JP2025097255A - Decorative sheets and decorative members - Google Patents

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

The present invention relates to decorative sheets and decorative members.

Decorative sheets are used on the surfaces of entrance doors, frames, fittings, furniture, etc., and are touched by many people. Touching them with hands can cause sebum to adhere to the surface of the decorative sheet, making fingerprints noticeable and changing the gloss, which can damage the appearance of the decorative sheet. Fingerprints are particularly noticeable on decorative sheets with dark patterns or low gloss.
As a countermeasure to this, it has been proposed to provide the surface of a decorative sheet with a specific uneven shape to impart fingerprint resistance to the decorative sheet (see, for example, Patent Document 1).

JP 2020-55108 A

Although the method of providing the surface of the decorative sheet with an uneven shape can impart fingerprint resistance, it is necessary to provide the uneven shape, and there are restrictions on the shape.
The present invention has been made in consideration of the above-mentioned points, and has an object to provide a decorative sheet and decorative member that are excellent in fingerprint resistance without being restricted by uneven shapes.

A decorative sheet according to one embodiment of the present invention is characterized in that it has a surface protective layer as an 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, a decorative member according to another aspect of the present invention is characterized by comprising the decorative sheet of the above-mentioned aspect and a substrate arranged on the outermost surface of the decorative sheet opposite the surface protective layer.

According to one aspect of the present invention, a decorative sheet and a decorative member having excellent fingerprint resistance can be obtained.

1 is a cross-sectional view showing a schematic example of a decorative sheet and a decorative member according to a first embodiment of the present invention. FIG. 4 is a cross-sectional view showing an example of a decorative sheet and a decorative member according to a second embodiment of the present invention.

Hereinafter, embodiments of the present technology will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. are different from the actual ones. As long as it is within the scope of the present disclosure, it is not necessary to stack in the order shown in the drawings. In addition, layers not shown in the drawings may be added. In addition, the embodiments shown below are examples of configurations for embodying the technical idea of the present disclosure, and the technical idea of the present disclosure is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of the present disclosure can be modified in various ways within the technical scope defined by the claims described in the claims.

In addition, the directions of "left and right" and "up and down" in the following explanation are merely defined for the convenience of explanation and do not limit the technical ideas of this disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and of course, if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left."

First Embodiment
First, a first embodiment of the present invention will be described.
The decorative sheet 1 according to the first embodiment is a decorative sheet containing a vinyl chloride resin as a main component.

(Configuration of decorative sheet)
FIG. 1 is a cross-sectional view that illustrates an example of a decorative sheet 1 according to a first embodiment of the present invention.
As shown in Fig. 1, the decorative sheet 1 comprises, in this order, a colored polyvinyl chloride resin layer (colored substrate layer) 2, a design layer 4, a transparent polyvinyl chloride resin layer (transparent resin layer) 6, and a surface protective layer 8. The surface protective layer 8, which is the outermost layer of the decorative sheet 1, has an uneven portion 10 formed from the surface side toward the transparent polyvinyl chloride resin layer 6.

(Colored polyvinyl chloride resin layer)
The colored polyvinyl chloride resin layer 2 functions as a support for the decorative sheet 1, and is colored opaquely to have concealing properties, which allows the colored polyvinyl chloride resin layer 2 to conceal color variations and defects on the surface of an adherend when the decorative sheet 1 is attached to an adherend such as a window frame.

The colored polyvinyl chloride resin layer 2 is formed, for example, from a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and further has printability.
Furthermore, the hue of the opaquely colored colored polyvinyl chloride resin layer 2 can be appropriately selected as the base color of the pattern layer 4. Furthermore, when utilizing the texture of the surface of the adherend, the colored polyvinyl chloride resin layer 2 preferably has a transparency to such an extent that the surface of the adherend can be seen through when viewed from the surface protective layer 8 side.

The colored polyvinyl chloride resin layer 2 can be obtained, for example, by mixing or kneading a coloring agent such as a pigment into polyvinyl chloride resin. As the coloring agent, organic or inorganic pigments can be used, but it is preferable to use inorganic pigments. In other words, it is preferable that the colored polyvinyl chloride resin layer 2 contains an inorganic substance as a coloring agent. For example, it is preferable that the colored polyvinyl chloride resin layer 2 contains one or more inorganic substances selected from calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

In addition, the colored polyvinyl chloride resin layer 2 may contain, as 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 adjusters.
Further, in the above description, the colored polyvinyl chloride resin layer 2 is provided as the colored substrate layer, but the colored substrate layer is not limited to polyvinyl chloride resin.

(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 to impart design properties to the decorative sheet 1.

The pattern layer 4 is formed using printing ink or paint. The printing ink or paint that forms the pattern layer 4 is formed by dissolving or dispersing a colorant such as a dye or pigment together with a suitable binder resin in a suitable dilution solvent. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

The printing ink or paint forming the design layer 4 is applied by using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
The binder resin contained in the design layer 4 is not particularly limited, but it is preferable to use a resin with good adhesion. That is, a resin having thermal adhesion to polyvinyl chloride resin, such as a vinyl chloride-vinyl acetate copolymer, an acrylic resin alone, or a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin, is preferable.

The pattern formed by the pattern layer 4 can be any pattern, such as a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, letters, symbols, a solid color, or a combination of these. In order to improve the concealment of the decorative sheet 1, a concealment layer may be provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2. The concealment layer is formed, for example, using an opaque printing ink or paint that contains a large amount of opaque pigments such as titanium dioxide or iron oxide.

It is preferable that the thickness of the pattern layer 4 is within 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, it is possible to make the printing clear. Also, when the thickness of the pattern layer 4 is 10 μm or less, it is possible to improve the printing workability when manufacturing the decorative sheet 1 and to reduce manufacturing costs.

In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, hardeners, hardening accelerators, and hardening retarders may be added to the design layer 4 in order to impart various functions.
In addition, the pattern layer 4 may be configured to have, for example, a solid colored polyvinyl chloride layer to conceal the color and pattern of the substrate to which the decorative sheet 1 is attached, and a pattern layer for adding a pattern to impart design appeal.

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

The transparent polyvinyl chloride resin layer 6 is preferably transparent enough to allow the pattern layer 4 provided on the surface of the colored polyvinyl chloride resin layer 2 (the lower surface in FIG. 1) to be seen through from the surface protection layer 8. The transparent polyvinyl chloride resin layer 6 is preferably, for example, colorless and transparent, colored and transparent, or translucent.

The resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less. In terms of the K value calculated in accordance with JIS K7367-2:1999, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having a K value of 60 or more and 75 or less.

The higher the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6, the stronger, easier to stretch, less likely to crack, and more durable the decorative sheet 1 will be. If the average degree of polymerization is too high, the gelling temperature will be high, causing fish eyes and the like, making it difficult to form the transparent polyvinyl chloride resin layer 6. For this reason, it is preferable that the resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin with an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500. In addition, if the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is 800 to 1500, the breaking elongation of the decorative sheet 1 at 0°C will be 10% to 400%, and production stability during processing such as wrapping will be good. If the breaking elongation at 0°C is less than 10%, the decorative sheet 1 will be hard, and whitening and cracking may occur. If the breaking elongation at 0°C is greater than 400%, the decorative sheet 1 will be soft and have no stiffness, making it difficult to handle, resulting in poor productivity and poor scratch resistance.

Similarly, when the K value of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is within the range of 60 to 75, the breaking elongation of the decorative sheet 1 at 0°C is 10% to 400%, and when the K value is less than 60 or greater than 75, the breaking elongation of the decorative sheet 1 at 0°C is less than 10% or greater than 400%.

A plasticizer may also be added to the transparent polyvinyl chloride resin layer 6. As the plasticizer, a high molecular weight polyester resin is preferred, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. In terms of viscosity, the viscosity of the plasticizer measured by a capillary viscometer in accordance with JIS K7367-5:2000 is preferably 500 MPa·s or more and 3000 MPa·s or less.

As a plasticizer, among polyester resins, high molecular weight polyesters are preferred. Phthalic acid resins (dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more prone to bleeding out than high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance.

If the plasticizer content is less than 20 PHR, cold resistance will be poor even if a phthalic acid resin is used, so if a high molecular weight polyester resin is used as the plasticizer, the plasticizer content is preferably 20 PHR or more. If the plasticizer content is more than 30 PHR, the decorative sheet 1 will become soft and lose its stiffness, making it difficult to handle and reducing productivity during processing. In addition, the scratch resistance of the decorative sheet 1 will also be low.

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

When the plasticizer content is within the range of 20 PHR or more and 30 PHR or less, the breaking elongation of the decorative sheet 1 at 0°C is 10% or more and 400% or less, and production stability is good during processing such as wrapping. As mentioned above, if the breaking elongation at 0°C is less than 10%, the decorative sheet 1 is hard and whitening and cracking occurs, and if it is more than 400%, the decorative sheet 1 is soft and has no stiffness, making it difficult to handle, resulting in poor productivity and poor scratch resistance.

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

The transparent polyvinyl chloride resin layer 6 may contain a NOR-type hindered amine light stabilizer (HALS) as a weathering agent. NOR-type HALS has low basicity, so it can suppress the de-HCl reaction of the transparent polyvinyl chloride resin layer 6, and is effective against recent acid rain. Examples of NOR-type hindered amine light stabilizers (HALS) that can be used in the transparent polyvinyl chloride resin layer 6 include "ADEKA STAB LA-81" manufactured by ADEKA Corporation, "TINUVIN 123" (decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester) manufactured by BASF Japan Ltd., and "TINUVIN XT850FF" manufactured by BASF Japan Ltd.

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

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

(Benzotriazole-based UV absorber)
Examples of "benzotriazole-based" ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and mixtures, modified products, polymers, and derivatives thereof.

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

(Cyanoacrylate-based UV absorber)
Examples of the "cyanoacrylate" ultraviolet absorbents include ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and the like.

The thickness of the transparent polyvinyl chloride resin layer 6 is preferably in the range of 50 μm to 150 μm, more preferably in the range of 50 μm to 100 μm, and even more preferably in the range of 60 μm to 80 μm. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 is reliably improved, and the unevenness of the adherend such as a window frame can be absorbed to improve the finish of the decorative sheet 1. Furthermore, 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, and the processability (e.g. bending processability) is improved and the manufacturing cost of the decorative sheet 1 can be reduced.

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

(Surface protective layer)
The surface protective layer 8 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 1. There are no particular limitations on the material constituting the surface protective layer 8, and it can be appropriately selected from, for example, urethane-based, acrylic-based, acrylic silicone-based, fluorine-based, and epoxy-based resin materials.

In order to further improve the weather resistance of the decorative sheet 1, an ultraviolet absorber and a light stabilizer are added to the surface protective layer 8 as weather resistance agents. In addition, the surface protective layer 8 may contain various additives, such as a heat stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as necessary.
Hereinafter, an example of the surface protection layer 8 according to this embodiment will be described with a specific example.

In this embodiment, the surface protection layer 8 may be mainly composed of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component. In this embodiment, cyclohexyl (meth)acrylate 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.

The content of cyclohexyl (meth)acrylate is preferably in the range of 5% by mass or more and 50% by mass or less among all the monomer components of the acrylic resin composition, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protective layer 8. By making the content of cyclohexyl (meth)acrylate 5% by mass or more, a sufficient deterioration suppression effect can be obtained. In addition, by making the content of cyclohexyl (meth)acrylate 50% by mass or less, it is possible to impart high weather resistance over time without significantly changing the various performances of the surface protective layer 8 of the decorative sheet, such as improving the maintenance of surface hardness, improving the resistance to contamination, and adjusting the surface gloss. Here, the above-mentioned "main component" means that the content of the acrylic resin composition that constitutes the surface protective layer 8 is 50% by mass or more with respect to the total mass of the surface protective layer 8.

In addition to cyclohexyl (meth)acrylate, examples of monomer components of the acrylic resin composition that can be used for the surface protective layer 8 in this embodiment include, 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. Among these, those containing isomers may be each isomer alone and/or each isomer mixture.

In addition, in this embodiment, the surface protective layer 8 may be formed by applying a coating liquid containing the above-mentioned acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component and a weathering agent such as an ultraviolet absorber described below to the outermost surface of the decorative sheet. Details will be described later, but for example, the coating liquid containing the above-mentioned acrylic resin composition and a weathering agent may be applied to the transparent polyvinyl chloride resin layer 6 on which the uneven portion 10 is formed, and then the coating liquid may be embedded in the uneven portion 10 by wiping to form the surface protective layer 8.

As a method for curing the coating liquid for forming the surface protective layer 8, for example, a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type that is cured by exposure to ultraviolet light or ionizing radiation can be used. However, when considering weather resistance, a two-component curing type or an active energy ray curing type is preferred, and when considering post-processability after being laminated to various substrates to become a decorative member, a two-component curing type that is crosslinked by isocyanate curing is desirable.

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

As an acrylic polyol having two or more hydroxyl groups in one molecule, in addition to the above-mentioned cyclohexyl (meth)acrylate, for example, a (meth)acrylic acid ester copolymer containing hydroxyethyl (meth)acrylate as a monomer component can be used. On the other hand, as a polyisocyanate compound having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer type, TMP adduct type, biuret type, etc., synthesized by a known technique using one or more compounds selected from these. In addition, a composition in which one or more types selected from these different types of polyisocyanates are mixed can be used. Among these, HDI, HDI trimer type, TMP adduct type, and biuret type are preferred from the viewpoint of weather resistance. The content of the isocyanate compound relative to the resin components described above can be set at will, but it is desirable to set the hydroxyl group/isocyanate group equivalent ratio to about 1/1 to 1/3. In particular, if the hydroxyl group equivalent is greater than the isocyanate group equivalent, crosslinking may not proceed sufficiently, and the desired performance may not be imparted to the surface protective layer 8, which is not preferred.

When the coating liquid for forming the surface protective layer 8 is cured by active energy ray curing, known monomers, oligomers, etc. having a (meth)acryloyl group can be used as the active energy ray curable acrylic resin composition, and the above-mentioned cyclohexyl (meth)acrylate can be blended in addition to these monomers and oligomers.

To improve the fingerprint resistance of the decorative sheet 1, a silicone resin is added to the surface protective layer 8. The silicone resin is preferably an amino-modified silicone resin. The surface protective layer 8 is formed so that the contact angle of oleic acid on the surface of the layer is 20° or more. The contact angle of oleic acid can be adjusted by adjusting the amount of silicone resin added to the surface protective layer 8. In addition, when the surface protective layer 8 has an uneven portion, the contact angle of oleic acid can also be adjusted by adjusting the shape of the uneven portion.

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

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) 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, the surface protective layer 8 may contain 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter, for convenience, referred to as "ultraviolet absorber A"). Note that 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, which is the ultraviolet absorber A, is generally known as the main component of "Tinuvin 479: manufactured by BASF Japan, Ltd."

In the surface protective layer 8 of this embodiment, the amount of the triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber added is preferably within the range of 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the resin composition (e.g., acrylic resin composition) forming the surface protective layer 8. By adding the ultraviolet absorber in an amount of 1 part by mass or more, the weather resistance improving effect is exerted, and by adding the amount of the ultraviolet absorber in an amount of 30 parts by mass or less, the effect on physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a level that does not cause practical problems.

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

In this embodiment, the ultraviolet absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter referred to as "ultraviolet absorber B" for convenience) are used together as triazine-based (hydroxyphenyltriazine-based) ultraviolet absorbers in the surface protective layer 8, thereby providing even better weather resistance. This is because ultraviolet absorber B has a high ultraviolet absorption capacity in the short wavelength region, which is relatively high energy among ultraviolet rays, and is chemically stable compared to other ultraviolet absorbers that absorb approximately the same wavelength region, and therefore the wavelength region in which ultraviolet rays are absorbed is broadened by using them together. Note that 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is ultraviolet absorber B, is generally known as the main component of "ADEKA STAB LA-46: manufactured by ADEKA Corporation".

In this embodiment, the amount of ultraviolet absorber A added to the surface protective layer 8 is preferably in the range of 10 parts by weight to 200 parts by weight, more preferably in the range of 20 parts by weight to 100 parts by weight, and even more preferably in the range of 40 parts by weight to 80 parts by weight, relative to 100 parts by weight of ultraviolet absorber B. By setting the amount of ultraviolet absorber A added within the above numerical range, even better weather resistance can be imparted.

(Light stabilizer)
For example, a radical scavenger can be used as the light stabilizer added to the surface protective layer 8. By using the above-mentioned triazine-based ultraviolet absorber in combination with the radical scavenger, the weather resistance of the decorative sheet 1 can be further improved. Examples of the hindered amine radical scavenger that can be used in the present embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidylstearate, 1,2,2,6,6-pentamethyl-4-piperidylstearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and tetrakis(2,2,6,6-tetramethyl-4-piperidyl). -1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6
-Tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2
,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2 ,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2 ,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate cyclohexane and a reaction product of N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide and 2-aminoethanol, but are not limited thereto.

In this embodiment, the amount of light stabilizer (e.g., a hindered amine radical scavenger) added to the surface protective layer 8 is preferably within the range of 1 part by mass to 30 parts by mass relative to 100 parts by mass of the resin composition (e.g., an acrylic resin composition) forming the surface protective layer 8. By adding 1 part by mass or more of the light stabilizer, the desired weather resistance can be obtained, and by adding 30 parts by mass or less, bleeding out of the weather resistance agent can be suppressed and the effect on other physical properties of the surface protective layer 8 can be suppressed.

In this embodiment, the surface protective layer 8 contains an ultraviolet absorber and a light stabilizer, but the present disclosure is not limited to this. The surface protective layer 8 may be provided with the desired weather resistance depending on the application, and may contain at least one of an ultraviolet absorber and a light stabilizer.

(Amount of Coating)
The coating amount of the surface protective layer 8, i.e., the coating amount of the material of the surface protective layer 8 on the transparent polyvinyl chloride resin layer 6, is preferably within a range of 3 g/ ^m2 or more and less than 10 g/ ^m2 . If the coating amount is less than 3 g/ ^m2 , good weather resistance cannot be obtained, and if it is 10 g/ ^m2 or more, there is a risk of impeding recyclability, so 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, it is possible to improve productivity and processability (e.g., bending processability).

(Uneven part)
As shown in Fig. 1, an uneven portion 10 is provided on the outermost surface of the decorative sheet 1. By providing the uneven portion 10 on the outermost surface, it is possible to improve fingerprint resistance while maintaining the matte feel of the surface of the decorative sheet 1. The uneven portion 10 can have various uneven shapes, such as wood grain duct grooves, stone slab surface unevenness (granite cleavage surface, etc.), cloth surface texture, matte finish, sand grain, hairline, and linear grooves, to impart a given design to the surface of the decorative sheet 1. The uneven portion 10 can have various uneven shapes, for example, according to the design of the picture layer 4 or according to the desired design.

The uneven portion 10 is formed on the surface (outermost surface) side of the surface protection layer 8, which is the outermost layer of the decorative sheet 1, and forms an uneven pattern. In this embodiment, the above-mentioned surface protection layer 8 is embedded in the uneven portion 10 that forms the uneven pattern. This point will be explained below.

In the decorative sheet 1 according to this embodiment, the uneven portion 10 is provided in the transparent polyvinyl chloride resin layer 6. In other words, the transparent polyvinyl chloride resin layer 6 is a 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 it is preferable that the shape of the uneven portion 10 constituting the uneven pattern is such that the opening diameter increases from the picture layer 4 side of the transparent polyvinyl chloride resin layer 6 toward the surface protection layer 8. With such a shape, it becomes easier to fill the uneven portion 10 when the surface protection layer composition (coating liquid) is filled in by wiping.

In addition, 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, it becomes easier to fill the uneven portion 10 with the surface protection layer composition (coating liquid) by wiping.
In addition, all of the side surfaces forming the uneven portion 10 may be covered with the surface protection layer 8 .

The depth of the uneven portion 10 is preferably within a range of 1 μm to 50 μm in the thickness direction of the transparent polyvinyl chloride resin layer 6. If the depth of the uneven portion 10 is within the above numerical range, it becomes easy to embed the surface protection layer composition (coating liquid) into the uneven portion 10 by wiping, and peeling of the surface protection layer can be prevented.

The width of the uneven portion 10 in the cross section shown in FIG. 1 is preferably in the range of 1 μm to 20 μm. If the width of the uneven portion 10 is in the above numerical range, the surface protection layer composition (coating liquid) can be easily embedded in the uneven portion 10 by wiping, and the surface protection layer embedded in the uneven portion 10 can be prevented from peeling off.

It is also preferable that the uneven portion 10 is completely filled (packed) with the surface protection layer composition (coating liquid), but the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is preferably 10% or more. If the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is 10% or more, the weather resistance of the uneven portion 10 can be improved. That is, if the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is 10% or more, for example, the occurrence of whitening or breakage in the conduit portion can be reduced. Also, as described above, it is preferable that the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is 100%, but it is more preferable that the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is 80% or less, and it is more preferable that the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is 60% or less. If the filling rate of the surface protection layer 8 with respect to the volume of the uneven portion 10 is 80% or less, a sufficient tactile sensation can be obtained in the uneven portion 10.

Furthermore, by setting the filling rate of the surface protection layer 8 relative to the volume of the uneven portion 10 to 100%, the surface of the surface protection layer 8 filled in the uneven portion 10 and the surface of the transparent polyvinyl chloride resin layer 6 in the area not having the uneven portion 10 can be made flush, so to speak.
It is not essential to provide the uneven portion 10. Instead, a gloss control layer may be provided.

(Total thickness of decorative sheet)
The total thickness of the decorative sheet 1, i.e., the sum of the thickness of the colored polyvinyl chloride resin layer 2, the thickness of the pattern layer 4, the thickness of the transparent polyvinyl chloride resin layer 6, and the thickness of the surface protective layer 8, is preferably in the range of 100 μm to 300 μm, more preferably in the range of 120 μm to 200 μm. If the total thickness of the decorative sheet 1 is thinner than 100 μm, the concealing property and scratch resistance are reduced, and further, when the decorative sheet 1 is processed, the sheet has no strength, and productivity is reduced. If the total thickness of the decorative sheet 1 is thicker than 300 μm, the processability such as bending is reduced. As a result, for example, a decorative sheet 1 having the same degree of concealing property as a decorative sheet formed using a conventional olefin-based resin and having good processability can be formed. Note that the total thickness of the decorative sheet 1 referred to here means, in the case of the decorative sheet 1 shown in FIG. 1, the sum of the thickness of the colored polyvinyl chloride resin layer 2, the thickness of the pattern layer 4, the thickness of the transparent polyvinyl chloride resin layer 6, and the thickness of the surface protective layer 8, i.e., the sum of the thicknesses of all layers constituting the decorative sheet 1. For example, in the decorative sheet 1 shown in Figure 1, if a concealing layer is provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2, the thickness refers to the total thickness of the decorative sheet 1, which is the sum of the thickness of the colored polyvinyl chloride resin layer 2, the thickness of the pattern layer 4, the thickness of the transparent polyvinyl chloride resin layer 6, the thickness of the surface protective layer 8, and the thickness of the concealing layer, in other words, the thickness of the entire decorative sheet 1 formed including the 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.

(Modification)
In the decorative sheet 1, the pattern of the pattern layer 4 and the uneven portion 10 may be in harmony with each other.

Although the decorative sheet 1 has a colored polyvinyl chloride resin layer 2, the colored polyvinyl chloride resin layer 2 is not necessarily required, that is, the decorative sheet 1 may be a single layer. When the decorative sheet 1 is a single layer, it is preferable to provide a concealing layer (not shown) on the surface of the pattern layer 4 opposite the transparent polyvinyl chloride resin layer 6.

(Decorative materials)
The decorative sheet 1 shown in FIG. 1 may be attached to a substrate 20 via an adhesive layer 12 as shown in FIG.

(Base material)
The substrate 20 may be a wood substrate or a metal substrate. The substrate 20 may be, for example, a wood veneer, a wood plywood, a laminated lumber, a particle board, a medium density fiberboard, or a hard fiberboard. The metal substrate may be, for example, a steel plate or an aluminum plate. The substrate 20 may be a resin such as plastic, or a composite material thereof. When the substrate 20 is a resin substrate, for example, a polyvinyl chloride resin may be used. The substrate 20 made of polyvinyl chloride resin has high thermal insulation properties and is in high demand as a window frame fixture (sash). The decorative member 50 in which the substrate 20 made of polyvinyl chloride resin is decorated with the decorative sheet 1 can be reused by dissolving both the substrate 20 and the decorative sheet 1, which can improve recyclability.

The base material 20 may be made of, for example, a fireproof steel plate or a fireproof material as specified in Ministry of Construction Notification No. 1400. The base material 20 may have a folded structure or a three-dimensional structure.
The configuration of the decorative member 50 is not limited to the example shown in Fig. 1. That is, the decorative member 50 may be configured to include a decorative sheet 1 laminated on one surface of the base material 20, as well as on the other surface of the base material 20 (the lower surface in Fig. 1).

When laminating the decorative sheet 1 to the substrate 20, an adhesive layer 12 may be provided by laminating the sheet via an adhesive selected as necessary, or the sheet may be laminated directly without an adhesive.
The adhesive may be selected depending on the material of the base material 20, and may be a two-component curing type or a hot melt type adhesive.

Methods for laminating and adhering the decorative sheet 1 to the substrate 20 include a method of pressing with a metal plate and using flat pressure, and a continuous lamination method using a circular pressure method. In particular, the continuous lamination method using an endless metal belt makes it possible to continuously produce a high-quality decorative member 50 at high speed without surface warping or waviness, with good adhesion between layers and a densely hardened and integrated structure.

(Method of manufacturing decorative sheet and decorative member)
An example of a method for producing the decorative sheet 1 according to this embodiment will now be briefly described.
For example, a design layer 4 is printed on a colored polyvinyl chloride resin layer 2 made of a colored polyvinyl chloride resin sheet.

Next, a transparent polyvinyl chloride resin layer 6 is formed by thermal lamination on the colored polyvinyl chloride resin layer 2 on which the pattern layer 4 has been formed, and at the same time, an uneven pattern is provided by embossing the surface of the transparent polyvinyl chloride resin layer 6 opposite the colored polyvinyl chloride resin layer 2 to form the uneven portion 10.

Next, a coating liquid for forming a surface protective layer 8 is applied to the surface of the transparent polyvinyl chloride resin layer 6 on which the uneven pattern (uneven portion 10) has been formed.
Finally, the coating liquid is wiped so as to fill the unevenness 10 and then cured to form a surface protection layer 8 on the transparent polyvinyl chloride resin layer 6 .
In this manner, the decorative sheet 1 according to this embodiment is formed.

An adhesive is applied to the surface of the decorative sheet 1 formed in this manner on the side of the colored polyvinyl chloride resin layer 2, and a substrate 20 is attached to it, thereby forming a decorative member 50 in which the decorative sheet 1 and the substrate 20 are bonded together via the adhesive layer 12.
The above-described embodiment is one example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even if the embodiment is a form other than the above-described embodiment, as long as the modifications do not deviate from the technical idea of the present invention.

(effect)
(1) In the decorative sheet 1 according to the first embodiment, a silicone 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. This makes it possible to impart fingerprint resistance to the decorative sheet 1. Also, while it is possible to provide the surface protective layer 8 with an uneven portion 10 as a method for imparting fingerprint resistance, it is possible to provide fingerprint resistance without providing the uneven portion 10. Therefore, it is possible to obtain a decorative sheet 1 with a desired surface shape without being restricted by providing the uneven portion 10 or the shape of the uneven portion 10.

(2) By bonding the decorative sheet 1 to an exterior fitting component (substrate 20), fingerprint resistance can be easily imparted to the fitting component.

(Modification)
In the above embodiment, a transparent polyvinyl chloride resin layer is used as the transparent resin layer. However, an acrylic resin layer may be used as the transparent resin layer instead of the transparent polyvinyl chloride resin layer.

Second Embodiment
Next, a second embodiment of the present invention will be described.
The decorative sheet 100 according to the second embodiment is a decorative sheet containing an olefin resin as a main component.

(Configuration of decorative sheet)
FIG. 2 is a cross-sectional view that illustrates an example of a decorative sheet 100 according to a second embodiment of the present invention.
2, the decorative sheet 100 comprises a colored thermoplastic resin layer (colored substrate layer) 51, a design 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, and further comprises a primer layer 57 on the surface of the colored thermoplastic resin layer 51 opposite the design layer 52. The surface protective layer 56, which is the outermost layer of the decorative sheet 100, has an uneven portion 110 formed from the surface side to the transparent thermoplastic resin layer 55.

(Colored thermoplastic resin layer)
The colored thermoplastic resin layer 51 functions as a support for the decorative sheet 100, and is colored opaquely to have concealing properties, so that when the decorative sheet 100 is attached to an adherend such as a window frame, the colored thermoplastic resin layer 51 can conceal color variations and defects on the surface of the adherend.
The colored thermoplastic resin layer 51 may be made of, for example, a polyolefin-based thermoplastic resin.

As the polyolefin resin, a polypropylene resin, i.e., a homopolymer or copolymer mainly composed of propylene, can be used. For example, homopolypropylene resin, random polypropylene resin, block polypropylene resin, etc. can be used alone or in appropriate combination, or resins in which atactic polypropylene is further added can be used. In addition, it may be a copolymer containing an olefin monomer other than propylene, for example, a propylene-α-olefin copolymer having a polypropylene crystal portion 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. 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 hydrogenated products thereof, which are usually used to soften polypropylene resins, can be added as appropriate.

Furthermore, the colored thermoplastic resin layer 51 may contain, as 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 adjusters.

(Pattern layer)
The pattern layer 52 is provided as necessary to impart a design to the decorative sheet 100 by a pattern. The pattern layer 52 can be omitted if the coloring of the colored thermoplastic resin layer 51 can be used instead. 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 together with a suitable binder resin in a suitable dilution solvent. The printing ink or paint is applied by various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating. In addition, as the binder resin, for example, urethane-based resin, acrylic resin, vinyl chloride acetate-based resin, polyimide-based resin, nitrocellulose, or a mixture thereof can be used, but urethane-based resin is particularly preferred. In addition, 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, a letter, a symbol, a solid color, or a combination of two or more of these. In addition, in order to improve the concealing properties of the decorative sheet 100, a concealing layer made of opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide may be provided between the pattern layer 52 and the colored thermoplastic resin layer 51.

(Anchor layer)
The anchor layer 53 is provided as necessary in order to improve adhesion with the transparent adhesive resin layer 54 used for bonding with the colored thermoplastic resin layer 51. The anchor layer 53 contains a urethane-based resin as a binder resin.

(Transparent adhesive resin layer)
The transparent adhesive resin layer 54 is provided as necessary 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. For example, a non-halogen thermoplastic resin can be used as the adhesive. In particular, from the standpoints of various physical properties, processability, versatility, economic efficiency, etc., it is desirable to use a polyolefin resin or a polyester resin as the non-halogen thermoplastic resin.

In addition, a triazine-based ultraviolet absorber is added to the transparent adhesive resin layer 54 to provide weather resistance. The ratio of the triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 1% by mass or less relative 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 decreases. Furthermore, if it is more than 1% by mass, there is a problem of precipitation such as bleed-out.

In addition, a hindered amine-based photoradical scavenger is added to the surface protection layer 56 described below 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 photoradical scavenger is preferably 0.1% by mass or more and 1% by mass or less relative 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 scavenging is insufficient and the resin itself is easily deteriorated. Furthermore, if it is more than 1% by mass, there is a problem of precipitation such as bleed-out.

(Transparent thermoplastic resin layer)
The transparent thermoplastic resin layer 55 may be made of, for example, a polyolefin-based thermoplastic resin, similar to the colored thermoplastic resin layer 51 .

As the polyolefin resin, a polypropylene resin, i.e., a homopolymer or copolymer mainly composed of propylene, can be used. For example, homopolypropylene resin, random polypropylene resin, block polypropylene resin, etc. can be used alone or in appropriate combination, or resins in which atactic polypropylene is further added can be used. In addition, it may be a copolymer containing an olefin monomer other than propylene, for example, a propylene-α-olefin copolymer having a polypropylene crystal portion 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. 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 hydrogenated products thereof, which are usually used to soften polypropylene resins, can be added as appropriate.

In order to provide weather resistance, a triazine-based ultraviolet absorbing agent is added to the transparent thermoplastic resin layer 55. The ratio of the triazine-based ultraviolet absorbing agent to the total mass of the transparent thermoplastic resin layer 55 is preferably 0.1% by mass or more and 1% by mass or less, and more preferably 0.2% by mass or more and 0.7% by mass or less. Examples of triazine-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, and 2-ethylhexanoic acid. 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and mixtures, modified products, polymers, and derivatives thereof can be used.

In addition, a hindered amine-based light radical scavenger (i.e., a "hindered amine-based light stabilizer") is added to the transparent thermoplastic resin layer 55 to capture radicals induced by light energy and radicals induced by heat energy converted from light energy by an ultraviolet absorber, and to prevent 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 relative to 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 scavenging is insufficient and the resin itself is easily deteriorated. Also, if it is more than 1% by mass, there is a problem of precipitation such as bleed-out. Examples of the hindered amine 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, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl). -1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensation 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- Hindered amine compounds such as 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, and 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, as well as mixtures, modified products, polymers, and derivatives thereof can be used.

(Surface protective layer)
When the decorative member 150 including the decorative sheet 100 is used as an exterior material, scratch resistance, weather resistance, durability, etc. are required, and for example, an acrylic urethane resin or an ionizing radiation curable resin can be used as the material for the surface protective layer 56. For example, a reaction product using an acrylic polyol compound as a base agent and an isocyanate compound as a curing agent can be used as the acrylic urethane resin. As the acrylic polyol compound, for example, an acrylic polymer compound having a hydroxyl group in a side chain obtained by blending and copolymerizing a monomer containing a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and a copolymerizable polymerizable monomer such as styrene, α-methylstyrene, vinyl toluene, divinylbenzene, vinyl acetate, vinyl butyrate, vinyl versatate, ethyl vinyl ether, acrylonitrile, or methacrylonitrile with a normal acrylic monomer such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, or the like, can be used.

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 decorative member 150 is used as an exterior member for an exterior, the surface protective layer 56 needs to be weather resistant. In consideration of weather resistance, a non-yellowing isocyanate compound that does not have an aromatic ring, that is, an aliphatic or alicyclic isocyanate compound, is preferable.

As the ionizing radiation curable resin, for example, a composition containing as its main component at least one of a prepolymer, oligomer, and monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group, which has the property of undergoing a crosslinking reaction when irradiated with ionizing radiation, can be used. As the ionizing radiation, for example, an electron beam or ultraviolet light can be used. If necessary, additives such as a polymerization initiator and a sensitizer can be added to the ionizing radiation curable resin.

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, etc. Examples of monomers that can be used include monofunctional monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate, bifunctional monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, and hexanediol diacrylate, and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

The thickness of the surface protective layer 56 is not particularly limited, but if it is too thin, it will be less effective, and if it is too thick, it will lose flexibility and become more susceptible to cracking. For this reason, for example, a thickness of 1 μm or more and 20 μm or less is preferable. Note that it is preferable that the surface protective layer 56 has a transparency that allows the surface of the transparent thermoplastic resin layer 55 disposed on one side of the surface protective layer 56 to be seen through. For example, it may be colorless and transparent, colored and transparent, or translucent.

In addition, a triazine-based ultraviolet absorber is added to the surface protective layer 56 to provide 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 protective 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 of reduced ultraviolet absorption performance. If it is more than 20% by mass, there is a problem of precipitation such as bleed-out. In addition, a hindered amine-based light radical scavenger is added to the surface protective layer 56 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 protective 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 of poor radical scavenging performance and easy deterioration of the resin itself. If it is more than 10% by mass, there is a problem of precipitation such as bleed-out. In addition, to further improve the weather resistance of the decorative sheet 100, a light stabilizer is added to the surface protective layer 56 as a weather resistance agent. The light stabilizer may be the same as that used for the surface protective layer 8.

Furthermore, in order to improve the fingerprint resistance of the decorative sheet 100, a silicone resin is added to the surface protective layer 56. As the silicone resin, an amino-modified silicone resin is preferable. Furthermore, the surface protective layer 56 is formed so that the contact angle of oleic acid on its surface is 20° or more. The contact angle of oleic acid can be adjusted by adjusting the amount of silicone resin added to the surface protective layer 56. Furthermore, when the surface protective layer 56 has an uneven portion, the contact angle of oleic acid can also be adjusted by adjusting the shape of the uneven portion.

(Uneven part)
The outermost surface of the decorative sheet 100, i.e., the surface of the surface protective layer 56, is provided with an uneven portion 110 formed by embossing. As the uneven portion 110, for example, a pattern that is in harmony with the pattern of the pattern layer 52 or a pattern that is not in harmony with the pattern can be used.

Note that the uneven portion 110 does not necessarily have to be provided. Instead, a gloss adjustment layer may be provided.

(Primer layer)
The primer layer 57 is provided as necessary in order to improve adhesion with the adhesive layer 59 used for bonding to the substrate 60 described below. Examples of materials that can be used for the primer layer 57 include urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, and polyester-based materials. In particular, a two-component curing urethane-based primer agent made by blending polyester polyol and polyisocyanate is preferable. In addition, the addition of inorganic powder such as silica, barium sulfate, or calcium carbonate is effective in preventing blocking during storage in a roll and in improving adhesive strength by an anchoring effect.

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

(Modification)
In the decorative sheet 100, the pattern of the pattern layer 52 and the uneven portion 110 may be coordinated.
Furthermore, although the decorative sheet 100 includes a colored thermoplastic resin layer 51, the colored thermoplastic resin layer 51 is not necessarily required, that is, the decorative sheet 100 may be a single layer. When the decorative sheet 100 is a single layer, it is preferable to provide a concealing layer (not shown) on the surface of the design layer 52 opposite the transparent thermoplastic resin layer 55.

(Decorative materials)
As shown in FIG. 2, the decorative sheet 100 may be attached to a substrate 60 via an adhesive layer 59 to form a decorative member 150 .

(Base material)
The material of the substrate 60 may be, for example, a metal-based material. Examples of the metal-based material include steel plate, brass plate, aluminum plate, duralumin plate, and stainless steel plate. By using a metal-based material, an exterior material that can be used for exteriors can be provided. For example, an adhesive layer may be provided between the substrate 60 and the decorative sheet 100, as necessary.

(Method of manufacturing decorative sheet and decorative member)
An example of a method for producing the decorative sheet 100 according to this embodiment will be briefly described below.

For example, a pattern layer 52 is formed on one side of a colored polyethylene resin (PE) sheet as the colored thermoplastic resin layer 51. Next, an anchor layer 53 is formed on the surface of the pattern layer 52, and a resin for the transparent thermoplastic resin layer 55 and a 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 by embossing on the surface of the transparent thermoplastic resin layer 55 opposite the transparent adhesive resin layer 54 to form the uneven portion 110. Then, a resin for the surface protective layer 56 is applied to the surface of the transparent thermoplastic resin layer 55 to form the surface protective layer 56. Furthermore, a primer is applied to the surface opposite the surface protective layer 56 of the colored thermoplastic resin layer 51 to form a primer layer 57, and the decorative sheet 100 is formed.

Then, an adhesive layer 59 is applied to the surface of the primer layer 57 and a substrate 60 is attached to it, thereby forming a decorative member 150 in which the decorative sheet 100 and the substrate 60 are bonded together via the adhesive layer 12 .
The above-described embodiment is one example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even if the embodiment is a form other than the above-described embodiment, as long as the modifications do not deviate from the technical idea of the present invention.

(effect)
(1) In the decorative sheet 100 according to the second embodiment, a silicone resin is added to the surface protective layer 56 so that the contact angle of oleic acid on the surface of the surface protective layer 56 is 20° or more. This makes it possible to impart fingerprint resistance to the decorative sheet 100. Also, while it is conceivable to provide an uneven portion 110 in the surface protective layer 56 as a method for imparting fingerprint resistance, fingerprint resistance can be imparted without providing the uneven portion 110. Therefore, a decorative sheet 1 having a desired surface shape can be obtained without being restricted by providing the uneven portion 110 or the shape of the uneven portion 110.

(2) By bonding the decorative sheet 100 to an exterior fitting component (substrate 60), fingerprint resistance can be easily imparted to the fitting component.
It should be noted that the decorative sheet according to this embodiment does not necessarily have to have all the layers shown in FIG. 1 or FIG. 2, and any decorative sheet having a surface protective layer can be used.

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
A decorative sheet for evaluation containing a vinyl chloride resin (acrylic resin) as the main component in embodiment 1, and a decorative sheet for evaluation containing an olefin resin as the main component in embodiment 2 were prepared and evaluated.

(Decorative sheet for evaluation, the main component of which is vinyl chloride resin (acrylic resin))
A decorative sheet for evaluation containing a vinyl chloride resin as a main component was prepared by the following procedure.

A colored polyvinyl chloride resin sheet was used as the colored substrate layer. A design layer was formed on one side of the colored polyvinyl chloride resin sheet by gravure printing using a printing ink for vinyl chloride. After that, a transparent polyvinyl chloride resin sheet was placed on top of the design layer as a transparent resin layer by doubling embossing and thermal lamination. Then, a resin composition mainly composed of an acrylic resin composition was laminated on top of the transparent polyvinyl chloride sheet as a surface protection layer.

This resulted in a decorative sheet for evaluation that was mainly composed of vinyl chloride resin. When preparing a decorative sheet for evaluation that was mainly composed of a vinyl chloride resin, it is sufficient to form a transparent resin layer using an acrylic resin instead of a transparent polyvinyl chloride sheet.

The composition of each layer is as follows:
(Colored polyvinyl chloride resin sheet)
Material: Polyvinyl chloride resin (PVC)
Thickness: 80μm
(Transparent polyvinyl chloride resin sheet)
Material: Polyvinyl chloride resin (PVC)
Thickness: 80μm
UV absorber: 0.5 parts by weight of triazine UV absorber HALS: 0.5 parts by weight of NOR type (Adeka STAB LA81, manufactured by ADEKA CORPORATION) (pattern layer)
Binder resin: Mixture of vinyl chloride resin-vinyl acetate resin copolymer and acrylic resin (surface protective layer)
Base: methyl methacrylate/2-hydroxyethyl methacrylate = 95/5 copolymer) 90 parts by weight UV absorber: Tinuvin 479 manufactured by BASF Japan Ltd. 9 parts by weight Light stabilizer: Tinuvin 123 manufactured by BASF Japan Ltd. 1 part by weight Amino-modified silicone additive (amino-modified silicone resin/solvent = 10/90) 5 parts by weight Hardener: Takenate D170 manufactured by Mitsui Chemicals Inc. 10 parts by weight Solvent: ethyl acetate 240 parts by weight Coating amount 3 g/ ^m2
(Decorative sheet for evaluation, mainly composed of olefin resin)
A decorative sheet for evaluation containing an olefin resin as a main component was prepared by the following procedure.

A layer made of colored thermoplastic resin was created with a thickness of 70 μm as the colored substrate layer. A design layer was printed on one side of the colored thermoplastic resin layer, and a primer layer was printed on the other side of the colored thermoplastic resin layer.

Next, an anchor layer was applied to the surface of the design layer opposite the colored thermoplastic resin layer, and a transparent adhesive resin layer and a transparent thermoplastic resin layer as a transparent resin layer were extruded and laminated on top of this anchor layer. At this time, an uneven pattern was provided by embossing the surface of the transparent thermoplastic resin layer opposite the transparent adhesive resin layer to form an uneven portion. Furthermore, a surface protection layer was applied on top of the transparent thermoplastic resin layer.

As a result, a decorative sheet for evaluation containing an olefin resin as a main component 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
(Picture ink layer, primer layer, anchor layer)
Binder resin: Urethane resin (surface protective layer)
It is the same as the surface protective layer of the "decorative sheet for evaluation whose main component is vinyl chloride resin."

(Decorative sheets for evaluation of Examples and Comparative Examples)
Example 1
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 concave and convex portions was made to have a matte finish.
Example 2
The transparent resin layer was made of polypropylene resin (PP), and the surface protection layer was made of silicone resin. The uneven portion had a wood grain pattern.
Example 3
The transparent resin layer was made of polyvinyl chloride resin (PVC), and the surface protection layer was made of silicone resin. The uneven portion had a wood grain pattern.
Example 4
The transparent resin layer was made of polyvinyl chloride resin (PVC), and the surface protection layer was made of silicone resin. The uneven portion had a matte finish.
Example 5
The transparent resin layer was made of acrylic resin (PMMA), and the surface protection layer was made of silicone resin. The unevenness was given a matte finish.
Example 6
The transparent resin layer was made of acrylic resin (PMMA), and the surface protection layer was made of silicone resin. The uneven portion had a wood grain pattern.
(Example 7)
The transparent resin layer was made of polyvinyl chloride resin (PVC), and the surface protection layer was made of silicone resin. The uneven portion had 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 concave and convex portions was made to have a matte finish.
(Comparative Example 1)
The transparent resin layer was made of polypropylene resin (PP). No silicone resin was added to the surface protection layer. The uneven portion had a matte finish.
(Comparative Example 2)
The transparent resin layer was made of polypropylene resin (PP). No silicone resin was added to the surface protection layer. The uneven portion had a wood grain pattern.
(Comparative Example 3)
The transparent resin layer was made of polyvinyl chloride resin (PVC). No silicone resin was added to the surface protection layer. The uneven portion had a matte finish.
(Comparative Example 4)
The transparent resin layer was made of polyvinyl chloride resin (PVC). No silicone resin was added to the surface protection layer. The uneven portion had a matte finish.
(Comparative Example 5)
The transparent resin layer was made of acrylic resin (PMMA), and no silicone resin was added to the surface protection layer. The uneven portion had a matte finish.

〔evaluation〕
For each of the decorative sheets for evaluation in the Examples and Comparative Examples, the contact angle with oleic acid was measured, and further a fingerprint resistance test was carried out.

(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 was measured after 3 seconds.

(Fingerprint resistance test)
(1) 1.0 g of oleic acid was mixed with 0.01 g of lecithin (emulsifier), and 1.0 g of peptone (protein) was kneaded with 0.4 g of water and mixed therewith to prepare a coating agent for the fingerprint resistance test.
(2) The gloss value at 60° on the surface of the decorative sheet was measured using a gloss meter (MICROGLOSS manufactured by BYK Corporation).
(3) The mixture prepared in the procedure of (1) was applied to the surface of a decorative sheet and allowed to stand for 1 minute, after which the applied coating agent for the fingerprint resistance test was wiped off with a dry cloth.
(4) The gloss value at 60° on the surface of the decorative sheet was measured again.
(5) The rate of change between the gloss value measured in (2) and the gloss value measured in (4) was calculated.
(6) In addition to measuring the gloss value, the color difference ΔE of the surface of each evaluation decorative sheet was measured before the application of the coating agent for the fingerprint resistance test and after the coating agent for the fingerprint resistance test was wiped off. The color difference ΔE was measured using a color difference meter CR-400 (manufactured by KONICA MINOLTA).

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 were as follows: "◯" or "◎" was deemed to be acceptable.
⊚: Gloss value change rate is less than 40% and color difference ΔE is less than 0.9. ◯: Gloss value change rate is less than 40% and color difference ΔE is 0.9 or more. ×: Gloss value change rate is 40% or more. The evaluation results for each of the above evaluation items are shown in Table 1.

As shown in Table 1, as the contact angle of oleic acid increases, the gloss value change rate and color difference ΔE tend to decrease. If the contact angle of oleic acid is 20° or more, the gloss value change rate is less than 40% and the color difference ΔE is less than 1.1, and fingerprint resistance can be obtained. If the contact angle of oleic acid is about 30° or more, the gloss value change rate is less than 40% and the color difference ΔE is less than 0.9, and better fingerprint resistance can be obtained. In other words, it was confirmed that by adding a silicone resin to the surface protection layer and setting the contact angle of oleic acid to 20° or more, it is possible to suppress changes in the gloss of the surface of the decorative sheet 1, 100 due to the adhesion of fingerprints, and fingerprint resistance is improved.

The present invention can have the following configurations, for example.
(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)
The decorative sheet according to (1) above, wherein the silicone resin is an amino-modified silicone resin.
(3)
The decorative sheet according to (1) or (2) above, wherein 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 the coating agent is wiped off, the rate of change in gloss value 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 (3) above, 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)
The decorative sheet according to any one of (1) to (4) above, 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,
The decorative sheet according to any one of (1) to (5) above, 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 (6) above, characterized in that the surface protective layer is provided with an uneven portion or a gloss adjustment layer that matches the pattern of the pattern layer.
(8)
The decorative sheet according to the above (6) or (7), wherein the transparent resin layer contains an ultraviolet absorbing agent and a light stabilizer.
(9)
The decorative sheet according to any one of (6) to (8) above, further comprising a colored substrate layer on the opposite side of the design layer from the transparent resin layer.
(10)
The decorative sheet according to (9) above, characterized in that it comprises, 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 (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,
A decorative member comprising: a substrate disposed on the outermost surface of the decorative sheet opposite the surface protective layer.

1, 100 Decorative sheet 2 Colored polyvinyl chloride resin layer (colored substrate layer)
4, 52 Picture layer 6 Transparent polyvinyl chloride resin layer (transparent resin layer)
8, 56 Surface protective layer 10, 110 Concave and 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 (12)

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. The decorative sheet according to claim 1, characterized in that the silicone resin is an amino-modified silicone resin. 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 rate of change in gloss value between the state before the coating agent is applied and the state after the coating agent is wiped off is less than 40%. 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. The decorative sheet according to claim 1 or 2, characterized in that the surface protective layer contains an ultraviolet absorber and a light stabilizer. 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. The decorative sheet according to claim 6, characterized in that the surface protective layer is provided with an uneven portion or a gloss adjustment layer that matches the pattern of the pattern layer. The decorative sheet according to claim 6, characterized in that the transparent resin layer contains an ultraviolet absorber and a light stabilizer. The decorative sheet according to claim 6, characterized in that a colored base layer is provided on the opposite side of the design layer from the transparent resin layer. The decorative sheet according to claim 9, characterized in that it comprises, in this order, a colored polyvinyl chloride resin layer as the colored base 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. The decorative sheet according to claim 9, characterized in that it comprises, in this order, a colored thermoplastic resin layer as the colored base layer, the pattern layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer as the transparent resin layer, and the surface protective layer. 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.

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