Laminate

Abstract

To provide a laminate (decorative sheet) excellent in weather resistance.SOLUTION: A decorative sheet 10 includes: a raw fabric layer 7 containing at least an olefin resin; and a lamination part 50 laminated on the raw fabric layer 7 and including at least a transparent resin layer 1. The lamination part 50 contains at least two kinds of light absorbers having maximum absorption wavelengths different from each other. The two kinds of light absorbers are an ultraviolet absorber having a maximum absorption wavelength of 280-330 nm and a visible light absorber having a maximum absorption wavelength of 380-430 nm.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a laminate. [Background technology]

[0002] The applications of decorative sheets are expanding from indoors to outdoors. An important required property of such decorative sheets is weather resistance. Conventionally, efforts have been made to improve weather resistance by adding an ultraviolet absorbing agent or a radical scavenger to a surface protective layer or a transparent resin layer (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2022-133017 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned conventional decorative sheets do not have sufficient weather resistance, which can cause problems such as a decrease in design.

[0005] The present disclosure has been made in view of the above circumstances, and has an object to provide a laminate (decorative sheet) that has excellent weather resistance. [Means for solving the problem]

[0006] In order to solve the above problems, a laminate according to one embodiment of the present disclosure is a laminate including a base sheet containing at least an olefin-based resin, and a laminate portion laminated on the base sheet and including at least a transparent resin layer, wherein the laminate portion contains at least two types of light absorbents having different maximum absorption wavelengths, and the two types of light absorbents are an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm. Effect of the Invention

[0007] According to one embodiment of the present disclosure, a laminate (decorative sheet) having excellent weather resistance can be provided. [Brief description of the drawings]

[0008] [Figure 1] 1 is a cross-sectional view illustrating a schematic configuration of a decorative sheet according to an embodiment of the present disclosure. [Diagram 2] FIG. 1 is a cross-sectional view showing a schematic configuration of a decorative sheet according to a first modified example of an embodiment of the present disclosure. [Diagram 3] 10 is a cross-sectional view illustrating a schematic configuration of a decorative material according to a second modified example of an embodiment of the present disclosure. [Figure 4] FIG. 11 is a cross-sectional view illustrating another configuration example of a decorative material according to a second modified example of an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the decorative sheet and decorative member according to the embodiment of the present disclosure 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 description are merely defined for the convenience of explanation and do not limit the technical ideas of the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left".

[0010] As a result of intensive research, the present inventors have found that by adding at least two types of light absorbing agents having different maximum absorption wavelengths (absorption wavelength regions) to a laminate portion that is laminated on a base sheet and includes at least a transparent resin layer, excellent weather resistance can be imparted to the laminate. This has led the present inventors to invent a decorative sheet (laminate) with excellent weather resistance.

[0011] In other words, the present disclosure proposes and provides a new design concept for improving the weather resistance of decorative sheets. This point will be described below. In the conventional design concept, in order to improve the weather resistance of decorative sheets, attention was focused on the ultraviolet absorbers added to the decorative sheets, and the type and amount of ultraviolet absorbers added, or the combination of ultraviolet absorbers and radical scavengers, was adjusted. This is because, traditionally, the wavelengths that cause degradation of polymeric materials were thought to be mainly in the UV-B range (280-320 nm), and ultraviolet absorbers were selected so that the maximum absorption wavelength matched (was included) this range.

[0012] In response to this, the present inventors have actually investigated the wavelengths of degradation in order to improve the weather resistance of decorative sheets, and have found that light in the 380-430 nm wavelength range, which is a wavelength range other than the UV-B range, also degrades transparent resin layers (for example, layers formed of polyolefin resins). In other words, they have newly discovered that in order to improve the weather resistance of decorative sheets, it is important to suppress not only the transmission of ultraviolet light in a specific range, but also the transmission of visible light in a specific range. As such, the design concept of the present disclosure is significantly different from conventional design concepts that focused only on ultraviolet absorbers, and aims to improve the weather resistance of the decorative sheet by suppressing the transmission of ultraviolet light in specific regions and the transmission of visible light in specific regions in the layers that make up the laminate, such as the surface protection layer and the transparent resin layer.

[0013] A first embodiment of the present disclosure (hereinafter, referred to as "the present embodiment") will be described below with reference to the drawings.

[0014] (Measurement of absorbance A) First, the "absorbance A" defined in this embodiment will be described. The absorbance A in this embodiment is a value measured using a method in accordance with JIS K0115:2004, and is a value measured for a laminate constituted only by a transparent resin layer and a surface protective layer.

[0015] In this embodiment, the absorbance A is measured for each of an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm. Hereinafter, regarding absorbance A, the value obtained by measuring an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm is referred to as absorbance A1, and the value obtained by measuring a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is referred to as absorbance A2.

[0016] In this embodiment, two types of light absorbents, i.e., an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm, are added to the laminate portion, which is a laminate including a surface protective layer, a transparent resin layer, etc. Furthermore, it is preferable that the ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm to the absorbance A2 of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is not less than 5. Note that the absorbance ratio (A1 / A2) in this embodiment is a value calculated from the intensity ratio of each absorbance A.

[0017] Moreover, it is preferable that the ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm is a triazine-based ultraviolet absorbing agent. It is also preferable that the laminated portion comprises, in order from the base sheet (raw material layer) side, a picture print layer, an adhesive layer, a transparent resin layer and a surface protective layer, and that the surface protective layer contains an ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm.

[0018] Furthermore, it is preferable that the laminated portion includes, in this order from the base sheet (raw material layer) side, a picture print layer, an adhesive layer, a transparent resin layer, and a surface protective layer, and that the surface protective layer contains an ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm, and the transparent resin layer contains a visible light absorber having a maximum absorption wavelength of 380 to 430 nm. It should be noted that the higher the value of absorbance A, the less light transmits, and the lower the value of absorbance A, the more light transmits.

[0019] (Composition of decorative sheet) Hereinafter, each component of the decorative sheet (one example of a laminate) of the present embodiment will be described. Note that in the present embodiment, the transparent resin layer (transparent resin layer) will be described as a single layer.

[0020] The decorative sheet 10 shown in Fig. 1 is a laminate comprising multiple layers, and comprises, from the top of the drawing, a surface protective layer 4, a transparent resin layer 1, an adhesive layer 5 (heat-sensitive adhesive layer, anchor coat layer, dry lamination adhesive layer), a picture print layer 6, a concealing layer 3, a base fabric layer 7, and an easy-adhesion layer 8. The base fabric layer 7 is a layer that serves as the base material for the decorative sheet 10, and is also referred to as a base material sheet or base material layer. The decorative sheet 10 according to this embodiment may be any decorative sheet having a surface protective layer 4 provided on one side of a transparent resin layer 1. In other words, the decorative sheet 10 may be a laminate comprising at least an original fabric layer 7, a transparent resin layer 1, and a surface protective layer 4 in this order. For the sake of convenience, in the decorative sheet 10 according to this embodiment, the laminate laminated on the original fabric layer 7 is referred to as the "laminate portion 50."

[0021] In order to improve the design, an embossed pattern may be appropriately provided on the surface of the transparent resin layer 1 on the side of the surface protective layer 4 . The total thickness of the decorative sheet 10 is preferably in the range of 60 μm to 250 μm. If the total thickness is less than 60 μm, there is a concern that the required performance of the decorative sheet may be reduced in terms of concealment (ability to hide the base of the decorative substrate) and scratch resistance. If the total thickness is more than 250 μm, there is a concern that the cost may increase and that the processability may decrease when bonding the decorative sheet to the decorative substrate. Moreover, the decorative sheet of the present embodiment preferably does not contain vinyl chloride resin. By using a decorative sheet that uses a non-vinyl chloride resin, concerns about the generation of toxic gases and the like during incineration can be reduced. Hereinafter, each layer constituting the decorative sheet of this embodiment will be described in detail.

[0022] (Original layer) When the decorative sheet is to be given design, scratch resistance and post-processing resistance, the raw cloth layer (raw cloth) 7 may be appropriately selected from, for example, paper such as tissue paper, titanium paper, and resin-impregnated paper, synthetic resins such as polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic, or foams of these synthetic resins, rubbers such as ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane, organic or inorganic nonwoven fabrics, synthetic paper, and metal foils such as aluminum, iron, gold, and silver. The raw cloth layer 7 may also be a sheet made of the same resin composition as the transparent resin layer 1. Among the above, it is preferable to use polyolefin-based materials such as polypropylene and polyethylene. In other words, the raw cloth layer 7 is preferably a layer containing at least an olefin-based resin.

[0023] Examples of the polyolefin resin contained in the raw fabric layer 7 include polypropylene, polyethylene, polybutene, and the like, as well as α-olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl These include homopolymers or copolymers of two or more types of α-olefins (e.g., 1-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) as well as copolymers of ethylene or α-olefins with other monomers, such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.

[0024] When a substrate having an inactive surface such as a polyolefin-based material is used as the raw fabric layer 7, it is preferable to perform, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, etc. on the front and back sides of the raw fabric layer 7. Furthermore, a primer layer (not shown) may be provided between the raw fabric layer 7 and the picture print layer 6 to ensure adhesion.

[0025] When it is desired to provide the decorative sheet with a concealing property, a concealing colored sheet may be used for the original fabric layer 7, or as shown in FIG. 1, a concealing layer 3 may be provided on the original fabric layer 7 and below the pattern printed layer 6. The concealing layer 3 will be described later. When a colored sheet is used as the original fabric layer 7, a coloring agent may be added to the resin material constituting the original fabric layer 7 to color it. As the coloring agent, for example, inorganic pigments (titanium oxide, carbon black, etc.) and organic pigments (phthalocyanine blue, etc.) as well as dyes can be used. The coloring agent of this embodiment can be selected from one or more known or commercially available coloring agents, and the amount added can be adjusted so as to obtain the desired concealing property and design.

[0026] If necessary, various additives such as fillers, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, crystal nucleating agents, ultraviolet absorbers, visible light absorbers, light stabilizers, heat stabilizers, colorants, and matting agents may be added to the raw fabric layer 7. The thickness of the raw fabric layer 7 is preferably within the range of 20 μm to 150 μm, taking into consideration printing workability, costs, and the like.

[0027] (Pattern printing layer) The pattern printed layer 6 may be formed on the base layer 7 or the transparent resin layer 1 by, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, or the like. When ink is used to form the picture print layer 6, the binder contained in the ink may be appropriately selected from, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., either alone or modified. These may be water-based, solvent-based, or emulsion type, and may be any one-component type or two-component type using a hardener. Furthermore, the ink can be cured by irradiation with ultraviolet light, electron beams, etc. Among these, the preferred method is to use a urethane-based ink and cure it with isocyanate. That is, in the decorative sheet 10 according to this embodiment, the picture-printed layer 6 preferably contains a urethane-based resin as a binder.

[0028] The urethane resin used in the pattern printing layer 6 is not particularly limited, and may be either one-component curing type or two-component curing type. For example, one-component ester polyurethane resin may be suitably used as the one-component curing type urethane resin. In addition, as the two-component curing type urethane resin, for example, one containing a polyol component having an OH group as a main agent and an isocyanate component as a curing agent component may be adopted. Examples of the polyol component having an OH group include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, the pattern printing layer 6 may be suitably used with a polyester urethane resin using a polyester polyol as a main agent.

[0029] In addition to the binder, the picture-printed layer 6 may contain pigments, colorants such as dyes, extender pigments, solvents, and various additives that are contained in normal inks. Particularly commonly used pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica. In addition to applying ink, it is also possible to apply designs by deposition or sputtering of various metals. The thickness of the pattern-printed layer 6 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 2 μm. By making the pattern-printed layer 6 sufficiently thick, it is possible to improve the interlayer adhesion (e.g., adhesion between the base fabric layer 7, the concealing layer 3, and the adhesive layer 5) in the decorative sheet 10. On the other hand, if the pattern-printed layer 6 is too thick, post-processability (e.g., bending processability) may be reduced. Therefore, by setting the thickness of the picture-printed layer 6 within the range of 1 μm or more and 10 μm or less as described above, it is possible to improve the adhesion between layers and the post-processing properties.

[0030] (Hidden layer) The concealing layer 3 can be provided on the original fabric layer 7 or on the pattern-printed layer 6 formed on the transparent resin layer 1 by the same printing method as that for the pattern-printed layer 6. The concealing layer 3 may be formed as necessary, and may be omitted, for example, when a concealing colored sheet is used for the original fabric layer 7. When applying the concealing layer 3, for example, a comma coater, a knife coater, a lip coater, metal vapor deposition, or a sputtering method may be used. The concealing layer 3 is generally provided as an upper layer of the original fabric layer 7 and as a lower layer of the pattern-printed layer 6.

[0031] The material used for the concealing layer 3 may basically be the same as that for the pattern printed layer 6. Since the concealing layer 3 needs to have a concealing property as its purpose, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide, etc. as a pigment. In addition, it is also possible to add metals such as gold, silver, copper, and aluminum to improve the concealing property. Generally, flake-shaped aluminum is often added. If the coating thickness, i.e., the thickness of the concealing layer 3, is less than 2 μm, it is difficult to impart concealing property, and if it exceeds 10 μm, the cohesive force of the resin layer tends to be weak. For this reason, the thickness of the concealing layer 3 is preferably in the range of 2 μm to 10 μm.

[0032] (adhesive layer) Any material can be selected for the adhesive layer 5, and examples of adhesion methods using the adhesive layer 5 include heat lamination, extrusion lamination, dry lamination, etc. The adhesive contained in the adhesive layer 5 can be selected from, for example, acrylic, polyester, polyurethane, phthalic acid (alkoxy acid)-based materials, etc. The adhesive contained in the adhesive layer 5 is usually desirably a two-liquid curing type adhesive due to its high cohesive strength, and it is particularly desirably a urethane-based material obtained by reaction with a polyol using an isocyanate due to its workability, cost, and high cohesive strength. In other words, the adhesive layer 5 preferably contains a urethane resin.

[0033] The urethane resin used in the adhesive layer 5 is not particularly limited, and may be either a one-component curing type or a two-component curing type. For example, a one-component ester polyurethane resin may be suitably used as the one-component curing type urethane resin. In addition, a two-component curing type urethane resin may be used that contains, for example, a polyol component having an OH group as a main agent and an isocyanate component as a curing agent component. Examples of the polyol component having an OH group include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, a polyester urethane resin using a polyester polyol as a main agent may be suitably used for the adhesive layer 5.

[0034] The thickness of the adhesive layer 5 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 5 μm. By making the thickness of the adhesive layer 5 sufficiently thick, it is possible to improve the interlayer adhesion (e.g., adhesion between the base layer 7, the concealing layer 3, and the transparent resin layer 1) in the decorative sheet 10. On the other hand, if the thickness of the adhesive layer 5 is too thick, post-processability (e.g., bending processability) may be reduced. Therefore, by setting the thickness of the adhesive layer 5 within the range of 1 μm or more and 10 μm or less as described above, it is possible to improve the adhesion between the layers and the post-processability.

[0035] (Transparent resin layer) The transparent resin layer 1 is formed on the adhesive layer 5. The transparent resin layer 1 may be a sheet formed by film formation, or may be a laminate of already formed sheets. The transparent resin layer 1 is preferably formed using a polyolefin resin. Specifically, it is preferable to use a polypropylene resin as the transparent resin layer 1. The transparent resin layer 1 is formed, for example, of a highly crystalline polypropylene resin. Furthermore, one or both surfaces of the transparent resin layer 1 may be activated, for example, by corona treatment, plasma treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, or the like, as necessary.

[0036] When the transparent resin layer 1 is formed from a sheet by film formation, for example, a method using an extruder is generally used. When the transparent resin layer 1 is laminated and formed, there is no particular restriction, and for example, a method using heat and pressure, an extrusion lamination method, a dry lamination method, etc. are generally used. In addition, when the embossed pattern 1a is applied, there is a method of embossing a sheet that has been once laminated by various methods, for example, by heat and pressure, or a method of providing an uneven pattern on a cooling roll and embossing the sheet at the same time as extrusion lamination using the cooling roll. More specifically, the embossed pattern 1a is directly applied to the transparent resin layer 1, for example, a highly crystalline polypropylene sheet, and the method includes a method of providing an embossed pattern on the sheet formed by film formation using an embossing plate having an uneven pattern by heat and pressure, and a method of providing an embossment at the same time as cooling using a cooling roll having an uneven pattern when forming a film using an extruder. Here, it is also possible to embed ink in the embossed pattern 1a as the embossed part to further improve the design. The embossed pattern 1a may be provided if necessary, but may not be provided if unnecessary.

[0037] The thickness of the transparent resin layer 1 is preferably in the range of 40 μm or more and 170 μm or less. If the thickness of the transparent resin layer 1 is less than 40 μm, the weather resistance and scratch resistance may decrease. If the thickness of the transparent resin layer 1 exceeds 170 μm, the manufacturing cost may increase and the flexibility may decrease. If necessary, various additives such as heat stabilizers, flame retardants, ultraviolet absorbers, visible light absorbers, light stabilizers, antiblocking agents, catalyst scavengers, and, as long as the characteristics of this embodiment are not impaired, colorants, light scattering agents, and gloss adjusters may also be added to the transparent resin layer 1.

[0038] More specifically, in this embodiment, the transparent resin layer 1 constituting the laminated portion 50 may contain an ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbing agent having a maximum absorption wavelength of 380 to 430 nm.

[0039] Among the olefin resins commonly used for the raw layer 7 (substrate) and the transparent resin layer 1, polypropylene (PP) undergoes oxidative degradation in the ultraviolet region of 290 nm (280 to 330 nm) and in the region of 370 to 430 nm, which is the short wavelength region of the visible region. Therefore, by adding a weathering agent (light absorber) that absorbs light in both wavelength regions, a decorative sheet with good weather resistance can be obtained. Note that the ultraviolet absorber added in the decorative sheet according to the conventional technology is mainly intended to avoid oxidative degradation only in the ultraviolet region of 290 nm. Therefore, for example, in a decorative sheet containing polypropylene (PP), since polypropylene (PP) also undergoes degradation in the visible region, sufficient weather resistance may be difficult to obtain. Thus, if the amount of ultraviolet absorber is increased in a decorative sheet according to the conventional technology, the weather resistance tends to improve, but there are cases in which sufficient weather resistance cannot be maintained.

[0040] Furthermore, the ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and the absorbance A2 of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm added to the transparent resin layer 1 is preferably 5 or more, and more preferably 8 or more, for the following reasons. The degradation wavelengths of polypropylene (PP) are roughly divided into around 290 nm and around 400 nm, but degradation by light in the ultraviolet region around 290 nm is prominent. Therefore, it is preferable that the absorbance ratio of the light absorbent is greater around 290 nm than around 400 nm.

[0041] The ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm to the absorbance A2 of the visible light absorber having a maximum absorption wavelength of 380 to 430 nm can be controlled by adjusting the content ratio of the ultraviolet absorber to the visible light absorber.

[0042] The content of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm is preferably in the range of 0.1 to 5 parts by mass, and more preferably in the range of 0.3 to 1 part by mass, relative to 100 parts by mass of the resin constituting the layer to which the ultraviolet absorbent is added (transparent resin layer 1). The content of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is preferably in the range of 0.1 to 5 parts by mass, and more preferably in the range of 0.3 to 1 part by mass, relative to 100 parts by mass of the resin constituting the layer to which the visible light absorbent is added (transparent resin layer 1). In addition, when a light stabilizer is added together with each of the light absorbents described above, the content of the light stabilizer is preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass of the resin constituting the layer (transparent resin layer 1) to which the light stabilizer is added, and more preferably in the range of 0.3 parts by mass or more and 1 part by mass or less.

[0043] The transparent resin layer 1 may contain only a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm without containing an ultraviolet light absorbent having a maximum absorption wavelength of 280 to 330 nm. When only a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is added to the transparent resin layer 1, it is sufficient that an ultraviolet light absorbent having a maximum absorption wavelength of 280 to 330 nm is added to the surface protective layer 4.

[0044] Furthermore, only an ultraviolet absorber having an absorption maximum wavelength of 280 to 330 nm may be added to the transparent resin layer 1 without containing a visible light absorber having an absorption maximum wavelength of 380 to 430 nm. When only an ultraviolet absorber having an absorption maximum wavelength of 280 to 330 nm is added to the transparent resin layer 1, it is sufficient that a visible light absorber having an absorption maximum wavelength of 380 to 430 nm is added to the surface protective layer 4. Moreover, the visible light absorbent may have a maximum absorption wavelength in the range of 380 to 430 nm, and preferably has a maximum absorption wavelength in the range of 390 to 430 nm.

[0045] As the ultraviolet absorbing agent, for example, a benzotriazole type, a triazine type, a benzophenone type, a benzoate type, or the like ultraviolet absorbing agent can be used. 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.

[0046] Examples of triazine-based ultraviolet absorbers that can be used 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, and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, as well as mixtures, modified products, polymers, and derivatives thereof.

[0047] Furthermore, as the benzophenone-based ultraviolet absorbing agent, for example, octabenzone, its modified product, polymer, and derivative can be used. As the visible light absorbing agent, for example, a visible light absorbing agent such as a dye can be used.

[0048] Examples of the light stabilizer that can be used include hindered amine light stabilizers (HALS). Examples of the light stabilizer that can be used include poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-dyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], dimethyl succinate·1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine polycondensate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and mixtures, modified products, polymers, and derivatives thereof.

[0049] Generally, the heat stabilizer is, for example, a phenol-based, sulfur-based, phosphorus-based, or hydrazine-based agent, the flame retardant is, for example, aluminum hydroxide, magnesium hydroxide, or the like, and the light stabilizer is, for example, a hindered amine-based agent, and these are added in any combination. The transparent resin layer 1 may also contain a crystal nucleating agent (nano-sized nucleating agent) that has been subjected to a vesicle treatment by supercritical reverse phase evaporation.

[0050] In addition, the crystalline polypropylene resin forming the transparent resin layer 1 can be appropriately selected and designed from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, lock polypropylene, and mixtures thereof, each having a different pentad fraction. More preferably, it is important that the crystalline polypropylene resin is a propylene homopolymer, i.e., a highly crystalline homopolypropylene resin, which is a homopolymer, having an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. In addition, resins other than the crystalline polypropylene constituting the transparent resin layer 1 can be appropriately selected depending on the purpose of the blending, as long as they do not significantly adversely affect the physical properties of the crystalline polypropylene. However, in order to maintain the V-groove bending processability, it is preferable that the resin has good compatibility with the crystalline polypropylene resin constituting the transparent resin layer 1. The material of the transparent resin layer 1 is not limited to this, and a highly flexible polyolefin resin such as a random polypropylene resin containing an ethylene content or a polyolefin thermoplastic elastomer can be used.

[0051] The terms used in the above description of the transparent resin layer 1 will be briefly explained below. A nucleating agent is added to promote the generation of crystal nuclei during the crystallization of a resin, or to make the nucleating agent itself a crystal nucleus. Nucleating agents include melting agents that melt into the resin of the base material when added and precipitate again to generate crystal nuclei, and non-melting agents that do not melt when added to the base material and become crystal nuclei with the same particle size. Examples of nucleating agents for polypropylene resin include metal phosphate salts, metal benzoate salts, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in this embodiment, in order to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoate salts, metal pimelate salts, and metal rosin salts that are non-melting and can be expected to have good transparency, but if the nano-processing can make the material transparent, colored quinacridone, cyanine blue, talc, etc. can also be used. In addition, melting benzylidene sorbitol may be appropriately mixed with the non-melting nucleating agent.

[0052] The isotactic pentad fraction (mmmm fraction) is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating the resin material constituting the transparent resin layer 1 at a predetermined resonance frequency by 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclear species) with a mass number of 13, and specifies the atomic arrangement, electronic structure, and molecular microstructure in the resin material. The isotactic pentad fraction of a polypropylene resin is the ratio of five propylene units lined up as determined by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. Such an isotactic pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface, and basically, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, and therefore the better the scratch resistance.

[0053] (Surface protective layer) As shown in Fig. 1, the surface protective layer 4 is formed on a transparent resin layer 1. That is, in the decorative sheet 10, the surface protective layer 4, which serves as the outermost layer, is laminated on the transparent resin layer 1. The surface protective layer 4 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 10. The surface protective layer 4 may contain various additives, such as an ultraviolet absorber, a visible light absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst trap, a colorant, a light scattering agent, and a gloss adjuster, as necessary.

[0054] For example, a curable resin composition can be used as a material for forming the surface protective layer 4. In this embodiment, the surface protective layer 4 may contain a cured product of the curable resin composition. More specifically, the curable resin composition constituting the surface protective layer 4 is preferably formed containing at least one of a resin that is cured by heat, i.e., a thermosetting resin, and a resin that is cured by ultraviolet light or electron beam irradiation, i.e., an ionizing radiation curable resin. In other words, the surface protective layer 4 may be formed containing only a thermosetting resin as the curable resin composition, or may be formed containing only an ionizing radiation curable resin. Furthermore, the surface protective layer 4 may be formed containing both a thermosetting resin and an ionizing radiation curable resin, i.e., a mixed composition of a thermosetting resin and an ionizing radiation curable resin.

[0055] The thermosetting resin used for the surface protective layer 4 can be appropriately selected from, for example, polyurethane, acrylic, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, etc. The form can be any of water-based, emulsion, and solvent-based, and the curing can be either a one-liquid type or a two-liquid type using a curing agent. Among them, a urethane-based top coat using an isocyanate reaction is preferable from the viewpoints of workability, cost, cohesive strength of the resin itself, etc. Specifically, it is preferable to use an acrylic urethane resin in which an acrylic polyol is combined with an isocyanate curing agent as the thermosetting resin used for the surface protective layer 4. In other words, it is preferable that the thermosetting resin constituting the surface protective layer 4 is composed of an acrylic polyol (an acrylic polyol compound) and an isocyanate curing agent.

[0056] The isocyanate can be appropriately selected from curing agents such as adducts, biurets, and isocyanurates, which are derivatives of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), and various prepolymers. However, in consideration of weather resistance, it is preferable to use a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI), which have a linear molecular structure, or hydrogenated MDI (hydrogenated MDI) or hydrogenated XDI (hydrogenated XDI).

[0057] The ionizing radiation curable resin used in the surface protective layer 4 can be appropriately selected from, for example, polyester acrylate, epoxy acrylate, urethane acrylate, acrylic acrylate, etc., but it is particularly preferable to use urethane acrylate and acrylic acrylate resins, which have good weather (light) resistance. As a curing method for the ionizing radiation curable resin, curing with active energy rays such as ultraviolet rays and electron beams is preferable from the viewpoint of workability. As an electron beam source, for example, light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, etc. can be used. The wavelength of the ultraviolet rays is preferably within the range of 180 nm to 400 nm.

[0058] It is more preferable to use, for example, a mixture of a urethane-based resin obtained by reacting an acrylic polyol with an isocyanate as the thermosetting resin and a urethane acrylate-based resin as the ionizing radiation curable resin as the mixture of thermosetting resin and ionizing radiation curable resin for the surface protective layer 4. By using a mixture of a thermosetting resin and an ionizing radiation curable resin, it is possible to improve the surface hardness and at least one of the suppression of cure shrinkage and the adhesion of inorganic fine particles (inorganic filler).

[0059] Moreover, the ionizing radiation curable resin constituting the surface protective layer 4 is preferably an ultraviolet curable resin that is cured by ultraviolet rays. The ultraviolet curing resin constituting the surface protective layer 4 preferably has 4 or more functional groups and contains one or more components with a mass average molecular weight of 500 or more. More preferably, the ultraviolet curing resin has 4 or more functional groups and contains one or more components with a mass average molecular weight in the range of 500 to 5,000. If the ultraviolet curing resin has less than 4 functional groups, the crosslinking density is low and the scratch resistance is significantly reduced, which is not preferable. If the ultraviolet curing resin has a mass average molecular weight of less than 500, the surface condition during coating is significantly deteriorated, which is not preferable. If the ultraviolet curing resin has a mass average molecular weight of more than 5,000, the viscosity of the coating liquid increases and the coating suitability is significantly reduced, which is not preferable.

[0060] The amount of the photoinitiator to be added is not particularly limited, and is preferably about 0.1 to 15 parts by mass relative to 100 parts by mass of the base resin. The type of photoinitiator is not particularly limited. In the case of a resin system having a radical polymerizable unsaturated group, at least one of the following photoinitiators can be selected: acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, isopropyl-N,N dimethylaminobenzoate, etc. In addition, it is desirable to design a combination of multiple types according to the light source and production environment. In the case of a resin system having a cationic polymerizable functional group, the photoinitiator can be selected from at least one of, for example, aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, and furyloxysulfoxonium diallyliodosyl salts.

[0061] The method for forming the surface protective layer 4 is not particularly limited, and the surface protective layer 4 may be formed by coating the above-mentioned material in a coating liquid form using a conventional method such as gravure coating, microgravure coating, comma coating, knife coating, or die coating, and then curing the liquid using a method suitable for the resin material, such as thermal curing or ultraviolet curing. This surface protective layer 4 may be provided on the transparent resin layer 1 after bonding the pattern printed layer 6 provided on the original fabric layer 7 to the transparent resin layer 1 via the adhesive layer 5, or it may be provided on the transparent resin layer 1 before bonding the transparent resin layer 1 to the original fabric layer 7. In order to further improve weather resistance, an ultraviolet absorbing agent or a visible light absorbing agent may be added to the surface protective layer 4.

[0062] In addition to the ultraviolet absorbing agent, a light stabilizer may be added to the surface protective layer 4 as appropriate. More specifically, in this embodiment, the surface protective layer 4 constituting the laminated portion 50 may contain an ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbing agent having a maximum absorption wavelength of 380 to 430 nm.

[0063] Among the olefin resins commonly used for the raw layer 7 (substrate) and the transparent resin layer 1, polypropylene (PP) undergoes oxidative degradation in the ultraviolet region of 290 nm (280 to 330 nm) and in the region of 370 to 430 nm, which is the short wavelength region of the visible region. Therefore, by adding a weathering agent (light absorber) that absorbs light in both wavelength regions, a decorative sheet with good weather resistance can be obtained. Note that the ultraviolet absorber added in the decorative sheet according to the conventional technology is mainly intended to avoid oxidative degradation only in the ultraviolet region of 290 nm. Therefore, for example, in a decorative sheet containing polypropylene (PP), since polypropylene (PP) also undergoes degradation in the visible region, sufficient weather resistance may be difficult to obtain.

[0064] Furthermore, the ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and the absorbance A2 of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm added to the surface protective layer 4 is preferably 5 or more, and more preferably 8 or more, for the following reasons. The degradation wavelengths of polypropylene (PP) are roughly divided into around 290 nm and around 400 nm, but degradation by light in the ultraviolet region around 290 nm is prominent. Therefore, it is preferable that the absorbance ratio of the light absorbent is greater around 290 nm than around 400 nm. The ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm to the absorbance A2 of the visible light absorber having a maximum absorption wavelength of 380 to 430 nm can be controlled by adjusting the content ratio of the ultraviolet absorber to the visible light absorber.

[0065] The content of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm is preferably in the range of 0.1 parts by mass or more and 10 parts by mass or less, and more preferably in the range of 3 parts by mass or more and 6 parts by mass or less, relative to 100 parts by mass of the resin constituting the layer to which the ultraviolet absorbent is added (surface protective layer 4). The content of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is preferably in the range of 0.1 to 5 parts by mass, and more preferably in the range of 1 to 5 parts by mass, relative to 100 parts by mass of the resin constituting the layer to which the visible light absorbent is added (surface protective layer 4). In addition, when a light stabilizer is added together with the above-mentioned light absorber, the content of the light stabilizer is preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass of the resin constituting the layer to which the light stabilizer is added (surface protective layer 4), and more preferably in the range of 0.3 parts by mass or more and 1 part by mass or less.

[0066] The surface protective layer 4 may contain only an ultraviolet absorber having an absorption maximum wavelength of 280 to 330 nm without containing a visible light absorber having an absorption maximum wavelength of 380 to 430 nm. When only an ultraviolet absorber having an absorption maximum wavelength of 280 to 330 nm is added to the surface protective layer 4, it is sufficient that a visible light absorber having an absorption maximum wavelength of 380 to 430 nm is added to the transparent resin layer 1.

[0067] Furthermore, only a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm may be added to the surface protective layer 4 without containing an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm. When only an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm is added to the surface protective layer 4, it is sufficient that a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is added to the transparent resin layer 1. Moreover, the visible light absorbent may have a maximum absorption wavelength in the range of 380 to 430 nm, preferably in the range of 390 to 430 nm, and more preferably in the range of 400 to 430 nm.

[0068] As the ultraviolet absorbing agent, for example, a benzotriazole type, a triazine type, a benzophenone type, a benzoate type, or the like ultraviolet absorbing agent can be used. 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.

[0069] Examples of triazine-based ultraviolet absorbers that can be used 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, and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, as well as mixtures, modified products, polymers, and derivatives thereof.

[0070] Furthermore, as the benzophenone-based ultraviolet absorbing agent, for example, octabenzone, its modified product, polymer, and derivative can be used. As the visible light absorbing agent, for example, a visible light absorbing agent such as a dye can be used.

[0071] As the light stabilizer, for example, a hindered amine light stabilizer (HALS) can be used. Examples of the hindered amine light stabilizer (HALS) include bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

[0072] In order to improve the scratch resistance of the surface or to adjust the luster (luster) associated with imparting design properties, it is desirable to add an inorganic filler as a luster adjuster to the surface protective layer 4 . Examples of inorganic fillers to be added to the surface protective layer 4 include alumina, silica, boehmite, iron oxide, magnesium oxide, aluminosilicate, diamond, silicon nitride, silicon carbide, glass beads, calcium titanate, barium titanate, magnesium pyroporate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, and glass fibers. As the inorganic filler, inorganic fine particles having an average particle size of 1 μm or more and 30 μm or less can be used, and inorganic fine particles having an average particle size of 1 μm or more and 10 μm or less are particularly suitable. When the average particle size of the inorganic filler is less than 1 μm, it tends to be difficult to obtain a matte effect. This is because, in order to achieve a matte effect, it is ideal for the particle size to be equal to or larger than the thickness of the film (layer) to which the inorganic filler is added. When the average particle size of the inorganic filler exceeds 30 μm, or more reliably, 10 μm, the inorganic filler is likely to fall off from the surface protective layer 4 under high load conditions, and the luster tends to change and the surface tends to look worse.

[0073] For example, when gravure printing is selected as the method for forming the surface protective layer 4, the coating thickness for one layer is appropriately in the range of 4 μm to 21 μm. In this case, as described above, it is preferable to select an inorganic filler having an average particle size of about the same size as the thickness that can be coated at one time. The content of the inorganic filler in the surface protective layer 4 is preferably within a range of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin constituting the surface protective layer 4. If the content of the inorganic filler is less than 1 part by mass, scratch resistance may decrease. If the content of the inorganic filler exceeds 20 parts by mass, the surface gloss may decrease significantly, which may impair the design and decrease weather resistance and stain resistance.

[0074] It is desirable to perform a surface treatment on the inorganic filler contained in the surface protective layer 4. By performing a surface treatment on the inorganic filler, it is possible to strengthen the bond with the surface protective layer 4. Note that the surface protective layer 4 may contain inorganic fillers whose surfaces are not treated. In addition, when carrying out the surface treatment, it is desirable that the inorganic filler has a functional group that hydrophobicizes the surface of the inorganic filler and imparts reactivity with the surface protective layer 4. In other words, it is desirable that the surface treatment agent used to treat the surface of the inorganic filler has a reactive group that reacts with the main resin constituting the surface protective layer 4. When carrying out the surface treatment of the inorganic filler, the method is not particularly limited, and a known method can be selected.

[0075] The surface treatment agent used for the surface treatment of the inorganic filler may be at least one of a surfactant, a fatty acid metal salt, a silane coupling agent, silicone, wax, and a modified resin. The surface treatment agent of this embodiment may be, for example, a silicone oil type, an alkylsilazane type, a trimethylsilylating agent, an alkoxysilane type, a siloxane, a silane coupling agent, a titanium coupling agent, a phosphoric acid type, or a fatty acid type surfactant, and may be one type or a combination of multiple types. Examples of silicone oil-based treatment agents that can be selected include straight silicone oils (dimethyl silicone oil, methylphenyl silicone oil, etc.) and modified silicone oils (amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, one-end reactive modified, heterogeneous functional group-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, specially hydrophilic modified, higher alkoxy-modified, higher fatty acid-containing modified, fluorine-modified silicone oil, etc.).

[0076] As the alkylsilazane-based treatment agent, for example, hexamethyldisilazane, vinylsilazane, etc. can be selected. Examples of the silane coupling agent include alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-hexyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, diethoxymethylphenylsilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminopropyltriethoxysilane, and aminopropyltrimethoxysilane; and chlorosilane compounds such as trimethylchlorosilane and diethyldichlorosilane.

[0077] As the trimethylsilylation agent, an alkoxysilane compound among silane coupling agents can be selected. Examples of titanate coupling agents that can be selected include isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(ditridecyl) phosphite titanate, and bis(dioctyl pyrophosphate) oxyacetate titanate. As the aluminate-based coupling agent, for example, acetoalkoxyaluminum diisopropylate can be selected.

[0078] When an embossed pattern 1a is applied to the surface of the transparent resin layer 1 on the side of the surface protective layer 4, the ink forming the surface protective layer 4 can be embedded into this embossed pattern by wiping processing to improve the design. Although not shown, an embossed pattern similar to the embossed pattern 1a may be provided on the outermost surface side of the surface protection layer 4. This can further improve the design.

[0079] Further, in FIG. 1, an example in which the surface protective layer 4 is a single layer has been described, but the surface protective layer 4 in the decorative sheet 10 according to this embodiment is not limited to a single layer. The surface protective layer 4 may be a single layer or a multi-layer structure. In other words, the surface protective layer 4 may be composed of one or more layers. Therefore, the surface protective layer 4 may have a total thickness in the range of 4 μm to 21 μm. Furthermore, when the surface protective layer 4 has a multi-layer structure, it may include layers formed from different resins.

[0080] Furthermore, when the surface protective layer 4 has a multi-layer structure, the gloss control agent may be contained in at least one layer of the multi-layer structure. Furthermore, when the surface protective layer 4 is a multi-layer structure, it is sufficient that at least the uppermost layer is configured to include a cured product of a curable resin composition, and layers formed from different types of resin materials may be included. When the surface protective layer 4 is a multi-layered layer, at least one layer (for example, the uppermost layer) may contain an ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbing agent having a maximum absorption wavelength of 380 to 430 nm. When the surface protective layer 4 is a multi-layer structure, one layer (e.g., the top layer) may contain an ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm, and the other layers may contain a visible light absorbing agent having a maximum absorption wavelength of 380 to 430 nm. Alternatively, one layer (e.g., the top layer) may contain a visible light absorbing agent having a maximum absorption wavelength of 380 to 430 nm, and the other layers may contain an ultraviolet absorbing agent having a maximum absorption wavelength of 280 to 330 nm.

[0081] (Easy adhesion layer) The adhesive layer 8 is a layer for bonding the adherend of the decorative sheet 10 (for example, a substrate for a decorative material) and the original fabric layer 7, and is also called a primer layer. The material used for the easy adhesion layer 8 may basically be the same as that for the picture print layer 6 and the concealing layer 3. In addition, considering that the easy adhesion layer 8 is applied to the back surface of the decorative sheet and is wound in a web form, inorganic fillers such as silica, alumina, magnesia, titanium oxide, barium sulfate, etc. may be added to the easy adhesion layer 8 to avoid blocking and improve adhesion with the adhesive. The coating thickness, i.e., the thickness of the easy adhesion layer 8 (primer layer) is intended to ensure adhesion with the base material layer 7, so that it is appropriate to be in the range of 0.1 μm to 10.0 μm, more preferably in the range of 0.1 μm to 3.0 μm. The easy-adhesion layer 8 is necessary when the surface of the base layer 7 is inactive, such as when the layer is made of an olefin-based material, but is not particularly necessary when the surface is active.

[0082] <First Modification> A first modified example of the decorative sheet according to the first embodiment will be described with reference to Fig. 2. Fig. 2 is a schematic cross-sectional view for explaining one configuration example of a decorative sheet 20 according to a first modified example of the first embodiment. The decorative sheet 20 according to this modified example differs from the decorative sheet 10 according to the above-mentioned first embodiment in that the transparent resin layer is not a single layer but a multi-layer.

[0083] The decorative sheet shown in Fig. 2 comprises, in order from the top of the drawing, a surface protective layer 4, a transparent resin layer 11, an adhesive layer 5 (heat-sensitive adhesive layer, anchor coat layer, dry lamination adhesive layer), a picture print layer 6, a concealing layer 3, a base fabric layer 7, and an easy-adhesion layer 8. As will be described in detail later, the transparent resin layer 11 has a multilayer structure and comprises a transparent resin layer 1 and a transparent resin layer 2. More specifically, the decorative sheet 20 according to this modified example may be any decorative sheet having a configuration in which a surface protective layer 4 is provided on one side of a transparent resin layer 11 having a multilayer structure. In other words, the decorative sheet 20 may be a laminate, and may be any decorative sheet having at least an original fabric layer 7, a transparent resin layer 11 (transparent resin layers 1, 2), and a surface protective layer 4, in that order. In the decorative sheet 20 according to this embodiment, the laminate laminated on the original fabric layer 7 is referred to as the "laminate portion 51" for the sake of convenience.

[0084] Below, a detailed description will be given of the transparent resin layer 11, which is a configuration of the decorative sheet 20 that differs from that of the decorative sheet 10. Note that the configuration of the decorative sheet 20 other than the transparent resin layer 11 is the same as that of the decorative sheet 10. For this reason, the same reference numerals as those in the decorative sheet 10 are used and detailed description will be omitted.

[0085] In this modification, the laminated portion 51 also contains at least two types of light absorbents with different maximum absorption wavelengths, an ultraviolet absorbent with a maximum absorption wavelength of 280 to 330 nm, and a visible light absorbent with a maximum absorption wavelength of 380 to 430 nm. This allows the decorative sheet 20 according to this modification to have good weather resistance. In this modification, at least one of the transparent resin layer 1 and the transparent resin layer 2 may contain an ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm and a visible light absorber having a maximum absorption wavelength of 380 to 430 nm. This allows the decorative sheet 20 according to this modification to have good weather resistance. In this modification, either the transparent resin layer 1 or the transparent resin layer 2 may contain an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm, and the other may contain a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm. This allows the decorative sheet 20 according to this modification to have good weather resistance.

[0086] (Transparent resin layer) 2, the decorative sheet 20 includes a transparent resin layer 11. The transparent resin layer 11 is a multi-layer (two layers in this example) structure including a transparent resin layer 1 and a transparent resin layer 2. More specifically, the transparent resin layer 11 is a multi-layer structure including the transparent resin layer 1 that serves as a first transparent resin layer, and the transparent resin layer 2 that serves as a second transparent resin layer located between the transparent resin layer 1 and the adhesive layer 5.

[0087] [First transparent resin layer] 2, transparent resin layer 1, which is the first transparent resin layer of transparent resin layer 11 in this modified example, is in contact with surface protective layer 4 and is located above transparent resin layer 2. Transparent resin layer 1, which is the first transparent resin layer of transparent resin layer 11, has the same configuration as transparent resin layer 1 of decorative sheet 10 according to the first embodiment described above, and therefore is given the same reference numeral and detailed description thereof is omitted. [Second transparent resin layer] As shown in FIG. 2, in the decorative sheet 20 according to this modification, a transparent resin layer 2 serving as a second transparent resin layer is provided between the transparent resin layer 1 serving as the first transparent resin layer and an adhesive layer 5. The transparent resin layer 2 may be provided when further laminate strength is required, particularly when the transparent resin layer is formed by the extrusion lamination method.

[0088] In general, the transparent resin layer 1 and the transparent resin layer 2 in the transparent resin layer 11 are laminated and formed by a co-extrusion method. The resin contained in the transparent resin layer 2 is preferably, for example, an acid-modified resin such as polypropylene, polyethylene, or an acrylic resin. For the purpose of improving adhesive strength, the thickness of the transparent resin layer 2 is desirably 2 μm or more. If the thickness of the transparent resin layer 2 is less than 2 μm, it tends to be difficult to obtain sufficient adhesive strength. Moreover, the thickness of the transparent resin layer 2 is desirably 20 μm or less. If the thickness of the transparent resin layer 2 exceeds 20 μm, the transparent resin layer 2 tends to deteriorate during long-term use, causing cohesive failure and making the layer more susceptible to peeling. In other words, the thickness of the transparent resin layer 2 is preferably within the range of 2 μm or more and 20 μm or less.

[0089] In addition, in the transparent resin layer 11, the sum of the thickness of the transparent resin layer 1 and the thickness of the transparent resin layer 2 is preferably 40 μm or more and 170 μm or less. In other words, the total thickness of the transparent resin layer 11 is preferably 40 μm or more and 170 μm or less. This makes it possible to suppress an increase in manufacturing costs and a decrease in flexibility while improving weather resistance and scratch resistance.

[0090] <Second Modification> The decorative material according to the second modified example of this embodiment will be described with reference to Fig. 3. The decorative sheet according to this embodiment can be suitably used for the purpose of producing a decorative material by laminating it with a base material for a decorative material. Fig. 3 is a cross-sectional view for explaining one configuration example of the decorative material 100 according to the second modified example of this embodiment.

[0091] 3, the decorative material 100 according to this modification is obtained by laminating the decorative sheet 10 according to this embodiment on a substrate 16 for a decorative material so that the surface protective layer 4 of the decorative sheet 10 is the outermost layer. That is, the decorative material 100 differs from the decorative sheet 10 according to the first embodiment in that it includes an adhesive 15 and a substrate 16 for a decorative material.

[0092] (Decorative materials) 3, in the decorative material 100, a concealing layer 3, a pattern printed layer 6, an adhesive layer 5, a transparent resin layer 1, and a surface protective layer 4 are laminated in this order on one surface of an original fabric layer 7 in a decorative sheet 10, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 are provided on the other surface of the original fabric layer 7. In other words, the decorative material 100 comprises the decorative material substrate 16 and the decorative sheet 10, which is a laminate bonded to the decorative material substrate 16. This makes it possible for the decorative material 100 to provide a decorative material with excellent weather resistance.

[0093] (Base material for cosmetic materials) The decorative material substrate 16 may be a wood substrate or a metal substrate. The wooden substrate may be, for example, a wood veneer, a wood plywood, a laminated lumber, a particle board, a medium density fiberboard, a hard fiberboard, or a chipboard. The metal substrate may be, for example, a steel plate or an aluminum plate. The decorative material substrate 16 may be a resin such as plastic, or a composite material thereof. When the decorative material substrate 16 is a resin substrate, for example, a polyvinyl chloride resin may be used.

[0094] The decorative material substrate 16 may be made of, for example, a non-combustible steel plate or a non-combustible material as specified by Notification No. 1400 of the Ministry of Construction. The shape of the base material 16 for decorative material is not particularly limited, but may be, for example, a flat plate. An adhesive 15 may be used to bond the base material 16 for decorative material and the decorative sheet 10. The adhesive 15 is the same as the adhesive 15 in the second modified example of the first embodiment, and therefore the same reference numeral is used and a description thereof is omitted.

[0095] When bonding the decorative material substrate 16 and the decorative sheet 10 together, a bonding device such as a cold press, a hot press, a roll press, a laminator, a wrapping machine, an edge bonding machine, or a vacuum press can be used. After bonding the decorative material substrate 16 and the decorative sheet 10, depending on the characteristics of the final product, it may be possible to perform processes such as cutting, tongue and groove processing using a tenon, V-shaped groove processing, and chamfering of the four sides (e.g., C-chamfering).

[0096] The decorative material 100 according to this modification may be provided with grooves and / or chamfers extending from the decorative sheet 10 side to the base material 16 for the decorative material, and the grooves and chamfers may be painted with a colored paint. The colored paint for painting the grooves and chamfers can be, for example, an ink made by dissolving or dispersing a colorant (organic pigment, inorganic pigment) that can also be used in the adhesive layer 5 in a vehicle. Specific examples of colorants are the same as those described above. Examples of vehicles include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyesters, polyurethanes made of isocyanates and polyols, polyacrylics, polyvinyl acetates, polyvinyl chlorides, vinyl chloride-vinyl acetate copolymers, cellulose-based resins, polyamide-based resins, and the like. These vehicles can be used alone or in combination of two or more. As described above, it is preferable to use a colored paint containing a curing agent such as isocyanate that chemically bonds with the silanol groups of the modified resin layer. In addition, solvents, auxiliary agents, and the like can be added as necessary.

[0097] The decorative material 100 according to this modification has been described above. Note that FIG. 3 illustrates an example in which the decorative material 100 is constructed using the decorative sheet 10 according to the first embodiment, but the present disclosure is not limited thereto. The decorative material 100 may be constructed using the decorative sheet 20 according to the first modification of this embodiment, as shown in FIG. 4. For example, the decorative material 100 may have a concealing layer 3, a picture print layer 6, an adhesive layer 5, a transparent resin layer 2, a transparent resin layer 11, and a surface protection layer 4 laminated in this order on one surface side of the original fabric layer 7 in the decorative sheet 20, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 provided on the other surface side of the original fabric layer 7. That is, the decorative material 100 may be configured to include a base material 16 for a decorative material and a decorative sheet 20 that is a laminate bonded to the base material 16 for a decorative material. This makes it possible for the decorative material 100 to provide a decorative material with excellent weather resistance.

[0098] (Effects of the first embodiment) The decorative sheet and decorative material according to this embodiment have the following effects. (1) The decorative sheet (decorative sheets 10, 20) according to this embodiment comprises an original fabric layer 7 containing at least an olefin-based resin, and a laminate portion (laminate portion 50, 51) laminated on the original fabric layer 7. The laminate portion (laminate portion 50, 51) contains at least two types of light absorbents having different maximum absorption wavelengths, and the two types of light absorbents are an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm. According to this configuration, the transmission of light (particularly light in the visible light range) that deteriorates the resin that constitutes the laminated parts (laminate parts 50, 51) is suppressed, making it possible to provide a decorative sheet (laminate) with excellent weather resistance.

[0099] Furthermore, the decorative sheet (laminate) according to this embodiment can also provide the following effects. In laminates (decorative sheets) according to conventional technology, it is necessary to increase the amount of weather resistant agents such as light absorbers to improve weather resistance, which can cause the weather resistant agents to bleed out. In contrast, in the decorative sheet (laminate) according to the present embodiment, by adding at least two types of weather resistant agents having different maximum absorption wavelengths as described above, the total amount of weather resistant agents added can be reduced, and the bleed out of the weather resistant agent can be reduced. In addition, in the laminate (decorative sheet) according to the conventional technology, the weather resistant agent bleeds out from the surface protective layer over time, which results in a decrease in the weather resistant agent concentration in the surface protective layer. In contrast, in the decorative sheet (laminate) according to the present embodiment, by adding at least two types of weather resistant agents having different maximum absorption wavelengths to the surface protective layer, the bleed-out of the weather resistant agent from the surface protective layer is reduced, and the decrease in the weather resistant agent concentration in the surface protective layer can be reduced.

[0100] Furthermore, in laminates (decorative sheets) according to conventional technology, the bleed-out of the weathering agent may cause the hue of the decorative sheet to change (the appearance may change). In contrast, in the decorative sheet (laminate) according to the present embodiment, by adding at least two types of weathering agents having different maximum absorption wavelengths as described above, the bleed-out of the weathering agent is reduced, and the hue change (appearance change) of the decorative sheet can be reduced. In addition, in laminates (decorative sheets) according to conventional technology, interlayer adhesion may be reduced due to bleeding out of the weathering agent. In contrast, in the decorative sheet (laminate) according to the present embodiment, by adding at least two types of weathering agents having different maximum absorption wavelengths as described above, bleeding out of the weathering agent is reduced, and the reduction in interlayer adhesion can be reduced.

[0101] (2) In the decorative sheets (decorative sheets 10, 20), the ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm to the absorbance A2 of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm may be 5 or more. According to this configuration, the transmission of ultraviolet rays that deteriorate the resin that constitutes the laminated parts (laminate parts 50, 51) is suppressed, so that a decorative sheet (laminate) with excellent weather resistance can be provided.

[0102] (3) In the decorative sheets (decorative sheets 10, 20), the ultraviolet absorbing agent may be a triazine-based ultraviolet absorbing agent. According to this configuration, the transmission of ultraviolet rays that deteriorate the resin that constitutes the laminated parts (laminate parts 50, 51) is further suppressed, so that a decorative sheet (laminate) with excellent weather resistance can be provided.

[0103] (4) In the decorative sheet (decorative sheets 10, 20) according to this embodiment, the laminate portion (laminate portion 50, 51) comprises, from the base layer 7 side, a picture printed layer 6, an adhesive layer 5, a transparent resin layer (transparent resin layers 1, 11) and a surface protective layer 4, and the surface protective layer 4 may contain a visible light absorber having a maximum absorption wavelength of 380 to 430 nm. According to this configuration, the transmission of ultraviolet rays that deteriorate the resin that constitutes the laminated parts (laminate parts 50, 51) is suppressed in the outermost surface protective layer 4, so that a decorative sheet (laminate) with excellent weather resistance can be provided.

[0104] (5) In the decorative sheet (decorative sheet 10, 20) according to this embodiment, the laminate portion (laminate portion 50, 51) comprises, in order from the base layer 7 side, a picture printed layer 6, an adhesive layer 5, a transparent resin layer (transparent resin layer 1, 11) and a surface protective layer 4, and the surface protective layer 4 may contain an ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm, and the transparent resin layer (transparent resin layer 1, 11) may contain a visible light absorber having a maximum absorption wavelength of 380 to 430 nm. According to this configuration, the transmission of ultraviolet rays that deteriorate the resin that constitutes the laminated parts (laminate parts 50, 51) is suppressed in the outermost surface protective layer 4, so that a decorative sheet (laminate) with excellent weather resistance can be provided.

[0105] (Example) The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the examples. Example 1 A polyethylene roll (approximately 70 μm) with opacifying properties that had been corona-treated on both sides was used as the base sheet (roll layer), and a primer layer (easy-adhesion layer: approximately 2 μm) was formed on the back side of the polyethylene roll. On the other hand, a wood grain pattern was printed on the surface of the polyethylene base roll using a pattern ink (V180: manufactured by Toyo Ink Co., Ltd.) to form a pattern printed layer (approximately 3 μm), and then a two-component curing urethane anchor coating agent (Takelac A540; manufactured by Mitsui Chemicals, Inc.) was applied on top of the pattern printed layer to form an adhesive layer (approximately 2 μm).

[0106] Next, a polypropylene resin that has been subjected to corona treatment on both sides is prepared as a transparent resin layer, and is thermally laminated with the adhesive layer described above to form a laminate. At this time, the transparent resin layer is made by extruding a resin containing 0.5 parts by mass of a hindered phenol antioxidant (Irganox 1010; manufactured by BASF) and 0.5 parts by mass of a NOR type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) per 100 parts by mass of polypropylene using a melt extruder, and a transparent resin sheet with a thickness of 90 μm is formed as the transparent resin layer adjacent to the adhesive layer. A two-part cured polyurethane resin layer consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxymethacrylate) and a curing agent (nurate of hexamethylene diisocyanate) was applied to the polypropylene resin side (transparent resin layer side) of the laminated laminate to form a surface protective layer (thickness 10 μm). At this time, 5 parts by mass of an ultraviolet absorber (Tinuvin 479: manufactured by BASF), 3 parts by mass of a light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.), and 3 parts by mass of a light stabilizer (Tinuvin 123: manufactured by BASF) were mixed with 100 parts by mass of the acrylic polyol as additives. In this way, the decorative sheet of Example 1 was obtained.

[0107] Example 2 A decorative sheet of Example 2 was obtained in the same manner as in Example 1, except that 0.5 parts by mass of an ultraviolet absorbing agent (Tinuvin 326: manufactured by BASF) was added to the transparent resin layer per 100 parts by mass of polypropylene.

[0108] Example 3 The decorative sheet of Example 3 was obtained in the same manner as Example 1, except that 0.5 parts by mass of an ultraviolet absorber (Tinuvin 326: manufactured by BASF) and 0.5 parts by mass of a light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) were added to the transparent resin layer per 100 parts by mass of polypropylene, and no light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) was added to the surface protective layer.

[0109] Example 4 The decorative sheet of Example 4 was obtained in the same manner as Example 1, except that 0.5 parts by mass of an ultraviolet absorber (LA-46: manufactured by ADEKA Corporation) and 0.5 parts by mass of a light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) were added to the transparent resin layer per 100 parts by mass of polypropylene.

[0110] Example 5 The decorative sheet of Example 5 was obtained in the same manner as Example 1, except that 0.5 parts by mass of an ultraviolet absorber (LA-46: manufactured by ADEKA Corporation) and 0.5 parts by mass of a light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) were added to the transparent resin layer per 100 parts by mass of polypropylene, and no light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) was added to the surface protective layer.

[0111] Comparative Example 1 The decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1, except that 0.5 parts by mass of a light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) was added to the transparent resin layer per 100 parts by mass of polypropylene, and no light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) was added to the surface protective layer.

[0112] Comparative Example 2 The decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that 0.5 parts by mass of an ultraviolet absorber (Tinuvin 326, manufactured by BASF) was added to the transparent resin layer per 100 parts by mass of polypropylene, and no ultraviolet absorber (Tinuvin 479, manufactured by BASF) was added to the surface protective layer.

[0113] Comparative Example 3 The decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1, except that 5 parts by mass of an ultraviolet absorber (LA-46: manufactured by ADEKA Corporation) was added to the transparent resin layer per 100 parts by mass of polypropylene, no ultraviolet absorber (Tinuvin 479: manufactured by BASF) or light absorber (FDB-009: manufactured by Yamada Chemical Industry Co., Ltd.) was added to the surface protective layer, and 5 parts by mass of an ultraviolet absorber (Tinuvin 384: manufactured by BASF) was added per 100 parts by mass of acrylic polyol.

[0114] Comparative Example 4 The decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1, except that 0.5 parts by mass of a light absorber (FDB-009, manufactured by Yamada Chemical Co., Ltd.) was added to the transparent resin layer per 100 parts by mass of polypropylene, no UV absorber (Tinuvin 479, manufactured by BASF) or a light absorber (FDB-009, manufactured by Yamada Chemical Co., Ltd.) was added to the surface protective layer, and 5 parts by mass of a UV absorber (Tinuvin 384, manufactured by BASF) was added per 100 parts by mass of acrylic polyol.

[0115] Comparative Example 5 The decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1, except that 0.5 parts by mass of an ultraviolet absorber (Tinuvin 326, manufactured by BASF) was added to the transparent resin layer per 100 parts by mass of polypropylene, no ultraviolet absorber (Tinuvin 479, manufactured by BASF) or light absorber (FDB-009, manufactured by Yamada Chemical Industry Co., Ltd.) was added to the surface protective layer, and 5 parts by mass of an ultraviolet absorber (Tinuvin 384, manufactured by BASF) was added per 100 parts by mass of acrylic polyol.

[0116] [Testing and evaluation methods] <Absorbance measurement> A transparent resin layer was prepared using the types and amounts of ultraviolet absorbents and light absorbents shown in Examples 1 to 5 and Comparative Examples 1 to 5, and a surface protective layer was formed thereon to prepare a laminate. In this example, the absorbances of the above-mentioned laminate, "absorbance A1" and "absorbance A2", were measured in accordance with JIS K0115:2004 using an ultraviolet-visible-near infrared spectrophotometer (manufactured by Hitachi, Ltd., product name: U-4100).

[0117] <Weather resistance test> The decorative sheet of this example was placed in a sealed device, and a weather resistance test was carried out using a xenon lamp as the light source. The sealed device was also connected to an oxygen supply device, a humidity supply device, a water supply device, etc., so that the oxygen concentration, humidity, and water spray intervals could be freely set. This test was carried out under the following conditions. Light conditions Illuminance 18mW / cm 2 , Black panel temperature 63℃, oxygen concentration 50%, humidity 90% RH for 20 hours Condensation conditions Illuminance 0mW / cm 2 , black panel temperature 30℃, oxygen concentration 50%, humidity 90% RH for 4 hours Water spray conditions 10 seconds before and after condensation conditions Evaluation criteria ◎: No change in appearance was observed across the entire decorative sheet ○: Minor changes in appearance were observed throughout the entire decorative sheet, but no significant changes such as cracks were observed. ×: A significant change in appearance was observed throughout the entire decorative sheet.

[0118] The evaluation results are shown in Table 1. In the table, "λmax" means the maximum absorption wavelength of each ultraviolet absorbent.

[0119] [Table 1]

[0120] Moreover, for example, this embodiment can have the following configuration. (1) A base sheet containing at least an olefin-based resin; A laminate including a laminate portion laminated on the base sheet and including at least a transparent resin layer, the laminated portion contains at least two types of light absorbing agents having maximum absorption wavelengths different from each other, The laminate is characterized in that the two types of light absorbents are an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm. (2) The laminate according to the above (1), wherein the ratio (A1 / A2) of the absorbance A1 of the ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm to the absorbance A2 of the visible light absorbent having a maximum absorption wavelength of 380 to 430 nm is 5 or more. (3) The laminate according to the above (1) or (2), wherein the ultraviolet absorbent is a triazine-based ultraviolet absorbent. (4) The laminated portion includes, in order from the base sheet side, a picture print layer, an adhesive layer, a transparent resin layer, and a surface protective layer, The laminate according to any one of the above (1) to (3), wherein the ultraviolet absorbing agent is contained in the surface protective layer. (5) The laminated portion includes, in order from the base sheet side, a picture print layer, an adhesive layer, a transparent resin layer, and a surface protective layer, The laminate according to any one of the above (1) to (4), wherein the ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm is contained in the surface protective layer, and the visible light absorber having a maximum absorption wavelength of 380 to 430 nm is contained in the transparent resin layer. [Explanation of symbols]

[0121] 1, 2 Transparent resin layer 1a Embossed pattern 3. Hidden Layer 4 Surface protective layer 5 Adhesive layer 6. Pattern printing layer 7 Original layer 8 Easy adhesive layer 10, 20 Decorative sheet 100 Cosmetic materials

Claims

1. A base sheet containing at least an olefin-based resin; A laminate including a laminate portion laminated on the base sheet and including at least a transparent resin layer, the laminated portion includes at least two types of light absorbing agents having maximum absorption wavelengths different from each other, The laminate is characterized in that the two types of light absorbents are an ultraviolet absorbent having a maximum absorption wavelength of 280 to 330 nm and a visible light absorbent having a maximum absorption wavelength of 380 to 430 nm.

2. The laminate according to claim 1, characterized in that a ratio (A1 / A2) of an absorbance A1 of the ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm to an absorbance A2 of the visible light absorber having a maximum absorption wavelength of 380 to 430 nm is 5 or more.

3. 2. The laminate according to claim 1, wherein the ultraviolet absorbing agent is a triazine-based ultraviolet absorbing agent.

4. The laminated portion includes, in order from the base sheet side, a picture print layer, an adhesive layer, a transparent resin layer, and a surface protective layer, 2. The laminate according to claim 1, wherein the ultraviolet absorbing agent is contained in the surface protective layer.

5. The laminated portion includes, in order from the base sheet side, a picture print layer, an adhesive layer, a transparent resin layer, and a surface protective layer, The laminate according to any one of claims 1 to 4, characterized in that the ultraviolet absorber having a maximum absorption wavelength of 280 to 330 nm is contained in the surface protective layer, and the visible light absorber having a maximum absorption wavelength of 380 to 430 nm is contained in the transparent resin layer.

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