Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material which have good bending workability even when formed using a polyvinyl chloride resin, and are excellent in productivity and recyclability during printing.SOLUTION: A decorative sheet 1 is formed by stacking at least a colored raw fabric layer 2, a pattern layer 3, a transparent resin layer 4 and a surface protective layer 5 in this order, wherein the colored raw fabric layer 2 is formed of a colored polyvinyl chloride resin, the transparent resin layer 4 is formed of a transparent polyvinyl chloride resin, a Martens hardness measured by a measurement method according to ISO 14577-1:2002 is within the range of 50 MPa or more and 150 MPa or less, and a total thickness of the sheet is within the range of 80 μm or more and 300 μm or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a cosmetic sheet and a cosmetic material.

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] As the interest in environmental problems has increased, the use of cosmetic sheets made of polyvinyl chloride resin has been temporarily suppressed, and the use of cosmetic sheets made of olefin resin as a substitute for polyvinyl chloride cosmetic sheets has been increasing.

[0005] However, in recent years, with the improvement of incineration facilities and exhaust gas treatment technologies, the generation of harmful substances has been suppressed, and the presence of polyvinyl chloride resin is being reexamined. In addition, more than half of the raw materials of polyvinyl chloride resin are made from salt, and the ethylene polymerization ratio derived from petrochemicals is also lower than that of olefin resins, so it is also said to be a resource-saving resin. Furthermore, polyvinyl chloride resin has the advantages of excellent processing suitability and easy recyclability. Therefore, from the viewpoint of reducing environmental impact, the demand for cosmetic sheets using polyvinyl chloride resin is increasing.

[0006] In addition, due to the increasing awareness of zero-energy houses (ZEH) and the like, the demand for highly heat-insulating resin sashes and window frames using polyvinyl chloride resin is increasing, and it is conceivable to decorate these base materials with decorative sheets. However, there are also problems such as the difficulty of recycling with olefin-based resin sheets. Therefore, by using a resin sash using polyvinyl chloride resin as described above and a decorative sheet using polyvinyl chloride resin together with the base material of the window frame, it can be expected to greatly contribute to reducing the environmental load.

[0007] Normally, when using a polyvinyl chloride sheet by laminating it on a base material such as a sash, bending processing is often performed. However, although conventional polyvinyl chloride sheets are excellent in processing suitability, cracks may occur during bending processing. The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a decorative sheet and a decorative material that have good bendability even when formed using a polyvinyl chloride resin, and are excellent in productivity and recyclability during printing.

Means for Solving the Problems

[0008] In order to solve the above problems, a decorative sheet according to one aspect of the present disclosure includes at least a coloring original reaction layer, a pattern layer, a transparent resin layer, and a surface protection layer, which are laminated in this order. The coloring original reaction layer is formed of a colored polyvinyl chloride resin, the transparent resin layer is formed of a transparent polyvinyl chloride resin, and the Martens hardness measured by a measurement method conforming to ISO 14577-1:2002 is in the range of 50 Mpa or more and 150 Mpa or less, and the total thickness of the sheet is in the range of 80 μm or more and 300 μm or less.

[0009] In addition, a decorative material according to another aspect of the present disclosure includes a base material for a decorative material and the above decorative sheet laminated on the base material for the decorative material.

Effects of the Invention

[0010] According to one aspect of the present disclosure, it is possible to provide a decorative sheet that has good bendability even when formed using a polyvinyl chloride resin, and further has excellent productivity and recyclability during printing.

Brief Description of the Drawings

[0011]

Figure 1

Embodiments for Carrying Out the Invention

[0012] Hereinafter, a decorative sheet and a decorative member according to an embodiment of the present disclosure 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 these drawings may be added. Further, the following embodiments illustrate 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 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. Also, 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 90 degrees, "left and right" and "up and down" are read in exchange, and if the paper surface is rotated 180 degrees, it goes without saying that "left" becomes "right" and "right" becomes "left".

[0013] Hereinafter, with reference to FIG. 1, the configuration of the decorative material 10 will be described. As shown in FIG. 1, the decorative material 10 includes a decorative sheet 1 and a base material 8 which is a base material for the decorative material and to which the decorative sheet 1 is adhered. In this example, on one surface of the base material 8 (the upper surface in FIG. 1), the decorative sheet 1 is laminated. That is, the decorative material 10 includes the base material 8 and the decorative sheet 1 laminated on one surface of the base material 8. The specific configurations of the decorative sheet 1 and the base material 8 will be described later.

[0014] (Configuration of the decorative sheet) As shown in FIG. 1, the decorative sheet 1 includes a coloring original layer 2, a pattern layer 3, a transparent resin layer 4, a surface protection layer 5, and an embossed portion 7. Specifically, in the decorative sheet 1, the pattern layer 3, the transparent resin layer 4, and the surface protection layer 5 are laminated in this order on the coloring original layer 2 (on one surface side of the coloring original layer 2). Further, an embossed portion 7 is formed on the surface of the surface protection layer 5 that is the outermost layer of the decorative sheet 1 (the surface on the side opposite to the transparent resin layer 4).

[0015] In addition, in the decorative sheet 1 according to the present embodiment, it can be provided as necessary. For example, since the coloring original layer 2 of the decorative sheet 1 has concealability, at least the coloring original layer 2, the transparent resin layer 4, and the surface protection layer 5 may be laminated in this order.

[0016] (Coloring original layer) The coloring original layer 2 is configured to be a support of the decorative sheet 1. The coloring original layer 2 in the present embodiment is opaque and colored, and has concealability. Thereby, when forming a decorative member by laminating the decorative sheet 1 and a predetermined substrate, for example, the coloring original layer 2 can conceal color variations, defects, etc. on the substrate surface.

[0017] In addition, as the material of the coloring original layer 2, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and further has printability is used. That is, in the decorative sheet 1 according to the present embodiment, the coloring original layer 2 is a colored polyvinyl chloride resin layer formed of a colored polyvinyl chloride resin. By forming the original layer with PVC, the edge material of the decorative sheet 1 during the production of the decorative material 10 or the used decorative sheet 1 can be melted and extruded by an extruder or the like and reused as a recycled base material. In addition, PVC is easier to reuse by melting than olefin-based resins. That is, the decorative sheet 1 according to the present embodiment can improve the processing suitability and recyclability by forming the coloring original layer 2 with PVC.

[0018] In addition, the coloring original layer 2 as an opaque colored polyvinyl chloride colored sheet (colored film) can appropriately select the hue as the base color of the pattern layer 3. Further, when making use of the texture of the surface of the base material 8 which is a base material for decorative materials, the coloring original layer 2 is preferably a colored polyvinyl chloride resin layer having a transparency that allows the surface of the base material 8 to be seen through.

[0019] For example, the coloring original layer 2 can be colored by mixing and kneading a coloring agent such as a pigment into the resin material (polyvinyl chloride) constituting the coloring original layer 2. As the coloring agent, organic and inorganic pigments can be used, but it is preferable to use an inorganic pigment. That is, the coloring original layer 2 preferably contains an inorganic substance as the coloring agent. For example, the coloring original layer 2 preferably contains any one or more inorganic substances such as calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. Thereby, the thermal stability of the decorative sheet 1 main body is improved. Further, since the concealability is improved by the inclusion of the inorganic substance, variations in the color of the surface of the base material and the like can be concealed during the process of bonding the decorative sheet 1 to the base material, and the designability can be improved.

[0020] In addition, 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 diffusing agents, and gloss modifiers may be added to the colorant precursor layer 2 as necessary.

[0021] (Pattern layer) The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colorant precursor layer 2 and is a layer for adding a pattern for imparting design properties. More specifically, the pattern layer 3 is provided between the colorant precursor layer 2 and the transparent resin layer 4. Note that the pattern layer 3 may be omitted when it is possible to substitute it with the coloring of the colorant precursor layer 2. In addition, the pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like for forming the pattern layer 3 is formed 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.

[0022] The printing ink, paint, or the like for forming the pattern layer 3 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. As the binder resin, for example, urethane resins, acrylic resins, vinyl chloride acetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but are not limited thereto. As the pattern, any pattern can be used. For example, wood grain patterns, stone grain patterns, cloth grain patterns, abstract patterns, geometric patterns, characters, symbols, solid colors, or combinations thereof can be used. In addition, a concealing layer may be provided between the pattern layer 3 and the colorant precursor layer 2 in order to improve the concealability of the decorative sheet 1. The concealing layer is formed using an opaque printing ink or paint containing a large amount of an opaque pigment such as titanium dioxide or iron oxide.

[0023] The thickness of the pattern layer 3 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 3 is 1 μm or more, printing can be made clear. Also, when the thickness of the pattern layer 3 is 10 μm or less, the printing workability when manufacturing the decorative sheet 1 is improved, and it is possible to suppress the manufacturing cost. In addition, to the pattern layer 3, in order to impart various functions, for example, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retarders may be added. Further, the pattern layer 3 may have a configuration having a solid-color original layer painted solid to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer for adding a pattern for imparting design.

[0024] (Transparent resin layer) The transparent resin layer 4 is a layer for improving the weather resistance of the decorative sheet 1. In the decorative sheet 1 according to the present embodiment, as the material of the transparent resin layer 4, a polyvinyl chloride (PVC) resin film having flexibility, thermoplasticity, good moldability and processing suitability, and printability is used. That is, in the decorative sheet 1 according to the present embodiment, the transparent resin layer 4 is a transparent polyvinyl chloride resin layer formed of a transparent polyvinyl chloride resin. As described above, PVC can be used as a recycled base material by melting and extruding it, and it is easier to reuse by melting compared to olefin-based resins.

[0025] That is, the decorative sheet 1 according to the present embodiment can surely improve the processing suitability and recyclability by forming the original layer 2 and the transparent resin layer 4 with PVC. Note that the transparent resin layer 4 preferably has transparency such that the pattern layer 3 provided on the surface on the side of the original layer 2 (the lower surface in FIG. 1) can be seen through. For example, it is colorless transparent, colored transparent, or translucent.

[0026] 〔Martens hardness〕 In this embodiment, the transparent resin layer 4 has a Martens hardness within the range of 50 Mpa or more and 150 Mpa or less. Thereby, the cosmetic sheet has a hardness suitable for production and use, the bendability is improved, and whitening cracks during bending can be suppressed. In addition to the bendability, the scratch resistance is improved, and the productivity during printing can be further improved. When the Martens hardness is less than 50 Mpa, the cosmetic sheet becomes excessively flexible, and the productivity and scratch resistance are reduced. Further, when the Martens hardness exceeds 150 Mpa, the cosmetic sheet becomes excessively hard, and whitening cracks are caused during bending or the like. The Martens hardness is measured using a Martens hardness tester by a measurement method conforming to ISO 14577-1:2002. The measurement conditions are, for example, an indentation speed of 2 μm / s and a load of 2.0 mN. The Martens hardness is measured, for example, for the transparent resin layer 4 formed as a single-layer vinyl chloride sheet. Further, the present invention is not limited to this, and the surface of the transparent resin layer 4 before the formation of the surface protective layer 5 may be measured, or the cross section of the transparent resin layer 4 exposed when the cosmetic sheet 10 is cut may be measured.

[0027] 〔Indentation elastic modulus〕 In this embodiment, the transparent resin layer 4 preferably has an indentation elastic modulus in the range of 1500 Mpa or more and 3500 Mpa or less. Thereby, the decorative sheet has a hardness more suitable for production and use, the bendability is further improved, and cracking and sheet springback during bending can be suppressed. In addition to the bendability, the scratch resistance is improved, and the productivity during printing can be further improved. When the indentation elastic modulus is less than 1500 Mpa, the decorative sheet becomes excessively flexible, and a decrease in productivity and a reduction in scratch resistance may occur during printing. Further, when the indentation elastic modulus exceeds 3500 Mpa, the decorative sheet becomes excessively hard, and sheet springback and cracking may occur during bending or the like. The indentation elastic modulus is measured under the same conditions as the above measurement conditions using the above martens hardness tester by a measurement method conforming to ISO 14577-1:2002. The indentation elastic modulus is measured, for example, with respect to the transparent resin layer 4 formed as a single-layer vinyl chloride sheet. Further, the present invention is not limited to this, and the surface of the transparent resin layer 4 before the formation of the surface protective layer 5 may be measured, or the cross section of the transparent resin layer 4 exposed when the decorative sheet 10 is cut may be measured.

[0028] 〔Plasticizer〕 A plasticizer may be added to the transparent resin layer 4 in order to further improve the bendability of the vinyl chloride resin. As the plasticizer, a polyester-based plasticizer or a phthalic acid-based plasticizer can be used. The addition amount of the plasticizer in the transparent resin layer 4 is preferably in the range exceeding 15 PHR and less than 40 PHR, and more preferably in the range of 20 PHR or more and 35 PHR or less. Thereby, the martens hardness and the indentation elastic modulus of the transparent resin layer 4 can be suitably controlled, and the bendability can be surely improved.

[0029] 〔Ultraviolet absorber〕 Further, in this embodiment, the transparent resin layer 4 contains an ultraviolet absorber. That is, in the decorative sheet 1 according to this embodiment, the transparent resin layer 4 is preferably formed of a transparent polyvinyl chloride resin and contains an ultraviolet absorber. Thereby, excellent weather resistance can be imparted to the transparent resin layer 4. More specifically, the transparent resin layer 4 preferably contains at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers as the ultraviolet absorber. Thereby, excellent weather resistance can be imparted to the transparent vinyl chloride resin forming the transparent resin layer 4, and the weather resistance of the decorative sheet 1 can be improved. For this reason, discoloration when used outdoors for a long period can be suppressed, and the decorative sheet 1 using polyvinyl chloride can be suitably used as an exterior sheet for outdoor use. The addition amount of the ultraviolet absorber in the transparent resin layer 4 may be added according to the desired weather resistance. For example, it is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the transparent vinyl chloride resin constituting the transparent resin layer 4. Thereby, the weather resistance of the decorative sheet 1 can be surely improved.

[0030] (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.

[0031] (Triazine-based ultraviolet absorber) Examples of the triazine-based ultraviolet absorber 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.

[0032] <Light stabilizer> In this embodiment, the transparent resin layer 4 may further contain a light stabilizer in addition to the ultraviolet absorber as a weathering agent. Thereby, the weather resistance performance of the cosmetic sheet 1 can be made better.

[0033] As the light stabilizer added to the transparent resin layer 4, for example, a radical scavenger can be used. By using the above-mentioned triazine-based ultraviolet absorber and the radical scavenger in combination, the weather resistance of the cosmetic sheet 1 can be further improved. Examples of the hindered amine-based radical scavenger that can be used in this embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / succinic acid diethyl polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl〕-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(1,2,2,6,(6-Pentamethyl-4-piperidyl)amino)-s-triazin-6-yl)-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate cyclohexane and the reaction product of N-butyl 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine with 2-aminoethanol, etc. are mentioned, but not limited thereto.,

[0034] In this embodiment, the addition amount of the light stabilizer (for example, a hindered amine-based radical scavenger) in the transparent resin layer 4 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 transparent vinyl chloride resin constituting the transparent resin layer 4. By adding 1 part by mass or more of the light stabilizer, desired weather resistance can be obtained, and by setting it to 30 parts by mass or less, bleed-out of the weathering agent can be suppressed, and the influence on other physical properties of the surface protective layer 5 can be suppressed.

[0035] The thickness of the transparent resin layer 4 is preferably in the range of 50 μm or more and 150 μm or less, more preferably in the range of 50 μm or more and 100 μm or less, and even more preferably in the range of 60 μm or more and 80 μm or less. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 can be surely improved, and further, unevenness of the adherend substrate (in this example, the substrate 8) can be absorbed to improve the construction finish of the decorative sheet 1. Also, when the thickness of the transparent resin layer 4 is 150 μm or less, the transparent resin layer 4 is not formed thicker than necessary, the processing propriety (for example, bend processability) is improved, and the manufacturing cost of the decorative sheet 1 can be reduced.

[0036] (Surface protective layer) The surface protection layer 5 of the cosmetic sheet 1 according to this embodiment is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design to the cosmetic sheet 1. The material constituting the surface protection layer 5 is not particularly limited, and for example, it can be appropriately selected and used from resin materials such as urethane-based, acrylic-based, acrylic-silicone-based, fluorine-based, and epoxy-based. The surface protection layer 5 may be blended with various additives such as, for example, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light diffusing agents, and gloss modifiers, as necessary. Hereinafter, an example of the surface protection layer 5 according to this embodiment will be described with specific examples.

[0037] In this embodiment, the surface protection layer 5 may mainly contain 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.

[0038] 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 acrylic resin compositions, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protection layer 5. By setting the content of cyclohexyl (meth) acrylate to 5% by mass or more, a sufficient deterioration suppression effect can be obtained. Also, 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 protection layer 5 of the cosmetic 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 protection layer 5 is 50% by mass or more with respect to the mass of the entire surface protection layer 5.

[0039] As monomer components of the acrylic resin composition that can be used for the surface protective layer 5 according to this embodiment, in addition to cyclohexyl (meth)acrylate, for example, cyclohexylmethyl (meth)acrylate, cyclohexylethyl (meth)acrylate, cyclohexylpropyl (meth)acrylate, cyclohexylbutyl (meth)acrylate, dimethylcyclohexane mono(meth)acrylate, dimethylcyclohexane di(meth)acrylate, trimethylcyclohexane mono(meth)acrylate, trimethylcyclohexane di(meth)acrylate, trimethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane mono(meth)acrylate, tetramethylcyclohexane di(meth)acrylate, tetramethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane tetra(meth)acrylate, dicyclohexylmethyl (meth)acrylate, dicyclohexylmethyl (meth)acrylate, phenoxycyclohexylmethyl (meth)acrylate, methoxycyclohexylmethyl (meth)acrylate, and the like can be mentioned. Among these, those containing isomers may be each isomer alone and / or a mixture of each isomer.

[0040] Also, in this embodiment, the surface protective layer 5 may be formed by applying 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 to the outermost surface of the decorative sheet. Although it will be described in detail later, for example, after applying a coating liquid containing the above-described acrylic resin composition and a weathering agent onto the transparent resin layer 4 on which the embossed portion 7 is formed, wiping it may embed the coating liquid into the embossed portion 7 to form the surface protective layer 5. As a method for curing the coating liquid for forming the surface protective layer 5, for example, any of a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type in which curing is performed by irradiating ultraviolet rays, ionizing radiation, etc. can be used. However, considering weather resistance, the two-component curing type or the active energy ray curing type is preferable. If the post-processability after being bonded to various substrates to form a decorative member is considered, a two-component curing type crosslinked by isocyanate curing is desirable.

[0041] 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.

[0042] 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)acrylate copolymer containing hydroxyethyl (meth)acrylate as a monomer component can be used. On the other hand, as the polyisocyanate compound having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, burette types, etc. synthesized from one or more of these compounds by known techniques can be mentioned. In addition, a composition in which one or more selected from these different types of polyisocyanates are mixed can be used. Among them, HDI, or the trimer type, TMP adduct type, burette type of HDI is preferable from the viewpoint of weather resistance. The content of the isocyanate compound with respect to the resin component described above can be arbitrarily set, but it is desirable to set it so that the equivalent ratio of hydroxyl group / isocyanate group is about 1 / 1 to 1 / 3. In particular, when the equivalent of the hydroxyl group is more than the equivalent of the isocyanate group, crosslinking does not proceed sufficiently and the desired performance is not added to the surface protective layer 5, which may not be preferable.

[0043] When the curing method of the coating liquid for forming the surface protective layer 5 is active energy ray curing, as the active energy ray curing type acrylic resin composition, known monomers, oligomers, etc. having a (meth)acryloyl group can be used. In addition to these monomers and oligomers, the cyclohexyl (meth)acrylate described above may be blended.

[0044] In order to further improve the weather resistance of the decorative sheet 1, in this embodiment, an ultraviolet absorber and a light stabilizer are added as weathering agents to the surface protective layer 5. That is, the surface protective layer 5 contains an ultraviolet absorber and a light stabilizer.

[0045] <Ultraviolet absorber> As the ultraviolet absorber, for example, known ones such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), benzophenone-based ones can be used. Among these, if a hydroxyphenyltriazine-based ultraviolet absorber is selected, the triazine skeleton suppresses bleed, and also, due to the fact that the triazine skeleton is chemically more stable compared to the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, it becomes possible to maintain long-term ultraviolet absorption performance. That is, it is preferable that the surface protective layer 5 contains a triazine-based ultraviolet absorber as the ultraviolet absorber.

[0046] 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 5. 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."

[0047] In the surface protection layer 5 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 5. By setting the addition amount of the above-mentioned ultraviolet absorber to 1 part by mass or more, the weather resistance improvement effect is exhibited, and by setting it to 30 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protection layer 5 can be suppressed to a practically acceptable level. In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber added to the surface protection layer 5, its addition amount is preferably in the range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition, more preferably in the range of 5 parts by mass or more and 15 parts by mass or less, and even more preferably in the range of 8 parts by mass or more and 12 parts by mass or less. By setting the addition amount of ultraviolet absorber A to 1 part by mass or more, the weather resistance improvement effect is exhibited, and by setting it to 20 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protection layer 5 can be suppressed to a practically acceptable level.

[0048] Further, 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 5, 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 in substantially the same wavelength region, so that the wavelength region for absorbing ultraviolet rays becomes wider by the combination. Note that 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is used as ultraviolet absorber B, is generally known as the main component of "ADEKA STAB LA-46: manufactured by ADEKA CORPORATION".

[0049] In this embodiment, it is preferable that the addition amount of the ultraviolet absorber A in the surface protective layer 5 is in the range of 10 parts by mass or more and 200 parts by mass or less, more preferably in the range of 20 parts by mass or more and 100 parts by mass or less, and even more preferably in the range of 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the ultraviolet absorber B. By setting the addition amount of the ultraviolet absorber A within the above numerical range, more excellent weather resistance can be imparted.

[0050] 〈Light stabilizer〉 In this embodiment, the surface protective layer 5 further contains a light stabilizer in addition to the ultraviolet absorber as a weathering agent. Thereby, the weather resistance performance of the decorative sheet 1 can be improved.

[0051] As the light stabilizer added to the surface protective layer 5, 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 decorative sheet 1 can be further improved. The hindered amine-based radical scavenger that can be used for the surface protective layer 5 in this embodiment is the same as that of the transparent resin layer 4, so detailed description is omitted.

[0052] In this embodiment, the addition amount of the light stabilizer (for example, a hindered amine-based radical scavenger) in the surface protective layer 5 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 5. By adding 1 part by mass or more of the light stabilizer, desired weather resistance can be obtained. By setting it to 30 parts by mass or less, bleeding out of the weathering agent can be suppressed, and the influence on other physical properties of the surface protective layer 5 can be suppressed. In addition, although it is assumed that the surface protective layer 5 contains an ultraviolet absorber and a light stabilizer in this embodiment, the present disclosure is not limited thereto. The surface protective layer 5 may be configured to have desired weather resistance according to the application, and the surface protective layer 5 may include at least one of an ultraviolet absorber and a light stabilizer.

[0053] <Coating amount> The coating amount of the surface protective layer 5, that is, the coating amount of the material of the surface protective layer 5 on the transparent resin layer 4, is 3 g / m 2 or more and 10 g / m 2 or less is preferable. If the coating amount is less than 3 g / m 2 , 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, good weather resistance and recyclability can be achieved simultaneously. Also, by setting the coating amount within this range, productivity and processability (e.g., bend processability) can be improved.

[0054] (Embossed part) As shown in FIG. 1, an embossed part 7 is provided on the outermost surface of the decorative sheet 1 according to this embodiment. By providing the embossed part 7 on the outermost surface, the design property is improved, and furthermore, for example, it becomes possible to improve the fingerprint resistance while maintaining the matte feeling on the surface of the decorative sheet 1. Also, the embossed part 7 can be formed into various uneven shapes such as wood grain board conduit grooves, stone slab surface irregularities (such as granite split surfaces), cloth surface textures, satin finish, sandblasted finish, hairline, and multi-line grooves, etc., to impart a given design property to the surface of the decorative sheet 1. The embossed part 7 can be formed into various uneven shapes according to, for example, the design of the pattern layer 3 or the desired design property. The embossed part 7 is formed on the surface (outermost surface) side of the surface protective layer 5 which is the outermost layer of the decorative sheet 1, and constitutes an uneven pattern. In this embodiment, the above-described surface protective layer 5 is embedded in the embossed part 7 that constitutes this uneven pattern. Hereinafter, this point will be explained.

[0055] In the cosmetic sheet 1 according to this embodiment, the embossed portion 7 is provided in the transparent resin layer 4. That is, the transparent resin layer 4 is the layer in which the embossed portion 7 is formed. The shape of the uneven pattern provided on the surface of the transparent resin layer 4 is not particularly limited, but the shape of the embossed portion 7 constituting the uneven pattern is preferably such that the opening diameter increases from the back side (in this example, the pattern layer 3) to the front side (the surface protective layer 5) of the transparent resin layer 4. With such a shape, when the surface protective layer composition (coating liquid) is embedded in the embossed portion 7 by wiping, the embedding becomes easy.

[0056] Also, the side surface forming the embossed portion 7 is preferably an inclined surface. If the side surface forming the embossed portion 7 is an inclined surface, when the surface protective layer composition (coating liquid) is embedded in the embossed portion 7 by wiping, the embedding becomes easy. Also, all of the side surfaces forming the embossed portion 7 may be covered with the surface protective layer 5. Also, the depth of the embossed portion 7 is preferably in the range of 1 μm or more and 50 μm or less with respect to the thickness direction of the transparent resin layer 4. If the depth of the embossed portion 7 is within the above numerical range, when the surface protective layer composition (coating liquid) is embedded in the embossed portion 7 by wiping, the embedding becomes easy, and peeling of the surface protective layer can be prevented.

[0057] Also, the width of the embossed portion 7 is preferably in the range of 1 μm or more and 20 μm or less. If the width of the embossed portion 7 is within the above numerical range, when the surface protective layer composition (coating liquid) is embedded in the embossed portion 7 by wiping, the embedding becomes easy, and peeling of the surface protective layer embedded in the embossed portion 7 can be prevented.

[0058] Further, it is preferable that the embossed portion 7 is entirely filled (packed) with the surface protective layer composition (coating liquid). However, the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is preferably 10% or more. If the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 10% or more, the weather resistance in the embossed portion 7 can be improved. That is, if the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 10% or more, the occurrence of whitening and breakage in the conduit portion can be reduced. Also, as described above, the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is preferably 100%. However, it is more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 80% or less, and it is even more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 60% or less. If the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 is 80% or less, a sufficient tactile sensation can be obtained in the embossed portion 7. Also, by setting the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 7 to 100%, the surface of the surface protective layer 5 filled in the embossed portion 7 and the surface of the transparent resin layer 4 in the region without the embossed portion 7 may be flush, so to speak.

[0059] (Weather-resistant resin layer) As described above, in the present embodiment, the transparent resin layer 4 contains an ultraviolet absorber, and further the surface protective layer 5 contains an ultraviolet absorber and a light stabilizer. In the present embodiment, the laminate combining the two layers of the transparent resin layer 4 and the surface protective layer 5 is also referred to as a weather-resistant resin layer. The weather-resistant resin layer imparts excellent weather resistance to the decorative sheet 1. By providing the weather-resistant resin layer (transparent resin layer 4 and surface protective layer 5), the decorative sheet 1 according to the present embodiment is imparted with excellent weather resistance, and for example, it can be expected to withstand long-term outdoor use as a decorative sheet for decorating the surface of a decorative material for exterior applications. Furthermore, in the cosmetic sheet 1 according to the present embodiment, when the two layers of the transparent resin layer 4 and the surface protective layer 5 are combined, the transmittance of ultraviolet rays with a wavelength of 380 nm is preferably 20%T or less. That is, in the weather-resistant resin layer, the transmittance of ultraviolet rays with a wavelength of 380 nm is preferably 20%T or less. Thereby, the weather resistance of the cosmetic sheet 1 can be further improved.

[0060] (Total thickness of the sheet) The thickness (total thickness) of the entire cosmetic sheet 1 according to the present embodiment may be in the range of 80 μm or more and 300 μm or less, and more preferably in the range of 120 μm or more and 200 μm or less. Thereby, for example, it is possible to form the cosmetic sheet 1 having concealability equivalent to that of a conventional cosmetic sheet formed using an olefin-based resin and having good processability. On the other hand, when the total thickness is less than 80 μm, the stiffness of the cosmetic sheet becomes insufficient during processing, and the productivity is reduced. Further, when the total thickness exceeds 300 μm, the bend processability is reduced. In this example, the total thickness of the coloring original reaction layer 2 and the transparent resin layer 4 is defined as the total thickness of the cosmetic sheet 1.

[0061] As described above, the cosmetic sheet 1 according to the present embodiment has at least a coloring original reaction layer 2, a transparent resin layer 4, and a surface protective layer 5 laminated in this order. The coloring original reaction layer 2 is formed of a colored polyvinyl chloride resin, the transparent resin layer 4 is formed of a transparent polyvinyl chloride resin and contains an ultraviolet absorber, and the surface protective layer 5 contains an ultraviolet absorber and a light stabilizer. Thereby, even when formed using a polyvinyl chloride resin, a cosmetic sheet having excellent weather resistance, further excellent processing suitability and recyclability can be obtained.

[0062] (Cosmetic material) In the present embodiment, the above-described cosmetic sheet 1 may be bonded to a base material 8 that is a base material for a cosmetic material to obtain a cosmetic material 10.

[0063] (Base material) As the base material 8, 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 fiberboard, or a hard fiberboard can be adopted. Further, as the metal base material, a steel plate, an aluminum plate, etc. can be adopted. Also, the base material 8 may be a resin such as plastic or a composite material thereof. When the base material 8 is a resin base material, for example, a vinyl chloride resin can be adopted. The base material 8 made of a vinyl chloride resin has high heat insulation properties and the demand as a window frame fitting (sash) is increasing. Further, the decorative material 10 obtained by decorating the base material 8 made of a vinyl chloride resin with the decorative sheet 1 can be dissolved and reused both the base material 8 and the decorative sheet 1, and the recyclability can be made better by monomaterialization. Also, the base material 8 may be composed of, for example, a non-combustible steel plate or a non-combustible material defined in the Ministry of Construction Notification No. 1400.

[0064] As shown in FIG. 1, the decorative sheet 1 is laminated on one surface (the upper surface in FIG. 1) of the base material 8. That is, the decorative material 10 according to the present embodiment includes the base material 8 which is a base material for a decorative material and the decorative sheet 1 bonded to the base material 8. By bonding the decorative sheet 1 according to the present embodiment to the base material 8, even when formed using a polyvinyl chloride resin, a decorative material having good bendability and excellent recyclability can be obtained. More specifically, the decorative material 10 includes the base material 8 and the decorative sheet 1 laminated on one surface of the base material 8. Note that the configuration of the decorative material 10 is not limited to the example shown in FIG. 1. That is, the configuration of the decorative material 10 may be such that, in addition to one surface of the base material 8, it includes the decorative sheet 1 laminated on the other surface (the lower surface in FIG. 1) of the base material 8.

[0065] (Manufacturing method of decorative sheet and decorative member) Hereinafter, an example of the manufacturing method of the decorative sheet 1 according to the present embodiment will be briefly described. Print the pattern layer 3 on the above-described colored original layer 2. Next, a transparent resin layer 4 is formed on the colored original reaction layer 2 on which the pattern layer 3 is formed by thermal lamination. At the same time, an embossed pattern is provided on the surface of the transparent resin layer 4 opposite to the colored original reaction layer 2 by embossing to form an embossed portion 7. Next, a coating liquid for forming a surface protective layer 5 is applied to the surface of the transparent resin layer 4 on which the concavo-convex pattern (embossed portion 7) is formed. Finally, the coating liquid is wiped so as to be embedded in the embossed portion 7 constituting the concavo-convex pattern, and the coating liquid is cured to form a surface protective layer 5 on the transparent resin layer 4. In this way, the decorative sheet 1 according to the present embodiment is formed. Hereinafter, an example of a method for manufacturing the decorative material 10 according to the present embodiment will be briefly described. The above-described decorative sheet 1 and the base material 8 are bonded together to form a decorative material 10.

[0066] <Modification example> Although the hydroxyphenyltriazine-based ultraviolet absorber that can be added to the surface protective layer 5 has been described, the hydroxyphenyltriazine-based ultraviolet absorber that can be used in the present embodiment is not limited to these. The surface protective layer 5 according to the present embodiment may contain, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1). Further, the surface protective layer 5 may contain an ultraviolet absorber having a structure represented by the following general formula (2). Specifically, it may contain 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl)]-6-(4-methoxyphenyl)-s-triazine shown in the following formula (3), or may contain a hydroxyphenyltriazine-based ultraviolet absorber shown in the following formula (4).

[0067]

Chem.

[0068] In general formula (1), R1 to R3 are each independent and represent a hydrogen atom, a methyl group, a phenyl group, or an alkoxy group, and at least two of them are alkoxy groups having 8 to 18 carbon atoms and not containing a carbonyl group. R4 and R5 are each independent and represent a hydroxyl group, a methyl group, or a hydrogen atom. R6 to R8 are each independent and represent a methyl group or a hydrogen atom.

[0069]

Chemical formula

[0070] In general formula (2), R1 and R2 are alkoxy groups having 8 to 18 carbon atoms, R3 is an alkoxy group having 1 to 4 carbon atoms, R4 is a hydroxyl group, and R5 to R8 are hydrogen atoms.

[0071]

Chemical formula

[0072]

Chemical formula

[0073] Furthermore, by using a combination of hydroxyphenyltriazine-based and benzotriazole-based ultraviolet absorbers as the ultraviolet absorber, excellent weather resistance can be imparted due to their interaction. This is because the benzotriazole-based ultraviolet absorber has an absorption peak on the longer wavelength side than the hydroxyphenyltriazine-based ultraviolet absorber, so that the wavelength region for absorbing ultraviolet rays is further widened by the combination. As the addition amount of the benzotriazole-based ultraviolet absorber, a range of 1 part by mass or more and 30 parts by mass or less is preferable with respect to 100 parts by mass of the acrylic resin composition. By adding 1 part by mass or more, a desired effect can be obtained, and by setting it to 30 parts by mass or less, bleed-out of the weathering agent can be suppressed. However, since the benzotriazole-based ultraviolet absorber has an absorption peak on the longer wavelength side, it may have a yellowish tint, and when attention is required for the hue, it is advisable to suppress the addition amount.

[0074] Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumenylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole, etc., but are not limited thereto.

[0075] (Effects of this embodiment) The cosmetic sheet 1 and the cosmetic material 10 according to this embodiment have the following effects. (1) The decorative sheet 1 has at least a coloring original layer 2, a pattern layer 3, a transparent resin layer 4, and a surface protective layer 5 laminated in this order. The coloring original layer 2 is formed of a colored polyvinyl chloride resin, and the transparent resin layer 4 is formed of a transparent polyvinyl chloride resin. The Martens hardness measured by a measurement method conforming to ISO 14577-1:2002 is in the range of 50 Mpa or more and 150 Mpa or less, and the total thickness of the sheet is in the range of 80 μm or more and 300 μm or less. According to the above configuration, since the Martens hardness of the transparent resin layer 4 is within the above range, even when formed using a polyvinyl chloride resin, the bend processability is good, the productivity during printing is excellent, and further, since the coloring original layer 2 and the transparent resin layer 4 are formed of polyvinyl chloride, a decorative sheet excellent in recyclability can be provided. (2) Also, in the decorative sheet 1, the transparent resin layer 4 has an indentation elastic modulus measured by a measurement method conforming to ISO 14577-1:2002 in the range of 1500 Mpa or more and 3500 Mpa or less. According to the above configuration, since the indentation elastic modulus of the transparent resin layer 4 is within the above range, the bend processability becomes better, and a decorative sheet excellent in productivity and recyclability during printing can be provided.

[0076] (3) Also, in the decorative sheet 1, the coloring original layer 2 contains any one or more inorganic substances among calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. According to the above configuration, the thermal stability of the main body of the decorative sheet 1 is improved, and further, the coloring original layer 2 can be colored well to improve the concealability. (4) Also, in the decorative sheet 1, an embossed portion 7 is formed on the surface side of the surface protective layer 5. According to the above configuration, the design property of the decorative sheet 1 can be improved, and the fingerprint resistance of the surface of the decorative sheet 1 can be improved. (5) The decorative material 10 includes a base material 8 and a decorative sheet 1 bonded to the base material 8. According to the above configuration, even when formed using a polyvinyl chloride resin, a decorative material with excellent bend processability, productivity during printing, and recyclability can be provided.

[0077] <Example> Hereinafter, the present disclosure will be described in detail by showing examples and comparative examples, but the present disclosure is not limited to the following examples.

[0078] (Example 1) A pattern layer was provided by gravure printing a printing ink for PVC on a polyvinyl chloride resin (hereinafter, PVC: Poly Vinyl Chloride) sheet colored with an inorganic colorant as a colored original layer. Then, a transparent PVC sheet was thermally laminated as a transparent resin layer on the colored original layer provided with the pattern layer, and a surface protection layer mainly composed of an acrylic resin composition was formed on the transparent resin layer. Thereafter, the decorative material according to Example 1 was obtained by bonding the surface of the colored original layer (colored PVC sheet) opposite to the pattern layer to a PVC substrate using a urethane-based adhesive. The configuration of each layer according to this example is shown below. 〔Colored original layer〕 Material: PVC, Thickness: 80 μm 〔Transparent resin layer〕 Material: PVC, Thickness: 80 μm · Additive: Polyester-based plasticizer (PN-7160 manufactured by ADEKA) ··· 25 PHR Triazine-based ultraviolet absorber ··· 0.5 part by mass with respect to 100 parts by mass of PVC 〔Surface protection layer〕 · Main agent (methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) ··· 90 parts by mass · Ultraviolet absorber (Tinuvin 479; manufactured by BASF Japan Ltd.) ··· 9 parts by mass · Light stabilizer (Tinuvin 123; manufactured by BASF Japan Ltd.) ··· 1 part by mass · Curing agent (Takenate D170; manufactured by Mitsui Chemicals, Inc.) ·· 10 parts by mass · Solvent (ethyl acetate) ··· 240 parts by mass · Coating amount: 3 g / m2 〔Total sheet thickness〕 160 μm (= Thickness of colored original layer: 80 μm + Thickness of transparent resin layer: 80 μm)

[0079] (Example 2) The thickness of the transparent resin layer was set to 20 μm. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 2 were obtained. (Example 3) The thickness of the transparent resin layer was set to 170 μm. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 3 were obtained. (Example 4) The amount of plasticizer added in the transparent resin layer was set to 20 PHR. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 4 were obtained. (Example 5) In the same manner as in Example 1, the decorative sheet and the decorative material of Example 5 were obtained. (Example 6) The amount of plasticizer added in the transparent resin layer was set to 30 PHR. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 6 were obtained. (Example 7) The amount of plasticizer added in the transparent resin layer was set to 35 PHR. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 6 were obtained. (Example 8) The plasticizer in the transparent resin layer was phthalic acid-based (DINP), and the added amount was set to 20 PHR. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 8 were obtained. (Example 9) The plasticizer in the transparent resin layer was phthalic acid-based (DINP), and the added amount was set to 30 PHR. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 9 were obtained. (Example 10) The colorant in the colored original layer was organic. Otherwise, in the same manner as in Example 1, the decorative sheet and the decorative material of Example 10 were obtained.

[0080] (Comparative Example 1) The thickness of the coloring original layer was set to 10 μm, and the thickness of the transparent resin layer was set to 40 μm. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 1 were obtained. (Comparative Example 2) The thickness of the transparent resin layer was set to 270 μm. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 2 were obtained. (Comparative Example 3) The amount of plasticizer added to the transparent resin layer was set to 10 PHR. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 3 were obtained. (Comparative Example 4) The amount of plasticizer added to the transparent resin layer was set to 15 PHR. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 4 were obtained. (Comparative Example 5) The amount of plasticizer added to the transparent resin layer was set to 40 PHR. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 5 were obtained. (Comparative Example 6) The plasticizer in the transparent resin layer was phthalic acid-based (DINP), and the added amount was set to 10 PHR. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 6 were obtained. (Comparative Example 7) The plasticizer in the transparent resin layer was phthalic acid-based (DINP), and the added amount was set to 40 PHR. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 7 were obtained. (Comparative Example 8) The transparent resin layer was formed of an olefin-based resin. Otherwise, in the same manner as in Example 1, a decorative sheet and a decorative material of Comparative Example 8 were obtained.

[0081] <Measurement of Martens hardness and indentation elastic modulus> Regarding the decorative sheets obtained in each Example and Comparative Example, the Martens hardness and indentation elastic modulus were measured using a Martens hardness tester (manufactured by Fischer) by a measurement method conforming to ISO 14577-1:2002. The measurement conditions were an indentation speed of 2 μm / s and a load of 2.0 mN.

[0082] <Evaluation> For the cosmetic sheets obtained in each example and comparative example, the scratch resistance, productivity, processability (bending processability), weather resistance, recyclability, and concealability were evaluated by the following methods. The evaluation results are shown in Table 1.

[0083] (Surface hardness) Using a pencil (manufactured by Hi-uni MITSU-BISHI) with the tip flattened with sandpaper, a load of 750 g was applied, and the sample surface of the cosmetic sheet obtained in each example and comparative example was pushed at a speed of 0.8 mm / s for a distance of 7 mm. The hardness of the hardest pencil (pencil hardness) that did not cause scratches on the surface was evaluated.

[0084] (Productivity) For the cosmetic sheets of each example and comparative example, the productivity was evaluated under the conditions of printing production on the film. When it was possible to produce under a wide range of production conditions, it was rated as "◎"; when it was possible to produce by limiting the production conditions, it was rated as "○"; when it was difficult to produce even by limiting the conditions, it was rated as "×". In this example, "〇" or above was considered a pass.

[0085] (Bending processability) Using the cosmetic sheets of each example and comparative example, wrapping processing was performed on the PVC substrate. The bent part of the surface of the cosmetic sheet after wrapping processing was visually observed to check for abnormalities such as whitening or cracks (cracks and fissures), and the state of the bending processability was evaluated. The evaluation criteria were as follows. ◎: No abnormalities were confirmed, and it had the same bending processability as a cosmetic sheet made of an olefin resin. 〇: Slight abnormalities were confirmed, and although it was inferior to a cosmetic sheet made of an olefin resin, bending processing was possible. ×: Abnormalities were confirmed over the entire surface, and bending processing was impossible. In this example, "〇" or above was considered a pass.

[0086] (Weather resistance test) The appearance of the cosmetic members of each example and comparative example after the weathering acceleration test was visually evaluated according to the following criteria. The weathering acceleration test was carried out using a Metal Weather Tester (KU-R5DCI-A) manufactured by Daipra Wintech Co., Ltd. at a black panel temperature of 63 °C and an illuminance of 65 mW / cm 2 2 ◎: The color difference before and after the weather resistance test is less than ΔE = 2 〇: The color difference before and after the weather resistance test is ΔE = 2 or more and 4 or less ×: Overall, the color difference before and after the weather resistance test is ΔE = 4 or more In this example, "〇" or above was regarded as passing.

[0087] (Recyclability test) For the decorative materials (PVC base material and decorative sheet) of each example and comparative example, the ease of decomposition into single materials was evaluated. The evaluation criteria are shown below. ◎: Easily decomposable 〇: Decomposable with some effort ×: Difficult to decompose In this example, "〇" or above was regarded as passing.

[0088] (Concealability) For the decorative sheets of each example and comparative example, a white plate and a black plate were placed under the colored original reaction layer (lower layer). When the color of each plate could not be distinguished through the colored original reaction layer, it was rated as "〇", and when the color could be distinguished, it was rated as "×".

[0089] The above evaluation results are shown in Table 1 together with the composition of the decorative sheet.

[0090]

Table 1

[0091] As can be seen from Table 1, in the cosmetic materials using the cosmetic sheets of Examples 1 to 10, the colored original layer is formed of a colored polyvinyl chloride resin, the transparent resin layer is formed of a transparent polyvinyl chloride resin, the Martens hardness is in the range of 50 MPa or more and 150 MPa or less, and the indentation elastic modulus is in the range of 1500 MPa or more and 3500 MPa or less. Further, the total thickness of the sheet is in the range of 80 μm or more and 300 μm or less. Thereby, in the cosmetic sheets of Examples 1 to 10, the bendability, productivity, and recyclability were all qualified (above "〇"). Also, the pencil hardness (surface hardness) was all 3B or 4B, and it was found that the cosmetic sheets of each example had both a surface hardness that could withstand actual use and appropriate flexibility. That is, it was found that the cosmetic sheets of Examples 1 to 10 had good bendability and were further excellent in productivity and recyclability.

[0092] Furthermore, it was found that the cosmetic sheets of each example also passed (above "〇") in terms of weather resistance by including an ultraviolet absorber in the transparent resin layer and a weathering agent (ultraviolet absorber and light stabilizer) in the surface protective layer, and had excellent weather resistance. Also, it was found that the cosmetic sheets of Examples 1 - 9 using an inorganic colorant in the colored original layer were superior in hiding power compared to the cosmetic sheet of Example 10 using an organic colorant.

[0093] On the other hand, in the cosmetic sheets of Comparative Examples 1 and 2, since the total thickness of the sheet was not in the range of 80 μm or more and 300 μm or less, the evaluation of bendability was unqualified ("×"). Also, in the cosmetic sheets of Comparative Examples 3, 4, and 6, the amount of plasticizer added was small, the flexibility of the transparent resin layer was not sufficient, and the Martens hardness and indentation elastic modulus exceeded the respective upper limit values, so the evaluation of bendability was unqualified ("×"). Also, in the cosmetic sheets of Comparative Examples 5 and 7, the amount of plasticizer added was large, the transparent resin layer became overly flexible, and the Martens hardness and indentation elastic modulus were less than the respective lower limit values, so the evaluation of bendability was unqualified ("×").

[0094] Also, as shown in Table 1, all of the cosmetic materials using the cosmetic sheets of Examples 1 to 10 passed the recyclability test (qualified with "△" or higher) as described above. In contrast, the cosmetic material of Comparative Example 8 using a cosmetic sheet that does not use polyvinyl chloride (PVC) in the transparent resin layer failed the recyclability test (×). That is, it was found that the cosmetic material using vinyl chloride resin in the cosmetic sheet and the base material has better recyclability than the case where vinyl chloride resin is not used in the cosmetic sheet.

[0095] Note that the cosmetic sheet and the cosmetic material of the present disclosure are not limited to the above-described embodiments and examples, and various modifications can be made without impairing the features of the invention.

[0096] Also, for example, the present disclosure can have the following configurations. (1) At least a coloring original reaction layer, a pattern layer, a transparent resin layer, and a surface protective layer are laminated in this order, The coloring original reaction layer is formed of a colored polyvinyl chloride resin, The transparent resin layer is formed of a transparent polyvinyl chloride resin and has a Martens hardness measured by a measurement method conforming to ISO 14577-1:2002 within a range of 50 Mpa or more and 150 Mpa or less, The total thickness of the sheet is within a range of 80 μm or more and 300 μm or less A cosmetic sheet characterized by the above. (2) The transparent resin layer has an indentation elastic modulus measured by a measurement method conforming to ISO 14577-1:2002 within a range of 1500 Mpa or more and 3500 Mpa or less The cosmetic sheet according to the above (1), characterized by the above. (3) The coloring original reaction layer contains any one or more inorganic substances among calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides The cosmetic sheet according to the above (1) or (2), characterized by the above. (4) An embossed portion is formed on the surface side of the surface protective layer. The decorative sheet according to any one of (1) to (3) above, characterized in that. (5) A base material for a decorative material, A decorative material comprising the decorative sheet according to any one of (1) to (4) above, laminated on the base material for the decorative material.

Industrial Applicability

[0097] The present disclosure is a technology suitable for surface decorative materials such as building exteriors and building quasi-exteriors, that is, entrance doors, frames, window frames, and projecting window counters.

Explanation of Symbols

[0098] 1 Decorative sheet 2 Coloring original reaction layer 3 Pattern layer 4 Transparent resin layer 5 Surface protective layer 7 Embossed portion 8 Base material 10 Decorative material

Claims

1. At least a colored base layer, a design layer, a transparent resin layer, and a surface protective layer are laminated in this order, The colored base layer is formed of a colored polyvinyl chloride resin, the transparent resin layer is formed of a transparent polyvinyl chloride resin, and has a Martens hardness measured by a measurement method in accordance with ISO 14577-1:2002 in the range of 50 MPa to 150 MPa; The total thickness of the sheet is within the range of 80 μm to 300 μm. A decorative sheet characterized by:

2. The transparent resin layer has an indentation elastic modulus in the range of 1500 MPa to 3500 MPa as measured by a measurement method conforming to ISO 14577-1:2002.

2. The decorative sheet according to claim 1.

3. The colored raw fabric layer contains one or more inorganic substances selected from the group consisting of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

3. The decorative sheet according to claim 2.

4. An embossed portion is formed on the surface side of the surface protective layer.

4. The decorative sheet according to claim 3.

5. A base material for a cosmetic material, The decorative sheet according to claim 1 , which is bonded to the substrate for decorative material; A decorative material comprising:

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