. Further, in order to improve the concealability of the decorative sheet 100, a concealment layer made of an opaque printing ink or paint containing a large amount of an opaque pigment such as titanium dioxide or iron oxide may be provided between the pattern layer 52 and the colored thermoplastic resin layer 51.

[0091] (Anchor layer) The anchor layer 53 is provided as needed to improve the adhesion to the transparent adhesive resin layer 54 used for adhesion to the colored thermoplastic resin layer 51. The anchor layer 53 contains a urethane resin as the binder resin.

[0092] (Transparent adhesive resin layer) The transparent adhesive resin layer 54 is provided as needed to bond the colored thermoplastic resin layer 51 and the transparent thermoplastic resin layer 55. The transparent adhesive resin layer 54 can be omitted when the adhesiveness of other layers can be utilized. The transparent adhesive resin layer 54 is formed using an adhesive. As the adhesive, for example, a non-halogen-based thermoplastic resin can be used. In particular, from the viewpoints of various physical properties, processability, versatility, economy, etc., it is desirable to use a polyolefin-based resin or a polyester-based resin as the non-halogen-based thermoplastic resin.

[0093] In addition, in order to formulate the transparent adhesive resin layer 54 to have weather resistance, a triazine-based ultraviolet absorber is added. The ratio of the triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 1% by mass or less with respect to the total mass of the transparent adhesive resin layer 54. More preferably, it is 0.2% by mass or more and 0.7% by mass or less. If it is less than 0.1% by mass, there is a problem that the ultraviolet absorption performance deteriorates. Also, if it is more than 1% by mass, there is a problem of precipitation such as bleed-out.

[0094] In addition, in the surface protection layer 56 described later, a hindered amine-based light radical scavenger is added in order to trap harmful radicals and prevent the resin itself from deteriorating due to light, heat, water, etc. The ratio of the hindered amine-based light radical scavenger is preferably 0.1% by mass or more and 1% by mass or less with respect to the total mass of the transparent adhesive resin layer 54. More preferably, it is 0.2% by mass or more and 0.7% by mass or less. If it is less than 0.1% by mass, there is a problem that radical trapping is insufficient and the resin itself is likely to deteriorate. Also, if it is more than 1% by mass, there is a problem of precipitation such as bleed-out.

[0095] (Transparent thermoplastic resin layer) The transparent thermoplastic resin layer 55 can be made of, for example, a polyolefin-based thermoplastic resin, similarly to the colored thermoplastic resin layer 51.

[0096] As the polyolefin resin, a polypropylene resin, that is, a homopolymer or copolymer mainly composed of propylene can be used. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, etc. can be used alone or in appropriate combination, or a resin obtained by appropriately blending atactic polypropylene with them can be used. Further, it may be a copolymer containing an olefin monomer other than propylene. For example, a copolymer having a polypropylene crystal part and containing 15 mol% or more of one or more comonomers of α-olefins having 2 to 20 carbon atoms other than propylene, preferably ethylene, butene-1, 4-methylpentene-1, hexene-1 or octene-1, such as a propylene-α-olefin copolymer, can be exemplified. In addition, modifiers such as low-density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, styrene-butadiene copolymer or its hydrogenated product, which are usually used for softening polypropylene resins, can be appropriately added.

[0097] In addition, a triazine-based ultraviolet absorber is added to the transparent thermoplastic resin layer 55 in order to formulate weather resistance. The ratio of the triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 1% by mass or less with respect to the total mass of the transparent thermoplastic resin layer 55. More preferably, it is 0.2% by mass or more and 0.7% by mass or less. Examples of the triazine-based ultraviolet absorber 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-dip enyl-[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, etc., and mixtures, modified products, polymers, and derivatives thereof can be employed.

[0098] Furthermore, in the transparent thermoplastic resin layer 55, a hindered amine-based light radical scavenger (i.e., "hindered amine-based light stabilizer") is added to trap radicals induced by light energy or radicals induced by thermal energy converted from light energy by an ultraviolet absorber, thereby preventing the deterioration of the resin itself. The ratio of the hindered amine-based light radical scavenger is preferably 0.1% by mass or more and 1% by mass or less based on the total mass of the transparent thermoplastic resin layer 132. More preferably, it is 0.2% by mass or more and 0.7% by mass or less. If it is less than 0.1% by mass, there is a problem that radical trapping is insufficient and the resin itself is likely to deteriorate. Also, if it is more than 1% by mass, there is a problem of precipitation such as bleed-out. Examples of the hindered amine-based light stabilizer include 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 and other hindered amine compounds, mixtures, modified products, polymers, derivatives, etc. thereof can be adopted.,

[0099] (Surface protective layer) As the material of the surface protective layer 56, when the decorative member 150 described later including the decorative sheet 100 is used as the exterior material, abrasion resistance, weather resistance, durability, etc. are required. For example, acrylic urethane resins and radiation-curable resins can be used. As the acrylic urethane resin, for example, a reaction product mainly composed of an acrylic polyol compound and an isocyanate compound as a curing agent can be used. As the acrylic polyol compound, for example, normal acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, etc., monomers containing a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, etc., and copolymerizable polymerizable monomers such as styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl butyrate, vinyl versatate, ethyl vinyl ether, acrylonitrile, methacrylonitrile, etc. can be blended and copolymerized to obtain an acrylic polymer compound having a hydroxyl group in the side chain can be adopted.,

[0100] In addition, as the isocyanate compound, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc. can be used. In particular, when the cosmetic member 150 is used as an exterior member of the exterior, weather resistance is required for the surface protective layer 56. Considering weather resistance, a non-yellowing type isocyanate compound having no aromatic ring, that is, an aliphatic or alicyclic isocyanate compound is preferable.

[0101] In addition, as the radiation-curable resin, for example, a composition mainly composed of at least any one of a prepolymer, an oligomer, and a monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group having a property of undergoing a crosslinking reaction by irradiation with radiation can be used. As the radiation, for example, an electron beam or ultraviolet rays can be used. Additives such as a polymerization initiator and a sensitizer may be added to the radiation-curable resin as necessary.

[0102] Examples of prepolymers and oligomers having a polymerizable unsaturated bond include melamine (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polyol (meth)acrylate, and the like. Examples of monomers include monofunctional monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and the like, bifunctional monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, and the like, and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.

[0103] The thickness of the surface protection layer 56 is not particularly limited, but if it is too thin, the effect will be poor, and if it is too thick, the flexibility will decrease and it will be easily cracked. Therefore, for example, it is preferably 1 μm or more and 20 μm or less. The surface protection layer 56 preferably has transparency that allows the surface of the transparent thermoplastic resin layer 55 disposed on one surface of the surface protection layer 56 to be seen through. For example, it is colorless and transparent, colored and transparent, or translucent.

[0104] In addition, a triazine-based ultraviolet absorber is added to the surface protection layer 56 in order to formulate weather resistance. The ratio of the triazine-based ultraviolet absorber is preferably 5% by mass or more and 20% by mass or less based on the total mass of the surface protection layer 56. More preferably, it is 6% by mass or more and 10% by mass or less. If it is less than 5% by mass, there is a problem that the ultraviolet absorption performance deteriorates. Also, if it is more than 20% by mass, there is a problem of precipitation such as bleed-out. Further, a hindered amine-based light radical scavenger is added to the surface protection layer 56 in order to capture harmful radicals and prevent deterioration of the resin itself due to light, heat, water, etc. The ratio of the hindered amine-based light radical scavenger is preferably 2.5% by mass or more and 10% by mass or less based on the total mass of the surface protection layer 56. More preferably, it is 3% by mass or more and 7% by mass or less. If it is less than 2.5% by mass, there is a problem that the radical scavenging performance is poor and the resin itself is likely to deteriorate. Also, if it is more than 10% by mass, there is a problem of precipitation such as bleed-out. Further, in order to further improve the weather resistance of the decorative sheet 100, a light stabilizer is added to the surface protection layer 56 as a weathering agent. As the light stabilizer, the same one as that of the surface protection layer 8 can be applied.

[0105] Furthermore, in order to improve the fingerprint resistance of the decorative sheet 100, a silicone resin is added to the surface protection layer 56. As the silicone resin, an amino-modified silicone resin is preferable. Also, the surface protection layer 56 is formed such that the contact angle of oleic acid on its surface is 20° or more. By adjusting the addition amount of the silicone resin added to the surface protection layer 56, the contact angle of oleic acid can be adjusted. Also, when the surface protection layer 56 is provided with uneven portions, the contact angle of oleic acid can also be adjusted by adjusting the shape of the uneven portions.

[0106] (Uneven portions) On the outermost surface of the decorative sheet 100, that is, on the surface of the surface protection layer 56, uneven portions 110 formed by embossing are provided. As the uneven portions 110, for example, patterns synchronized with the pattern of the pattern layer 52 and patterns not synchronized with the pattern can be used.

[0107] Note that the concavo-convex portion 110 is not necessarily provided. Instead, a gloss adjustment layer may be provided.

[0108] (Primer layer) The primer layer 57 is provided as necessary to improve the adhesion to the adhesive layer 59 used for adhesion to the base material 60 described later. As the material of the primer layer 57, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, etc. can be used. In particular, a two-component curable urethane-based primer agent obtained by blending polyester polyol and polyisocyanate is preferable. Further, for example, adding inorganic powders such as silica, barium sulfate, and calcium carbonate is effective in preventing blocking during winding storage and improving the adhesive strength due to the anchoring effect.

[0109] (Total thickness of the decorative sheet) The total thickness of the decorative sheet 100 is preferably 40 μm or more and 300 μm or less.

[0110] (Modified example) In the decorative sheet 100, the pattern of the pattern layer 52 and the concavo-convex portion 110 may be synchronized. Further, the decorative sheet 100 includes the colored thermoplastic resin layer 51, but the colored thermoplastic resin layer 51 is not necessarily provided, that is, the decorative sheet 100 may be a single-layer specification. When the decorative sheet 100 is a single-layer specification, it is preferable to provide a concealment layer (not shown) on the surface opposite to the transparent thermoplastic resin layer 55 of the pattern layer 52.

[0111] (Decorative member) As shown in FIG. 2, the decorative sheet 100 may be bonded to the base material 60 via the adhesive layer 59 to form the decorative member 150.

[0112] (Base material) As the material of the base material 60, for example, a metallic material can be used. As the metallic material, for example, a steel plate, a brass plate, an aluminum plate, a duralumin plate, or a stainless steel plate can be adopted. By using the metallic material, an exterior material that can be used for the exterior can be provided. Between the base material 60 and the decorative sheet 100, an adhesive layer, for example, may be provided as necessary.

[0113] (Manufacturing Method of Decorative Sheet and Decorative Member) Hereinafter, an example of the manufacturing method of the decorative sheet 100 according to the present embodiment will be briefly described.

[0114] For example, as the colored thermoplastic resin layer 51, a pattern layer 52 is formed on one surface of a sheet of colored polyethylene resin (PE). Subsequently, an anchor layer 53 is formed on the surface of the pattern layer 52, and the resin for the transparent thermoplastic resin layer 55 and the resin for the transparent adhesive resin layer 54 are laminated on the anchor layer 53 using a co-extrusion lamination method. At this time, the transparent adhesive resin layer 54 and the transparent thermoplastic resin layer 55 are laminated on the anchor layer 53 in this order, and at the same time, an uneven pattern is provided on the surface of the transparent thermoplastic resin layer 55 on the side opposite to the transparent adhesive resin layer 54 by embossing to form uneven portions 110. Then, a resin for the surface protection layer 56 is applied to the surface of the transparent thermoplastic resin layer 55 to form the surface protection layer 56. Further, a primer is applied to the surface of the colored thermoplastic resin layer 51 on the side opposite to the surface protection layer 56 to form a primer layer 57, and the decorative sheet 100 is formed.

[0115] Then, an adhesive layer 59 is applied to the surface of the primer layer 57, and the base material 60 is attached, whereby a decorative member 150 in which the decorative sheet 100 and the base material 60 are bonded via the 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, and various modifications can be made according to the design and the like as long as they do not depart from the technical idea of the present invention in forms other than this embodiment.

[0116] (Effect) (1) The cosmetic sheet 100 according to the second embodiment has a silicon resin added to the surface protection layer 56 so that the contact angle of oleic acid on the surface of the surface protection layer 56 is 20° or more. Therefore, fingerprint resistance can be imparted to the cosmetic sheet 100. Further, as a method of imparting fingerprint resistance, it is also conceivable to provide the uneven portions 110 on the surface protection layer 56. However, since fingerprint resistance can be imparted without providing the uneven portions 110, the cosmetic sheet 1 having a desired surface shape can be obtained without providing the uneven portions 110 or being restricted by the shape or the like of the uneven portions 110.

[0117] (2) By bonding the cosmetic sheet 100 to an exterior fitting member (base material 60), fingerprint resistance can be easily imparted to the fitting member. Note that the cosmetic sheet according to the present embodiment does not necessarily need to be provided with all the layers shown in FIG. 1 or FIG. 2, and any cosmetic sheet having a surface protection layer can be applied.

Example

[0118] Hereinafter, 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. An evaluation cosmetic sheet mainly composed of a vinyl chloride resin (acrylic resin) in Embodiment 1 and an evaluation cosmetic sheet mainly composed of an olefin resin in Embodiment 2 were prepared and evaluated.

[0119] (Evaluation cosmetic sheet mainly composed of vinyl chloride resin (acrylic resin)) The evaluation cosmetic sheet mainly composed of a vinyl chloride resin was prepared by the following procedure.

[0120] A colored polyvinyl chloride resin sheet was used as the 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 a transparent resin layer was subjected to doubling embossing and heat lamination on the pattern layer. And as a surface protective layer, a resin composition mainly composed of an acrylic resin composition was laminated on the transparent polyvinyl chloride sheet.

[0121] Thereby, a decorative sheet for evaluation mainly composed of a vinyl chloride-based resin was obtained. In the case of preparing a decorative sheet for evaluation mainly composed of an acrylic resin, as the transparent resin layer, instead of the transparent polyvinyl chloride sheet, an acrylic resin may be used to form the transparent resin layer.

[0122] The formulation of each layer is as follows. (Colored polyvinyl chloride resin sheet) Material: Polyvinyl chloride resin (PVC) Thickness: 80 μm (Transparent polyvinyl chloride resin sheet) Material: Polyvinyl chloride resin (PVC) Thickness: 80 μm Ultraviolet absorber: 0.5 part by mass of a triazine-based ultraviolet absorber HALS: 0.5 part by mass of NOR type (manufactured by ADEKA Corporation, Adeka Stab LA81) (pattern layer) Binder resin: A mixture of a vinyl chloride resin-vinyl acetate resin copolymer resin and an acrylic resin (Surface protective layer) Main agent: 90 parts by mass of methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) Ultraviolet absorber: 9 parts by mass of Tinuvin 479 manufactured by BASF Japan Ltd. Light stabilizer: 1 part by mass of Tinuvin 123 manufactured by BASF Japan Ltd. Amino-modified silicone additive (amino-modified silicone resin / solvent = 10 / 90) 5 parts by mass Curing agent: 10 parts by mass of Takenate D170 manufactured by Mitsui Chemicals, Inc. Solvent: 240 parts by mass of ethyl acetate Coating amount: 3 g / m 2 (Evaluation cosmetic sheet mainly composed of olefin resin) The evaluation cosmetic sheet mainly composed of olefin resin was prepared by the following procedure.

[0123] As the colored base material layer, a layer made of a colored thermoplastic resin was formed with a thickness of 70 μm. A pattern layer was printed on one surface of the colored thermoplastic resin layer, and a primer layer was printed on the other surface of the colored thermoplastic resin layer.

[0124] Next, an anchor layer was coated on the surface of the pattern layer opposite to the colored thermoplastic resin layer, and a laminate was formed by laminating an extruded product of a transparent adhesive resin layer and a transparent thermoplastic resin layer as a transparent resin layer on this anchor layer. At this time, an uneven pattern was provided by embossing on the surface of the transparent thermoplastic resin layer opposite to the transparent adhesive resin layer to form uneven portions. Further, a surface protective layer was coated on the transparent thermoplastic resin layer.

[0125] Thereby, an evaluation cosmetic sheet mainly composed of olefin resin was obtained. The composition of each layer is as follows. (Colored thermoplastic resin layer) Material: Polypropylene resin Thickness: 70 μm (Transparent thermoplastic resin layer) Material: Polypropylene resin Thickness: 70 μm (Pattern ink layer, primer layer, anchor layer) Binder resin: Urethane resin (Surface protective layer) It is the same as the surface protective layer of the "evaluation cosmetic sheet mainly composed of vinyl chloride resin".

[0126] (Evaluation cosmetic sheets of Examples and Comparative Examples) (Example 1) As the material of the transparent resin layer, polypropylene resin (PP) was used, and a silicone resin was added to the surface protective layer. The shape of the uneven portions was a matte finish. (Example 2) Polypropylene resin (PP) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a wood grain pattern. (Example 3) Polyvinyl chloride resin (PVC) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a wood grain pattern. (Example 4) Polyvinyl chloride resin (PVC) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a satin finish. (Example 5) Acrylic resin (PMMA) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a satin finish. (Example 6) Acrylic resin (PMMA) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a wood grain pattern. (Example 7) Polyvinyl chloride resin (PVC) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a wood grain pattern. (Example 8) Polypropylene resin (PP) was used as the material for the transparent resin layer, and silicone resin was added to the surface protection layer. The shape of the uneven portion was made to have a satin finish. (Comparative Example 1) Polypropylene resin (PP) was used as the material for the transparent resin layer. Silicone resin was not added to the surface protection layer. The shape of the uneven portion was made to have a satin finish. (Comparative Example 2) Polypropylene resin (PP) was used as the material for the transparent resin layer. Silicone resin was not added to the surface protection layer. The shape of the uneven portion was made to have a wood grain pattern. (Comparative Example 3) Polyvinyl chloride resin (PVC) was used as the material for the transparent resin layer. Silicone resin was not added to the surface protection layer. The shape of the uneven portion was made to have a satin finish. (Comparative Example 4) As the material of the transparent resin layer, polyvinyl chloride resin (PVC) was used. Silicon resin was not added to the surface protective layer. The shape of the uneven portion was made into a matte finish. (Comparative Example 5) As the material of the transparent resin layer, acrylic resin (PMMA) was used, and silicon resin was not added to the surface protective layer. The shape of the uneven portion was made into a matte finish.

[0127] 〔Evaluation〕 For each of the decorative sheets for evaluation of the examples and comparative examples, the contact angle of oleic acid was measured, and further a fingerprint resistance test was conducted.

[0128] (Contact Angle of Oleic Acid) 2 μL of oleic acid was dropped onto the surface of the decorative sheet for evaluation, and the contact angle after 3 seconds was measured.

[0129] (Fingerprint Resistance Test) (1) 0.01 g of lecithin (emulsifier) was mixed with 1.0 g of oleic acid, and 1.0 g of peptone (protein) kneaded with 0.4 g of water was mixed therewith, and this was used as the coating agent for the fingerprint resistance test. (2) The 60° gloss value of the surface of the decorative sheet was measured. The measurement of the gloss value was performed using a gloss meter (Micro Gloss manufactured by BYK). (3) The mixture prepared in the procedure of (1) was applied to the surface of the decorative sheet, allowed to stand for 1 minute, and then the applied coating agent for the fingerprint resistance test was wiped off with a dry cloth. (4) Again, the 60° gloss value of the surface of the decorative sheet was measured. (5) The rate of change between the gloss value measured in (2) and the gloss value measured in (4) was calculated. (6) Also, together with the measurement of the gloss value, the color difference ΔE of the surface of each decorative sheet for evaluation was determined in the state before applying the coating agent for the fingerprint resistance test and the state after wiping off the applied coating agent for the fingerprint resistance test. The measurement of the color difference ΔE was performed using a color difference meter CR-400 (manufactured by KONICA MINOLTA).

[0130] The evaluation criteria for the rate of change between the gloss value measured in (2) and the gloss value measured in (4), and the color difference ΔE are as follows. Pass is indicated by "○" or "◎". ◎: The rate of change of the gloss value is less than 40%, and the color difference ΔE is less than 0.9 ○: The rate of change of the gloss value is less than 40%, and the color difference ΔE is 0.9 or more ×: The rate of change of the gloss value is 40% or more The evaluation results of each of the above evaluation items are shown in Table 1.

[0131]

Table 1

[0132] As shown in Table 1, as the contact angle of oleic acid increases, the rate of change of the gloss value and the color difference ΔE tend to decrease slightly. When the contact angle of oleic acid is 20° or more, the rate of change of the gloss value is less than 40%, and the color difference ΔE is less than 1.1, and fingerprint resistance can be obtained. When the contact angle of oleic acid is about 30° or more, it was confirmed that the rate of change of the gloss value is less than 40% and the color difference ΔE is less than 0.9, and better fingerprint resistance can be obtained. That is, by adding a silicone resin to the surface protection layer and setting the contact angle of oleic acid to 20° or more, it was confirmed that the change in the gloss of the surfaces of the decorative sheets 1 and 100 due to the adhesion of fingerprints can be suppressed, and the fingerprint resistance is improved.

[0133] Incidentally, the present invention can have, for example, the following configurations. (1) Having a surface protection layer on the outermost layer, The decorative sheet, wherein the surface protection layer contains a silicone resin and the contact angle of oleic acid on the surface of the surface protection layer is 20° or more. (2) The decorative sheet according to (1) above, wherein the silicone resin is an amino-modified silicone resin. (3) The surface protective layer is characterized in that when a test coating agent is applied to the surface of the surface protective layer and then wiped off, the change rate of gloss value between the state before applying the coating agent and the state after wiping off the coating agent is less than 40%. The cosmetic sheet according to (1) or (2) above. (4) The surface protective layer is characterized in that when a test coating agent is applied to the surface of the surface protective layer and then wiped off, the color difference ΔE between the state before applying the coating agent and the state after wiping off the coating agent is less than 0.9. The cosmetic sheet according to (3) above. (5) The surface protective layer contains an ultraviolet absorber and a light stabilizer. The cosmetic sheet according to any one of (1) to (4) above. (6) It includes a pattern layer, a transparent resin layer, and the surface protective layer in this order. The transparent resin layer contains an olefin-based resin, a vinyl chloride-based resin, or an acrylic-based resin as a main component. The cosmetic sheet according to any one of (1) to (5) above. (7) The surface protective layer is provided with concavo-convex portions or a gloss adjustment layer that synchronizes with the pattern of the pattern layer. The cosmetic sheet according to (6) above. (8) The transparent resin layer contains an ultraviolet absorber and a light stabilizer. The cosmetic sheet according to (6) or (7) above. (9) A colored base material layer is provided on the side of the pattern layer opposite to the transparent resin layer. The cosmetic sheet according to any one of (6) to (8) above. (10) It includes a colored polyvinyl chloride resin layer as the colored base material layer, the pattern layer, a transparent polyvinyl chloride resin layer or an acrylic resin layer as the transparent resin layer, and the surface protective layer in this order. The cosmetic sheet according to (9) above. (11) A decorative sheet according to (9) above, characterized in that it comprises, in this order, a colored thermoplastic resin layer as the colored base material layer, the pattern layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer as the transparent resin layer, and the surface protective layer. (12) The decorative sheet according to any one of (1) to (11) above, and a base material disposed on the outermost surface of the decorative sheet on the side opposite to the surface protective layer, characterized in that it comprises a decorative member.

Explanation of reference numerals

[0134] 1, 100 Decorative sheet 2 Colored polyvinyl chloride resin layer (colored base material layer) 4, 52 Pattern layer 6 Transparent polyvinyl chloride resin layer (transparent resin layer) 8, 56 Surface protective layer 10, 110 Concavo-convex portion 12, 59 Adhesive layer 20, 60 Base material 50, 150 Decorative member 51 Colored thermoplastic resin layer (colored base material layer) 55 Transparent thermoplastic resin layer (transparent resin layer)

Claims

1. It has a surface protection layer on the outermost surface, The decorative sheet, wherein the surface protective layer contains a silicone resin, and the contact angle of oleic acid on the surface of the surface protective layer is 20° or more.

2. 2. The decorative sheet according to claim 1, wherein the silicone resin is an amino-modified silicone resin.

3. The decorative sheet according to claim 1 or 2, characterized in that when a test coating agent is applied to the surface of the surface protective layer and then the coating agent is wiped off, the gloss value change rate between the state before the coating agent is applied and the state after the coating agent is wiped off is less than 40%.

4. The decorative sheet according to claim 3, characterized in that, when a test coating agent is applied to the surface of the surface protective layer and then the coating agent is wiped off, the color difference ΔE between the state before the coating agent is applied and the state after the coating agent is wiped off is less than 0.

9.

5. 3. The decorative sheet according to claim 1, wherein the surface protective layer contains an ultraviolet absorbing agent and a light stabilizer.

6. A design layer, a transparent resin layer, and the surface protective layer are provided in this order, 3. The decorative sheet according to claim 1, wherein the transparent resin layer contains an olefin resin, a vinyl chloride resin, or an acrylic resin as a main component.

7. The decorative sheet according to claim 6, characterized in that said surface protective layer is provided with an uneven portion or a gloss adjusting layer that matches the pattern of said pattern layer.

8. 7. The decorative sheet according to claim 6, wherein the transparent resin layer contains an ultraviolet absorbing agent and a light stabilizer.

9. The decorative sheet according to claim 6, further comprising a colored base layer on the opposite side of the design layer from the transparent resin layer.

10. 10. The decorative sheet according to claim 9, comprising, in this order, a colored polyvinyl chloride resin layer as the colored base material layer, the design layer, a transparent polyvinyl chloride resin layer or an acrylic resin layer as the transparent resin layer, and the surface protective layer.

11. The decorative sheet according to claim 9, characterized in that it comprises, in this order, a colored thermoplastic resin layer as the colored base material layer, the pattern layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer as the transparent resin layer, and the surface protective layer.

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

Images