laminate

Abstract

To provide a laminate capable of improving weather resistance compared to conventional laminates, even when an addition amount of a weather-resistant agent is approximately the same as a conventional addition amount.SOLUTION: A decorative sheet 10 includes a transparent resin layer 1 and a surface protective layer 4 in this order on a base sheet layer 7 containing at least an olefinic resin, wherein an oxygen permeability at 30°C / 0%RH of an oxygen barrier laminate 50 composed of the transparent resin layer 1 and the surface protective layer 4 before a weather resistance test is 1,500 cc / (m2 day atm) or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] In recent years, many decorative sheets using olefin resins have been proposed as alternatives to decorative sheets made of polyvinyl chloride (see, for example, Patent Document 1). The use of decorative sheets is expanding from indoors to outdoors, so they need to be weather resistant for a long period of time. Up until now, efforts have been made to improve weather resistance by adding weather resistance agents such as ultraviolet absorbers and radical scavengers to the surface protective layer and transparent resin layer that make up the decorative sheet. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2-128843 Summary of the Invention [Problem to be solved by the invention]

[0004] However, if the amount of weather resistant agent is increased too much in an attempt to further improve weather resistance, bleeding out of the decorative sheet occurs, which can result in changes in appearance (e.g., color change) and reduced interlayer adhesion. Thus, in many decorative sheets according to conventional technology, it has been difficult to further improve weather resistance, etc., even if the amount of weather resistant agent added is increased.

[0005] The present disclosure has been made in consideration of the above circumstances, and aims to provide a laminate that can improve weather resistance compared to conventional weather resistance agents even when the amount of added weather resistance agent is approximately the same as that of conventional weather resistance agents. [Means for solving the problem]

[0006] In order to solve the above problems, a laminate according to one embodiment of the present disclosure comprises a substrate sheet containing at least an olefin-based resin, a transparent resin layer, and a surface protective layer in this order, and the oxygen barrier laminate comprising the transparent resin layer and the surface protective layer has an oxygen permeability of 1500 cc / (m ) at 30°C / 0% RH before a weather resistance test. 2 ·day·atm) or less. [Effects of the Invention]

[0007] According to one aspect of the present disclosure, it is possible to provide a laminate that can improve weather resistance compared to conventional weather resistance agents even when the amount of the weather resistance agent added is approximately the same as that of conventional weather resistance agents. More specifically, according to one aspect of the present disclosure, it is possible to provide a laminate that has good weather resistance by suppressing oxygen permeation from the surface of the laminate. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a cross-sectional view showing a schematic configuration of a laminate (decorative sheet) according to one embodiment of the present disclosure. [Figure 2] FIG. 1 is a cross-sectional view illustrating a schematic configuration of a laminate (decorative sheet) according to a first modified example of an embodiment of the present disclosure. [Figure 3] FIG. 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. 10 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 INVENTION

[0009] Hereinafter, a laminate (hereinafter also referred to simply as "decorative sheet") and a decorative member according to an embodiment of the present disclosure will be described with reference to the drawings. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, and the like differ from the actual ones. The layers do not necessarily need to be stacked in the order shown in the drawings, as long as they fall within the scope of the present disclosure. Layers not shown in the drawings may also be added. Furthermore, the embodiments shown below exemplify configurations for embodying the technical concept of the present disclosure, and the technical concept of the present disclosure is not limited to the materials, shapes, structures, etc. of the components described below. The technical concept of the present disclosure may be modified in various ways within the technical scope defined by the claims. Furthermore, the directions of "left and right" and "up and down" in the following explanation are merely definitions for the convenience of explanation and do not limit the technical idea 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 extensive research, the present inventors have focused on the fact that in decorative sheets, peroxy radicals formed by the combination of radicals and oxygen are involved in the deterioration of weather resistance, such as changes in appearance, and have discovered that it is possible to reduce the deterioration of weather resistance in decorative sheets by suppressing the amount of peroxy radicals produced by reducing the amount of oxygen that permeates from the surface side of the decorative sheet. This has led the present inventors to invent a decorative sheet that can improve weather resistance compared to conventional decorative sheets, even when the amount of weather resistance agent added is about the same as conventional amounts.

[0011] In other words, the present disclosure proposes and provides a new design concept for improving the weather resistance of decorative sheets, as will be explained below. In conventional design concepts, in order to improve the weather resistance of decorative sheets, as described above, attention has been focused on the type of weather resistant agent (e.g., type of ultraviolet absorber or type of radical scavenger) added to the decorative sheet and the amount of weather resistant agent added, and these have been adjusted. In response to this, the present inventors have newly discovered that in order to improve the weather resistance of decorative sheets, it is important not only to adjust the type and amount of weather resistant agent added to the decorative sheet, but also to prevent oxygen from penetrating from the surface side of the decorative sheet. More specifically, the inventors focused on the mechanism of degradation of polymeric materials. Degradation of polymeric materials often occurs as follows: (1) first, light irradiation or heat cleaves the main chain or side chain, generating radicals; (2) these radicals combine with oxygen to generate peroxy radicals; and (3) these peroxy radicals cause autoxidation. Therefore, they reasoned that even if radicals are generated, if there is no oxygen to combine with them (or if the amount of oxygen is small), degradation (oxidative degradation) can be suppressed, leading to the invention of the decorative sheet of this application.

[0012] Thus, the design concept of the present disclosure is significantly different from conventional design concepts, and focuses on and adjusts the oxygen permeability of a laminate (oxygen barrier laminate) composed of two layers, a transparent resin layer and a surface protective layer, that make up the decorative sheet, in order to improve the weather resistance of the decorative sheet. By adjusting the oxygen permeability of a laminate (oxygen barrier laminate) composed of two layers, a transparent resin layer and a surface protective layer, that make up the decorative sheet, that is, by limiting the amount of oxygen that permeates from the surface side of the decorative sheet, it is possible to prevent a decrease in the weather resistance (particularly changes in appearance) of the decorative sheet. A first embodiment of the present disclosure (hereinafter referred to as "the present embodiment") will be described below with reference to the drawings.

[0013] (Oxygen permeability measurement) First, the "oxygen permeability" defined in this embodiment will be explained. The oxygen permeability in this embodiment is a value measured using a gas permeability measuring device by differential pressure gas chromatography according to JIS K7126A method (differential pressure method), and is a value measured under the measurement conditions of 30°C / 0%RH (temperature 30°C, relative humidity 0%). In this embodiment, the oxygen permeability is measured for a two-layer sheet consisting of a transparent resin layer 1 and a surface protective layer 4, i.e., a two-layer sheet (oxygen barrier laminate 50) in which the surface protective layer 4 is laminated on top of the transparent resin layer 1.

[0014] In this embodiment, the oxygen permeability of the oxygen barrier laminate 50 at 30°C / 0% RH before the weather resistance test is 1500 cc / (m 2 ·day·atm) or less. The oxygen permeability of the oxygen barrier laminate 50 before the weather resistance test is 1500cc / (m 2 ·day·atm) or less, oxygen permeation (oxygen diffusion) from the surface of the oxygen barrier laminate 50 is sufficiently suppressed, making it possible to suppress oxidative degradation of each layer that makes up the decorative sheet. In this way, in this embodiment, by designing the oxygen permeability near the outermost layer to be sufficiently low, oxygen permeation to the lower layers is restricted, and as a result, the weather resistance of the entire decorative sheet can be improved. It should be noted that a higher oxygen permeability value means a lower barrier property against oxygen gas, and a lower oxygen permeability value means a higher barrier property against oxygen gas.

[0015] Furthermore, it is preferable that the rate of change in oxygen permeability of the oxygen barrier laminate 50 before and after the weather resistance test (1000-hour super xenon test) is 35% or less. In this embodiment, the "change rate of oxygen permeability of the oxygen barrier laminate 50 before and after the weather resistance test (1000-hour super xenon test)" is a value calculated by the following formula (1). "(Oxygen permeability of the oxygen barrier laminate 50 after the weather resistance test / Oxygen permeability of the oxygen barrier laminate 50 before the weather resistance test) - 1" × 100 Formula (1)

[0016] The super xenon test in this embodiment was conducted using a super xenon testing machine (Toyo Seiki Atlas Weatherometer Ci4000) under test conditions of 180W light irradiation, 12 minutes of rainfall / 120 minutes cycle, and a test time of 1000 hours.

[0017] (Composition of decorative sheet) The following describes each component of the decorative sheet (an example of a laminate) of this embodiment. Note that this embodiment will be described assuming that the transparent resin layer (transparent resin layer) is a single layer. The decorative sheet 10 shown in Figure 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 the layer that serves as the base material for the decorative sheet 10, and is also referred to as the base sheet or base fabric layer.

[0018] The decorative sheet 10 according to this embodiment may be any decorative sheet having at least an adhesive layer 5 and a base fabric layer 7 on one side of a transparent resin layer 1, and a surface protective layer 4 on the other side of the transparent resin layer 1. In other words, the decorative sheet 10 may be a laminate having at least a base fabric layer 7, an adhesive layer 5, a transparent resin layer 1, and a surface protective layer 4 in this order. In addition, in the decorative sheet 10 according to this embodiment, the laminate (a two-layer sheet) consisting of the transparent resin layer 1 and the surface protective layer 4 is referred to as an "oxygen barrier laminate 50." In order to improve the design, an embossed pattern may be appropriately provided on the surface of the transparent resin layer 1 on the surface protection layer 4 side.

[0019] The total thickness of the decorative sheet 10 is preferably in the range of 60 μm to 250 μm. If the total thickness is thinner than 60 μm, there is a concern that the required performance of the decorative sheet, such as hiding ability (ability to hide the underlying surface of the substrate for decorative material) and scratch resistance, may be reduced. Furthermore, if the total thickness is thicker than 250 μm, there is a concern that costs may increase and processability may be reduced when bonding the decorative sheet to the substrate for decorative material. Furthermore, the decorative sheet of this embodiment preferably does not contain vinyl chloride resin. By using a decorative sheet that does not contain vinyl chloride resin, concerns about the generation of toxic gases and the like during incineration are reduced. Hereinafter, each layer constituting the decorative sheet of this embodiment will be described in detail.

[0020] (Original layer) To impart design, scratch resistance, and post-processing resistance to the decorative sheet, the base fabric layer (substrate sheet) 7 may be appropriately selected from the following materials: paper (e.g., tissue paper, titanium paper, resin-impregnated paper); synthetic resins (e.g., polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic), or foams of these synthetic resins; rubbers (e.g., ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, polyurethane); organic or inorganic nonwoven fabrics; synthetic paper; and metal foils (e.g., aluminum, iron, gold, silver). The base fabric layer 7 may also be a sheet made of the same resin composition as the transparent resin layer 1. Among these, thermoplastic resins, particularly polyolefin-based materials such as polypropylene and polyethylene, are preferred. In other words, the base fabric layer 7 is preferably a layer containing at least an olefin-based resin.

[0021] 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 ... Examples of such copolymers include those obtained by homopolymerizing or copolymerizing 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.) and those obtained by copolymerizing 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.

[0022] When a substrate with an inactive surface such as a polyolefin-based material is used as the raw fabric layer 7, it is desirable to perform, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, etc. on the front and back of the raw fabric layer 7. Furthermore, a primer layer (not shown) may be provided between the raw fabric layer 7 and the picture printed layer 6 to ensure adhesion.

[0023] If it is desired to impart hiding properties to the decorative sheet, a hiding colored sheet may be used for the base fabric layer 7, or as shown in FIG. 1, a hiding layer 3 may be provided above the base fabric layer 7 and below the picture-printed layer 6. The hiding layer 3 will be described later. When a colored sheet is used as the base fabric layer 7, the resin material constituting the base fabric layer 7 can be colored by adding a colorant. Examples of colorants that can be used include inorganic pigments (titanium oxide, carbon black, etc.) and organic pigments (phthalocyanine blue, etc.), as well as dyes. The colorant used in this embodiment can be one or more types selected from known or commercially available colorants, and the amount added can be adjusted to obtain the desired hiding properties and design. If necessary, various additives such as fillers, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, nucleating agents, ultraviolet 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 the ease of printing and costs.

[0024] (Picture printing layer) The pattern printed layer 6 can be formed on the raw fabric 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 selected appropriately from, for example, soluble 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 either a one-component type or a two-component type using a hardener. Furthermore, the ink can also 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. In other words, in the decorative sheet 10 according to this embodiment, the picture-printed layer 6 preferably contains a urethane-based resin as a binder.

[0025] The urethane-based resin used in the picture-printed layer 6 is not particularly limited, and either a one-component curing type or a two-component curing type can be used. For example, a one-component ester-based polyurethane resin can be suitably used as a one-component curing type urethane-based resin. Furthermore, a two-component curing type urethane-based resin can be used that contains, for example, a polyol component having OH groups as a main component and an isocyanate component as a curing agent component. Examples of polyol components having OH groups include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of isocyanate components include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, a polyester urethane resin using a polyester polyol as a main component can be suitably used for the picture-printed layer 6.

[0026] In addition to the binder, the picture print layer 6 may contain pigments, colorants such as dyes, extender pigments, solvents, and various additives that are commonly contained in ink. 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. Furthermore, apart from applying ink, designs can also be applied by vapor deposition or sputtering of various metals.

[0027] The thickness of the picture-printed layer 6 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 3 μm. By making the film thickness of the picture-printed layer 6 sufficiently thick, it may be possible to improve interlayer adhesion in the decorative sheet 10 (for example, adhesion between the base fabric layer 7, the concealing layer 3, and the adhesive layer 5). On the other hand, if the thickness of the picture-printed layer 6 is too thick, post-processability (for example, 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-processability. It is preferable that the pattern printed layer 6 be in contact with the base fabric layer 7 from the viewpoint of adhesion.

[0028] (hidden layer) The concealing layer 3 can be provided on the base fabric layer 7 or on the pattern-printed layer 6 formed on the transparent resin layer 1 by the same printing method as for the pattern-printed layer 6. The concealing layer 3 may be formed as needed, and can be omitted, for example, when a concealing colored sheet is used for the base fabric layer 7. When applying the concealing layer 3, for example, a comma coater, knife coater, lip coater, metal vapor deposition, sputtering, or the like may be used. The concealing layer 3 is generally provided as an upper layer of the base fabric layer 7 and as a lower layer of the pattern-printed layer 6.

[0029] The material used for the concealing layer 3 can basically be the same as that used for the picture-printed layer 6. Since the purpose of the concealing layer 3 is to provide concealment, it is preferable to use, for example, opaque pigments, titanium oxide, iron oxide, etc. as pigments. Metals such as gold, silver, copper, and aluminum can also be added to improve concealment. Flake-shaped aluminum is commonly added. If the coating thickness, i.e., the thickness of the concealing layer 3, is less than 2 μm, it is difficult to provide concealment, and if it exceeds 10 μm, the cohesive strength of the resin layer tends to be weakened. Therefore, the thickness of the concealing layer 3 is preferably in the range of 2 μm to 10 μm.

[0030] (adhesive layer) Any material can be selected for the adhesive layer 5, and bonding methods using the adhesive layer 5 include, for example, thermal lamination, extrusion lamination, and dry lamination. The adhesive contained in the adhesive layer 5 can be selected from, for example, acrylic, polyester, polyurethane, and phthalic acid (alkyd acid)-based materials. The adhesive contained in the adhesive layer 5 is usually a two-component curing type due to its high cohesive strength, and it is particularly desirable to use a urethane-based material obtained by reacting isocyanate with a polyol due to its workability, cost, and high cohesive strength. In other words, the adhesive layer 5 preferably contains a urethane resin.

[0031] The urethane-based resin used in the adhesive layer 5 is not particularly limited, and either a one-component curing type or a two-component curing type can be used. For example, a one-component ester-based polyurethane resin can be suitably used as a one-component curing type urethane-based resin. Furthermore, a two-component curing type urethane-based resin can be used that contains, for example, a polyol component having an OH group as a main component and an isocyanate component as a curing agent component. Examples of polyol components having an OH group include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of isocyanate components include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, a polyester urethane resin using a polyester polyol as a main component can be suitably used for the adhesive layer 5.

[0032] 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 adhesive layer 5 sufficiently thick, it may be 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 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 layers and the post-processability.

[0033] (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, from a highly crystalline polypropylene resin. Furthermore, one or both surfaces of the transparent resin layer 1 may be activated, if necessary, by, for example, corona treatment, plasma treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, or the like.

[0034] When forming the transparent resin layer 1 as a film-forming sheet, a method using an extruder is typically used. When forming the transparent resin layer 1 by lamination, there are no particular restrictions, and methods using, for example, heat and pressure, extrusion lamination, and dry lamination are commonly used. Furthermore, when forming an embossed pattern 1a, there are methods, for example, where a sheet is first laminated by various methods and then embossed by heat and pressure, or where a pattern is formed on a cooling roll and embossed using the cooling roll simultaneously with extrusion lamination. More specifically, the embossed pattern 1a is directly applied to, for example, a highly crystalline polypropylene sheet, which is the transparent resin layer 1. Methods include applying the embossed pattern to the formed sheet using an embossing plate with a patterned pattern under heat and pressure, or using a cooling roll with a patterned pattern to form an embossed pattern simultaneously with cooling during film formation using an extruder. Here, ink can be embedded in the embossed pattern 1a as an embossed portion to further improve the design. The embossed pattern 1a may be provided if necessary, and may not be provided if unnecessary.

[0035] 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, weather resistance and scratch resistance may be reduced. If the thickness of the transparent resin layer 1 exceeds 170 μm, the manufacturing cost may be increased and post-processing may be reduced. If necessary, various additives such as heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, and catalyst scavengers may also be added to the transparent resin layer 1, as long as the features of this embodiment are not impaired.

[0036] More specifically, in this embodiment, one or more types of ultraviolet absorbers (UVA) may be added, or a light stabilizer (HALS) may be added, to the transparent resin layer 1. In other words, it is sufficient that the transparent resin layer 1 contains at least one of an ultraviolet absorber (UVA) and a light stabilizer (HALS). Alternatively, the transparent resin layer 1 may contain both an ultraviolet absorber (UVA) and a light stabilizer (HALS). The content of the ultraviolet absorber (UVA) is preferably in the range of 0.1 to 2 parts by mass relative to 100 parts by mass of the resin constituting the layer (transparent resin layer 1) to which the ultraviolet absorber (UVA) is added.

[0037] The content of the light stabilizer (HALS) is preferably in the range of 0.1 to 2 parts by mass relative to 100 parts by mass of the resin constituting the layer (transparent resin layer 1) to which the light stabilizer (HALS) is added. By adding an ultraviolet absorber (UVA) or a light stabilizer (HALS) to the transparent resin layer 1, it is possible to suppress oxidative degradation due to light (exposure light) during weathering tests such as the Super Xenon test, and to prevent changes in appearance such as cracks and breaks. As a result, an increase in oxygen permeability of the transparent resin layer 1 is suppressed, and deterioration in weather resistance (particularly changes in appearance) can be further suppressed.

[0038] Typically, any combination of heat stabilizers, such as phenols, sulfur compounds, phosphorus compounds, and hydrazine compounds, flame retardants, such as aluminum hydroxide and magnesium hydroxide, UV absorbers, such as benzotriazoles, benzoates, benzophenones, and triazines, and light stabilizers, such as hindered amines (HALS), is added. Weather resistance must be considered when using the transparent resin layer 1. In this case, a UV absorber and a light stabilizer may be added to the transparent resin layer 1, with the appropriate amounts being 0.1% by mass to 2.0% by mass, based on 100% by mass of the transparent resin layer 1. The transparent resin layer 1 may also contain a nucleating agent (nano-sized nucleating agent) that has been subjected to vesiculation treatment by supercritical reverse phase evaporation.

[0039] 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.

[0040] 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, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof. Furthermore, as the benzophenone-based ultraviolet absorber, for example, octabenzone, its modified products, polymers and derivatives can be used.

[0041] Examples of hindered amine light stabilizers (HALS) 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]], polycondensation product of dimethyl succinate and 1-(2 hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and mixtures, modified products, polymers, and derivatives thereof.

[0042] The crystalline polypropylene resin forming the transparent resin layer 1 can be appropriately selected from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof, each having a different pentad fraction. It is more important that the crystalline polypropylene resin be a highly crystalline homopolypropylene resin, i.e., a homopolymer of propylene, having an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. Resins other than the crystalline polypropylene forming the transparent resin layer 1 can be appropriately selected depending on the purpose of blending, as long as they do not significantly adversely affect the physical properties of the crystalline polypropylene. However, to maintain suitability for V-groove bending, resins with good compatibility with the crystalline polypropylene resin forming the transparent resin layer 1 are preferred. 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.

[0043] The terms used in the above description of the transparent resin layer 1 will be briefly explained below. Nucleating agents are added to promote the formation of crystal nuclei during resin crystallization or to convert the nucleating agent itself into a crystal nucleus. Nucleating agents include melting agents, which melt into the base resin upon addition and re-precipitate to form crystal nuclei, and non-melting agents, which do not melt and remain as crystal nuclei after addition to the base resin. Examples of nucleating agents for polypropylene resin include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in this embodiment, in order to maximize the effects of nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts, which are non-melting agents that are expected to have good transparency. However, if transparency can be achieved by nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. Furthermore, melting benzylidene sorbitol may be appropriately mixed with a non-melting nucleating agent.

[0044] 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 using 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclear species) with a mass number of 13, and defines 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 arranged in a row, as determined by C-NMR, and is used as a measure of crystallinity or stereoregularity. This isotactic pentad fraction is one of the important factors that determine the scratch resistance of the surface. Basically, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, and therefore the better the scratch resistance.

[0045] (Surface protective layer) As shown in Fig. 1, the surface protective layer 4 is formed on the transparent resin layer 1. That is, the decorative sheet 10 has the surface protective layer 4, which serves as the outermost layer, 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 designability to the decorative sheet 10. The surface protective layer 4 may contain various additives, such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as needed.

[0046] 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 to contain 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. That is, the surface protective layer 4 may be formed to contain only a thermosetting resin as the curable resin composition, or may be formed to contain only an ionizing radiation curable resin. Furthermore, the surface protective layer 4 may be formed to contain 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.

[0047] The thermosetting resin used for the surface protective layer 4 can be appropriately selected from, for example, polyurethane, acrylic, acrylic silicone, fluorine-based, 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-component type or a two-component type using a curing agent. Among these, a urethane-based top coat that utilizes an isocyanate reaction is desirable from the viewpoints of workability, cost, and the cohesive strength of the resin itself. 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 (acrylic polyol compound) and an isocyanate curing agent.

[0048] 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.

[0049] The ionizing radiation curable resin used in the surface protective layer 4 can be appropriately selected from, for example, polyester acrylates, epoxy acrylates, urethane acrylates, acrylic acrylates, etc., but it is particularly preferable to use urethane acrylates and acrylic acrylates, which have good weather (light) resistance. From the viewpoint of workability, the ionizing radiation curable resin is preferably cured with active energy rays such as ultraviolet rays or electron beams. Examples of electron beam sources that can be used include light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, and metal halide lamps. The wavelength of the ultraviolet light is preferably in the range of 180 nm to 400 nm.

[0050] It is more preferable to use a mixture of a thermosetting resin and an ionizing radiation curable resin used in the surface protective layer 4, for example, 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. 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).

[0051] The ionizing radiation curable resin constituting the surface protective layer 4 is preferably an ultraviolet curable resin that is cured by ultraviolet rays. The UV-curable resin constituting the surface protective layer 4 preferably has four or more functional groups and contains one or more components with a mass-average molecular weight of 500 or more. More preferably, it has four or more functional groups and contains one or more components with a mass-average molecular weight in the range of 500 to 5,000. UV-curable resins with fewer than four functional groups are undesirable because the crosslinking density is low and scratch resistance is significantly reduced. UV-curable resins with a mass-average molecular weight of less than 500 are undesirable because the surface condition during coating is significantly deteriorated. UV-curable resins with a mass-average molecular weight of more than 5,000 are undesirable because the viscosity of the coating liquid increases and coating suitability is significantly reduced.

[0052] The amount of the photoinitiator to be added is not particularly limited, but is preferably about 0.1 to 15 parts by mass per 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 radically polymerizable unsaturated group, the photoinitiator can be selected from at least one of, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, and isopropyl-N,N dimethylaminobenzoate. It is also desirable to combine multiple types to suit the light source and production environment. In the case of a resin system having a cationically 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.

[0053] The method for forming the surface protection layer 4 is not particularly limited, and the surface protection layer 4 may be formed by applying a coating liquid of the above-mentioned material 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.

[0054] To further improve weather resistance, an ultraviolet absorber may be added to the surface protective layer 4. The ultraviolet absorber may be selected from, for example, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. In addition to the ultraviolet absorber, a light stabilizer may be added to the surface protective layer 4 as appropriate. As described above, in this embodiment, the surface protective layer 4 may contain one or more ultraviolet absorbers (UVA) or a light stabilizer (HALS). That is, the surface protective layer 4 may contain at least one of an ultraviolet absorber (UVA) and a light stabilizer (HALS). Alternatively, the surface protective layer 4 may contain both an ultraviolet absorber (UVA) and a light stabilizer (HALS).

[0055] The content of the ultraviolet absorber (UVA) is preferably in the range of 1 part by mass to 20 parts by mass relative to 100 parts by mass of the resin constituting the layer (surface protective layer 4) to which the ultraviolet absorber (UVA) is added. The content of the light stabilizer (HALS) is preferably in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of the resin constituting the layer (surface protective layer 4) to which the light stabilizer (HALS) is added. By adding ultraviolet absorbers (UVA) and light stabilizers (HALS) to the surface protective layer 4, it is possible to suppress oxidative degradation due to light (exposure light) during weathering tests such as the Super Xenon test, and to prevent changes in appearance such as cracks and breaks. As a result, the oxygen permeability of the surface protective layer 4 is suppressed, and changes in the appearance of the entire decorative sheet 10 (decrease in weather resistance) can be suppressed.

[0056] 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.

[0057] 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, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

[0058] Furthermore, as the benzophenone-based ultraviolet absorber, for example, octabenzone, its modified products, polymers and derivatives can be used. Examples of the light stabilizer that can be used include hindered amine light stabilizers (HALS), such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Furthermore, in order to improve the scratch resistance of the surface or to adjust the gloss (luster) associated with imparting design properties, it is desirable to add an inorganic filler to the surface protective layer 4 as a gloss adjuster.

[0059] Examples of inorganic fillers that may 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 fiber. Inorganic fine particles having an average particle size of 1 μm to 30 μm can be used as the inorganic filler, with inorganic fine particles having an average particle size of 1 μm to 10 μm being particularly preferred. If the average particle size of the inorganic filler is less than 1 μm, it tends to be difficult to achieve a matte finish. This is because, to achieve a matte finish, the inorganic filler should ideally have a particle size equal to or larger than the thickness of the film (layer) to which it is added. If the average particle size of the inorganic filler exceeds 30 μm, or more precisely, 10 μm, the inorganic filler is likely to fall off from the surface protective layer 4 under high load conditions, resulting in a change in gloss and a deterioration in the appearance of the surface.

[0060] For example, when gravure printing is selected as the method for forming the surface protective layer 4, the coating thickness of one layer is appropriate to be 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 equal to or smaller than the thickness that can be coated at one time. The content of the inorganic filler in the surface protective layer 4 is preferably in the range of 1 part by mass to 20 parts by mass relative 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. On the other hand, if the content of the inorganic filler exceeds 20 parts by mass, the surface gloss may be significantly reduced, which may impair the design and reduce weather resistance and stain resistance.

[0061] 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 inorganic fillers with untreated surfaces may also be added to the surface protective layer 4. Furthermore, when performing the surface treatment, it is desirable that the inorganic filler have a functional group that hydrophobicizes the surface 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 that constitutes the surface protective layer 4. When the inorganic filler is subjected to the surface treatment, the method is not particularly limited, and any known method can be selected.

[0062] The surface treatment agent used for the surface treatment of the inorganic filler can be at least one of surfactants, fatty acid metal salts, silane coupling agents, silicones, waxes, and modified resins. Examples of the surface treatment agent of this embodiment include silicone oils, alkyl silazanes, trimethylsilylating agents, alkoxysilanes, siloxanes, and silane coupling agents, as well as titanium coupling agents and phosphoric acid- and fatty acid-based surfactants, and may be one type or a combination of multiple types.

[0063] 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, methacrylic-modified, mercapto-modified, phenol-modified, one-end reactive-modified, heterofunctional group-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, specially hydrophilic-modified, higher alkoxy-modified, higher fatty acid-containing-modified, and fluorine-modified silicone oils).

[0064] 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.

[0065] As the trimethylsilylating agent, an alkoxysilane compound among silane coupling agents can be selected. Furthermore, examples of titanate coupling agents that may 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. Furthermore, as an aluminate-based coupling agent, for example, acetoalkoxyaluminum diisopropylate may be selected.

[0066] When an embossed pattern 1a is applied to the surface of the transparent resin layer 1 on the surface protective layer 4 side, the ink forming the surface protective layer 4 can be embedded into this embossed pattern by wiping processing to improve the design. From the viewpoint of weather resistance, in order to protect the transparent resin layer 1 as a substrate, one method is to impart weather resistance to the surface protective layer 4 and the transparent resin layer 1 as described above. In addition to this, there is also a method in which an ultraviolet absorber and a light stabilizer are added to the adhesive layer 5 and the picture printed layer 6 themselves, respectively, in order to protect the picture printed layer 6. Although not shown, an embossed pattern similar to the embossed pattern 1a may be provided on the outermost surface of the surface protection layer 4. This can further improve the design.

[0067] Furthermore, although an example in which the surface protective layer 4 is a single layer has been described in FIG. 1, 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 may have 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 an overall 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. 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 contains a cured product of a curable resin composition, and layers formed from different types of resin materials may be included.

[0068] [Oxygen Permeability of Oxygen Barrier Laminate 50] In this embodiment, the oxygen barrier laminate 50, which is a laminate consisting of only the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability of 1500 cc / (m) at 30°C / 0% RH before the weather resistance test. 2 ·day·atm). By setting the oxygen permeability of the oxygen barrier laminate 50 within the above numerical range, it is possible to prevent oxygen permeation (oxygen diffusion) from the surface side of the decorative sheet 10, thereby reducing changes in appearance of the decorative sheet 10 such as cracks and breaks. The oxygen permeability of the oxygen barrier laminate 50 is a value measured using a gas permeability measuring device by differential pressure gas chromatography according to JIS K7126A method (differential pressure method), and is a value measured under the measurement conditions of 30°C / 0%RH (temperature 30°C, relative humidity 0%). The oxygen permeability of the oxygen barrier laminate 50 can be controlled, for example, by selecting the materials and combining the formation conditions (curing method and hardness adjustment) of the transparent resin layer 1 and the surface protective layer 4. The oxygen permeability of the oxygen barrier laminate 50 can also be controlled by adjusting the degree of curing of the transparent resin layer 1 and the surface protective layer 4 based on the temperature history until the decorative sheet is in its final form. The oxygen permeability of the oxygen barrier laminate 50 can also be controlled, for example, by adjusting the layer thickness of the transparent resin layer 1 and the surface protective layer 4.

[0069] [Change in oxygen permeability of oxygen barrier laminate 50 before and after weathering test] Before the weather resistance test, the oxygen barrier laminate 50, which is a laminate composed of the transparent resin layer 1 and the surface protective layer 4, had an oxygen permeability of 1500 cc / (m at 30°C / 0% RH. 2By setting the temperature at or below 100°C (day·atm), the rate of change in oxygen permeability of the oxygen barrier laminate 50 before and after the weather resistance test can be kept to 35% or less. If the rate of change in oxygen permeability of the oxygen barrier laminate 50 before and after weather resistance testing is within the above numerical range, it will be possible to prevent oxygen permeation (oxygen diffusion) from the surface side of the decorative sheet 10, even if the decorative sheet 10 is used for a long period of time outdoors, etc., and changes in the appearance of the decorative sheet 10, such as cracks and breaks, can be reduced. In this embodiment, the rate of change in oxygen permeability before and after the weather resistance test is a value calculated from the oxygen permeability before and after the super xenon test, and is a value measured under measurement conditions with an exposure time (test time) of 1000 hours. The super xenon test in this embodiment was conducted using a super xenon testing machine (Toyo Seiki Atlas Weatherometer Ci4000) under test conditions of 180W light irradiation, 12 minutes of rainfall / 120 minutes cycle, and a test time of 1000 hours.

[0070] (Easy adhesion layer) The easy-adhesion layer 8 is a layer for bonding the adherend of the decorative sheet 10 (for example, a substrate for a decorative material) and the raw 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 the material for the picture-printed layer 6 and the concealing layer 3. Furthermore, considering that the easy-adhesion layer 8 is applied to the back surface of the decorative sheet and therefore wound up in web form, inorganic fillers such as silica, alumina, magnesia, titanium oxide, and barium sulfate may be added to the easy-adhesion layer 8 to avoid blocking and improve adhesion to the adhesive. The coating thickness, i.e., the thickness of the easy-adhesion layer 8 (primer layer), is intended to ensure adhesion to the base fabric layer 7, and therefore is appropriately 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 adhesive layer 8 is necessary when the surface of the raw fabric layer 7 is inactive, such as when it is made of an olefin-based material, but is not particularly necessary when the surface is active.

[0071] <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 illustrating one structural example of a decorative sheet 20 according to the 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 first embodiment in that the transparent resin layer is not a single layer but a multi-layer. 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 more detail below, the transparent resin layer 11 has a multi-layer structure and includes a transparent resin layer 1 and a transparent resin layer 2.

[0072] More specifically, the decorative sheet 20 according to this modification may be any decorative sheet having at least an adhesive layer 5 and a base fabric layer 7 on one side (transparent resin layer 2 side) of a multilayer transparent resin layer 11, and a surface protective layer 4 on the other side (transparent resin layer 1 side) of the transparent resin layer 11. In other words, the decorative sheet 20 may be a laminate, and may be any decorative sheet having at least a base fabric layer 7, an adhesive layer 5, a transparent resin layer 11 (transparent resin layers 1 and 2), and a surface protective layer 4, in this order. In addition, in the decorative sheet 20 according to this embodiment, the laminate (a three-layer sheet) consisting of the transparent resin layer 11 and the surface protective layer 4 will be referred to as an "oxygen barrier laminate 51" for convenience.

[0073] Below, we will explain in detail the transparent resin layer 11, which is a configuration of the decorative sheet 20 that differs from 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 will be used and detailed explanations will be omitted.

[0074] In this modified example, the oxygen barrier laminate 51 in which the surface protective layer 4 is laminated on the transparent resin layer 11 (transparent resin layers 1 and 2) before the weather resistance test has an oxygen permeability of 1500 cc / (m 21·day·atm) or less. This makes it possible to reduce changes in appearance such as discoloration of the picture printed layer 6 in the decorative sheet 20 according to this modification. In this modification, too, it is preferable that the oxygen barrier laminate 51, in which the surface protective layer 4 is laminated on the transparent resin layer 11 (transparent resin layers 1 and 2), has an oxygen permeability change rate of 35% or less before and after the weathering test. This makes it possible to reduce appearance changes such as cracks and breaks in the decorative sheet 20 according to this modification.

[0075] (Transparent resin layer) As shown in Fig. 2, the decorative sheet 20 has a transparent resin layer 11. The transparent resin layer 11 is a multi-layer (two-layer in this example) structure, and is made up of a transparent resin layer 1 and a transparent resin layer 2. More specifically, the transparent resin layer 11 is made up of a multi-layer structure, and has the transparent resin layer 1 which becomes the first transparent resin layer, and the transparent resin layer 2 which becomes the second transparent resin layer located between the transparent resin layer 1 and the adhesive layer 5.

[0076] [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 will not be described in detail.

[0077] [Second transparent resin layer] 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 the adhesive layer 5. In other words, the transparent resin layer 2 is located below the transparent resin layer 1. The transparent resin layer 2 may be provided when further laminate strength is required, particularly when the transparent resin layer is formed by extrusion lamination.

[0078] The transparent resin layer 1 and the transparent resin layer 2 in the transparent resin layer 11 are generally laminated and formed by a co-extrusion method. The resin contained in the transparent resin layer 2 is preferably 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.

[0079] The thickness of the transparent resin layer 2 is preferably 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. That is, the thickness of the transparent resin layer 2 is preferably within the range of 2 μm to 20 μm. 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 improve weather resistance and scratch resistance while suppressing an increase in manufacturing costs and a decrease in post-processability.

[0080] <Second Modification> A decorative material according to a 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 producing a decorative material by laminating it with a substrate for a decorative material. Fig. 3 is a cross-sectional view illustrating an example of the configuration of a decorative material 100 according to a second modified example of this embodiment. As shown in Figure 3, the decorative material 100 according to this modification is obtained by laminating the decorative sheet 10 according to this embodiment onto 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.

[0081] (decorative materials) 3, in 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 side of raw fabric layer 7 in decorative sheet 10, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 are provided on the other side of raw fabric layer 7. In other words, decorative material 100 comprises substrate 16 for decorative material and decorative sheet 10, which is a laminate bonded to substrate 16 for decorative material. This makes it possible to provide a decorative material 100 that improves the weather resistance of the decorative sheet 10 caused by long-term use, and more specifically, that can reduce the occurrence of changes in appearance such as cracks and breaks.

[0082] (Base material for decorative materials) The decorative material substrate 16 can be a wood substrate or a metal substrate. Examples of wood substrates that can be used include wood veneers, wood plywood, laminated lumber, particle board, medium-density fiberboard, hard fiberboard, and chipboard. Examples of metal substrates that can be used include steel plates and aluminum plates. The decorative material substrate 16 can also be made of a resin such as plastic, or a composite material thereof. When the decorative material substrate 16 is a resin substrate, for example, vinyl chloride resin can be used.

[0083] The decorative material substrate 16 may also be made of, for example, a non-combustible steel plate or a non-combustible material as specified in Notification No. 1400 of the Ministry of Construction. The shape of the decorative material substrate 16 is not particularly limited, but it can be, for example, a flat plate. Adhesive 15 can be used to bond the decorative material substrate 16 and the decorative sheet 10. Since adhesive 15 is the same as the adhesive 15 in the second modified example of the first embodiment, it is given the same reference numeral and a description thereof will be omitted.

[0084] When bonding the decorative material substrate 16 and the decorative sheet 10 together, bonding devices such as a cold press, a hot press, a roll press, a laminator, a wrapping machine, an edge bonding machine, a vacuum press, or the like 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 cut, tongued using a tenon, V-shaped grooved, or chamfered on all four sides (e.g., C-chamfered).

[0085] The decorative material 100 according to this modification may have grooves and / or chamfers extending from the decorative sheet 10 side to the decorative material substrate 16, and the grooves and chamfers may be painted with a colored paint. The colored paint for coating the grooves and chamfered portions can be, for example, an ink prepared by dissolving or dispersing a colorant (organic pigment or 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 composed of isocyanates and polyols, polyacrylics, polyvinyl acetates, polyvinyl chlorides, vinyl chloride-vinyl acetate copolymers, cellulose-based resins, and polyamide-based resins. 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, etc. can also be added as needed.

[0086] The decorative material 100 according to this modified example has been described above. Note that while FIG. 3 illustrates an example in which the decorative material 100 is constructed using the decorative sheet 10 according to the first embodiment, the present disclosure is not limited to this. The decorative material 100 may also be constructed using the decorative sheet 20 according to the first modified example 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 side of the raw fabric layer 7 of the decorative sheet 20, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 provided on the other side of the raw fabric layer 7. That is, the decorative material 100 may be configured to include a decorative material substrate 16 and a decorative sheet 20 that is a laminate bonded to the decorative material substrate 16. This makes it possible for the decorative material 100 to provide a decorative material that improves the weather resistance of the decorative sheet 20 that occurs over long periods of use, and more specifically, can reduce the occurrence of changes in appearance such as cracks and breaks.

[0087] (Effects of this embodiment) The decorative sheet and decorative material according to this embodiment have the following effects. (1) The decorative sheet (decorative sheet 10, 20) according to this embodiment comprises a base fabric layer 7 containing at least an olefin-based resin, a transparent resin layer (transparent resin layer 1, 11) and a surface protective layer 4 in this order, and the oxygen barrier laminate (oxygen barrier laminate 50, 51) consisting of the transparent resin layer (transparent resin layer 1, 11) and the surface protective layer 4 has an oxygen permeability of 1500 cc / (m) at 30°C / 0% RH before weather resistance testing. 2 ·day·atm). This configuration makes it possible to provide a decorative sheet (laminate) that can improve the weather resistance of the decorative sheet (decorative sheets 10, 20) (reduce the occurrence of appearance changes such as cracks and breaks). (2) In the oxygen barrier laminate (oxygen barrier laminate 50, 51) constituting the decorative sheet (decorative sheet 10, 20), the rate of change in oxygen permeability before and after weather resistance testing (1000-hour super xenon test) may be 35% or less. This configuration makes it possible to provide a decorative sheet (laminate) that can improve the weather resistance of the decorative sheet (decorative sheets 10, 20) (reduce the occurrence of appearance changes such as cracks and breaks). (3) The surface protective layer 4 constituting the decorative sheet (decorative sheets 10, 20) may contain at least one of a thermosetting resin and an ionizing radiation curable resin. This configuration makes it possible to provide a decorative sheet (laminate) that can improve the weather resistance of the decorative sheet (decorative sheets 10, 20) (reduce the occurrence of appearance changes such as cracks and breaks).

[0088] (4) In the decorative sheets (decorative sheets 10, 20) according to this embodiment, the surface protective layer 4 may contain at least one of an ultraviolet absorber and a light stabilizer. This configuration makes it possible to provide a decorative sheet (laminate) that can improve the weather resistance of the decorative sheet (decorative sheets 10, 20) (reduce the occurrence of appearance changes such as cracks and breaks) even after long-term use. (5) In the decorative sheets (decorative sheets 10, 20) according to this embodiment, the transparent resin layers (transparent resin layers 1, 11) may contain at least one of an ultraviolet absorber and a light stabilizer. This configuration makes it possible to provide a decorative sheet (laminate) that can improve the weather resistance of the decorative sheet (decorative sheets 10, 20) (reduce the occurrence of appearance changes such as cracks and breaks) even after long-term use.

[0089] (Example) The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. In this example, the transparent resin layer 1 was formed using the following polypropylene resin, the following polyester resin, or the following acrylic resin.

[0090] [Polypropylene resin] Homopolypropylene resin "F-300SP" (Prime Polymer Co., Ltd.)

[0091] [Polyester resin] Polyethylene terephthalate resin "Mitsui Pet J125" (Mitsui Chemicals, Inc.)

[0092] [Acrylic resin] Polymethyl methacrylate resin (PMMA) "Delpet 80HD" (manufactured by Asahi Kasei HD)

[0093] In this example, the surface protection layer 4 was formed using the following urethane resin or the following fluorine resin. [Urethane resin A] As acrylic monomers, 90 parts by mass of methyl methacrylate and 10 parts by mass of 2-hydroxyethyl methacrylate were prepared. Furthermore, as a polymerization initiator, 2,2'-azobisisobutyronitrile was prepared in an amount of 1 mol % relative to the acrylic monomers, and as a solvent, butyl acetate was prepared in an amount of 30 wt % relative to the acrylic monomers. Next, these were placed in a reaction vessel equipped with a stirrer and a reflux condenser, and while introducing nitrogen gas into the reaction vessel, the mixture was stirred and refluxed for 8 hours while being heated to 70°C. In this way, urethane resin A was produced. The curing agent used was the nurate form of hexamethylene diisocyanate "TPA-100" (manufactured by Asahi Kasei HD).

[0094] [Urethane resin B] Urethane resin B was prepared in the same manner as urethane resin A, except that 93 parts by mass of methyl methacrylate and 7 parts by mass of 2-hydroxyethyl methacrylate were used as the acrylate monomers.

[0095] [Urethane resin C] Urethane resin C was prepared in the same manner as urethane resin A, except that 90 parts by mass of butyl methacrylate and 10 parts by mass of 2-hydroxybutyl methacrylate were used as the acrylate monomers.

[0096] [Fluorine-based resin] As the fluorine-based resin, polyvinylidene fluoride resin was used.

[0097] Example 1 A wood grain pattern was gravure printed on a concealable polyethylene base film (thickness 70 μm) to form a pattern printed layer 6 (thickness 3 μm) using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.), and a transparent resin layer 1 was dry laminated onto the base film layer 7 using an adhesive (Takelac A540; manufactured by Mitsui Chemicals, Inc.) (thickness 2 μm) as the adhesive layer 5. The transparent resin layer 1 was formed from a resin material obtained by blending various additives with the polypropylene resin. More specifically, a resin material obtained by blending 0.5 parts by mass of an ultraviolet absorber (UVA) (Cyasorb UV-1164; manufactured by Sun Chemical Co., Ltd.) and 0.5 parts by mass of a light stabilizer (HALS) (Tinuvin XT-850; manufactured by BASF) with 100 parts by mass of the polypropylene resin was extruded using a melt extruder to form a transparent resin sheet having a thickness of 75 μm to be used as the transparent resin layer 1. The conditions for forming the transparent resin layer 1 (film formation conditions) were as follows: the extrusion temperature of the polypropylene resin was 200°C, and the cooling roll water temperature during film formation was 25°C.

[0098] Next, a resin material containing 100 parts by mass of the urethane resin A, 5 parts by mass of an ultraviolet absorber (UVA) (Tinuvin 400; manufactured by BASF), and 5 parts by mass of a light stabilizer (HALS) (Tinuvin 123; manufactured by BASF) was applied (layer thickness: 9 μm) onto the transparent resin layer 1 to form a surface protective layer 4. In this way, the decorative sheet 10 of Example 1 was obtained. The oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability (oxygen permeability before weathering test) of 872 cc / (m 2 ·day·atm). Furthermore, after a weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1042 cc / (m 2 ·day·atm). The oxygen permeability of the oxygen barrier laminate 50 before and after the weather resistance test was measured using a gas permeability measuring device based on the differential pressure gas chromatography method of JIS K7126A (differential pressure method) under the measurement conditions of 30°C / 0%RH (temperature 30°C, relative humidity 0%).

[0099] <Example 2> In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. In addition, no NOR-type light stabilizer was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 2 was obtained in the same manner as in Example 1. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 696 cc / (m 2 ·day·atm). Furthermore, after a weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 891 cc / (m 2 ·day·atm).

[0100] Example 3 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. In addition, no hindered phenol-based antioxidant was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 3 was obtained in the same manner as in Example 1. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 759 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 943 cc / (m 2 ·day·atm).

[0101] Example 4 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. Furthermore, no hindered phenol-based antioxidant or NOR-type light stabilizer was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 4 was obtained in the same manner as in Example 1. The oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability (oxygen permeability before weathering test) of 754 cc / (m 2 ·day·atm). Furthermore, after a weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 992 cc / (m 2 ·day·atm).

[0102] <Example 5> In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature during film formation of 25°C. The urethane resin B was used to form the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 5 was obtained in the same manner as in Example 1. The oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability (oxygen permeability before weathering test) of 1197 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1452 cc / (m 2 ·day·atm).

[0103] Example 6 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polyester resin of 200°C and a cooling roll water temperature of 25°C during film formation. Furthermore, no hindered phenol-based antioxidant or NOR-type light stabilizer was added to the transparent resin layer 1. Otherwise, the decorative sheet 10 of Example 6 was obtained in the same manner as in Example 4. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 731 cc / (m 2 ·day·atm). Furthermore, after a weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1002 cc / (m 2 ·day·atm).

[0104] Example 7 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. Furthermore, no hindered phenol-based antioxidant or NOR-type light stabilizer was added to the transparent resin layer 1. Otherwise, the decorative sheet 10 of Example 7 was obtained in the same manner as in Example 4. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 789 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1094 cc / (m 2 ·day·atm).

[0105] Example 8 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. In addition, no NOR-type light stabilizer was added to the transparent resin layer 1. Otherwise, the decorative sheet 10 of Example 8 was obtained in the same manner as in Example 4. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 746 cc / (m 2 ·day·atm). Furthermore, after a weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1012 cc / (m 2 ·day·atm).

[0106] Example 9 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. Furthermore, no hindered phenol-based antioxidant was added to the transparent resin layer 1. Furthermore, neither a hindered phenol-based antioxidant nor a NOR-type light stabilizer was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 9 was obtained in the same manner as in Example 5. The oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability (oxygen permeability before weathering test) of 1241 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1821 cc / (m 2 ·day·atm).

[0107] Example 10 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. Furthermore, no hindered phenol-based antioxidant or NOR-type light stabilizer was added to the transparent resin layer 1. Furthermore, no hindered phenol-based antioxidant was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 10 was obtained in the same manner as in Example 5. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 1382 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1895 cc / (m 2 ·day·atm).

[0108] Example 11 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. Furthermore, no hindered phenol-based antioxidant or NOR-type light stabilizer was added to the transparent resin layer 1. Furthermore, no NOR-type light stabilizer was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 11 was obtained in the same manner as in Example 5. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 1321 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1799 cc / (m 2 ·day·atm).

[0109] Example 12 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature during film formation of 25°C. The urethane resin C was used to form the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 12 was obtained in the same manner as in Example 7. The oxygen barrier laminate 50 thus formed, consisting of the transparent resin layer 1 and the surface protective layer 4, had an oxygen permeability (oxygen permeability before weathering test) of 901 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1245 cc / (m 2 ·day·atm).

[0110] Example 13 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature during film formation of 25°C. The urethane resin C was used to form the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 13 was obtained in the same manner as in Example 8. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 934 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1302 cc / (m 2 ·day·atm).

[0111] Example 14 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature during film formation of 25°C. The urethane resin C was used to form the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 14 was obtained in the same manner as in Example 9. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 947 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1279 cc / (m 2 ·day·atm).

[0112] Example 15 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. The urethane resin C was used to form the surface protective layer 4. A NOR-type light stabilizer was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 15 was obtained in the same manner as in Example 7. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 987 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1102 cc / (m 2·day·atm).

[0113] Example 16 In this example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. The urethane resin C was used to form the surface protective layer 4. A hindered phenol-based antioxidant was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Example 16 was obtained in the same manner as in Example 7. The oxygen barrier laminate 50 thus formed, consisting of the transparent resin layer 1 and the surface protective layer 4, had an oxygen permeability (oxygen permeability before weathering test) of 1004 cc / (m 2 ·day·atm). Furthermore, after a weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1290 cc / (m 2 ·day·atm).

[0114] Example 17 In this example, the above-mentioned fluororesin was used to form the surface protective layer 4, and the above-mentioned acrylic resin was used to form the transparent resin layer 1. Specifically, the above-mentioned fluororesin and the above-mentioned acrylic resin (acrylic resin layer-forming mixture) were melted in a T-die, and each resin was extruded to form a laminate consisting of a surface protective layer 4 formed from the fluororesin and a surface protective layer 4 formed from the acrylic resin. Otherwise, the decorative sheet 10 of Example 17 was obtained in the same manner as in Example 8. The oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability (oxygen permeability before weathering test) of 645 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 707 cc / (m 2 ·day·atm).

[0115] Example 18 In this example, the above-mentioned fluororesin was used to form the surface protective layer 4, and the above-mentioned acrylic resin was used to form the transparent resin layer 1. Specifically, the above-mentioned fluororesin and the above-mentioned acrylic resin (acrylic resin layer-forming mixture) were melted in a T-die, and each resin was extruded to form a laminate consisting of a surface protective layer 4 formed from the fluororesin and a surface protective layer 4 formed from the acrylic resin. Otherwise, the decorative sheet 10 of Example 18 was obtained in the same manner as in Example 9. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 672 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 734 cc / (m 2 ·day·atm).

[0116] Example 19 In this example, the above-mentioned fluororesin was used to form the surface protective layer 4, and the above-mentioned acrylic resin was used to form the transparent resin layer 1. Specifically, the above-mentioned fluororesin and the above-mentioned acrylic resin (acrylic resin layer-forming mixture) were melted in a T-die, and each resin was extruded to form a laminate consisting of a surface protective layer 4 formed from the fluororesin and a surface protective layer 4 formed from the acrylic resin. Otherwise, the decorative sheet 10 of Example 19 was obtained in the same manner as in Example 10. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 694 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 712 cc / (m 2 ·day·atm).

[0117] Example 20 In this example, the above-mentioned fluororesin was used to form the surface protective layer 4, and the above-mentioned acrylic resin was used to form the transparent resin layer 1. Specifically, the above-mentioned fluororesin and the above-mentioned acrylic resin (acrylic resin layer-forming mixture) were melted in a T-die, and each resin was extruded to form a laminate consisting of a surface protective layer 4 formed from the fluororesin and a surface protective layer 4 formed from the acrylic resin. Otherwise, the decorative sheet 10 of Example 20 was obtained in the same manner as in Example 11. The oxygen permeability of the oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4 (oxygen permeability before weathering test) is 688 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 705 cc / (m 2 ·day·atm).

[0118] <Comparative Example 1> In this comparative example, the conditions for forming the transparent resin layer 1 (film-forming conditions) were an extrusion temperature of the polypropylene resin of 200°C and a cooling roll water temperature of 25°C during film formation. The urethane resin C was used to form the surface protective layer 4. Neither a hindered phenol-based antioxidant nor a NOR-type light stabilizer was added to the surface protective layer 4. Otherwise, the decorative sheet 10 of Comparative Example 1 was obtained in the same manner as in Example 1. The oxygen barrier laminate 50 thus formed, which is made up of the transparent resin layer 1 and the surface protective layer 4, has an oxygen permeability (oxygen permeability before weathering test) of 1800 cc / (m 2 ·day·atm). Furthermore, after the weather resistance test described later, the oxygen permeability of the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 was 1566 cc / (m 2 ·day·atm).

[0119] Table 1 shows the oxygen permeability of the oxygen barrier laminate measured for each of the decorative sheets 10 of Examples 1 to 20 and Comparative Example 1 before and after the weather resistance test.

[0120] [Table 1]

[0121] The weather resistance (change in appearance) evaluation carried out on each of the decorative sheets 10 of Examples 1 to 20 and Comparative Example 1 will be explained below.

[0122] <Evaluation method> Weather resistance (appearance change) evaluation <Weather resistance test> After 1000 hours of testing in the super xenon test, the change in appearance was evaluated. ◎: No change in appearance was observed across the entire decorative sheet ○: Minor changes in appearance were observed throughout the decorative sheet, but no significant changes such as cracks or breaks were observed. ×: A significant change in appearance was observed throughout the entire decorative sheet. In addition, if the evaluation was "Good" or "Good", it was at a practical level and was therefore considered "passed".

[0123] As shown in Table 1, the oxygen barrier laminate 50 consisting of the transparent resin layer 1 and the surface protective layer 4 had an oxygen permeability of 1500 cc / (m) at 30°C / 0% RH before the weather resistance test. 2 ·day·atm) or less, deterioration of weather resistance (especially change in appearance) can be reduced.

[0124] Furthermore, for example, this embodiment can have the following configuration. (1) a transparent resin layer and a surface protective layer provided in this order on a substrate sheet containing at least an olefin-based resin; Before the weather resistance test, the oxygen barrier laminate consisting of the transparent resin layer and the surface protective layer had an oxygen permeability of 1500 cc / (m 2 A laminate characterized in that the temperature is 1000°C or less (100°F / day·atm). (2) The oxygen barrier laminate according to (1) above, wherein the rate of change in oxygen permeability before and after a weather resistance test (super xenon test for 1000 hours) is 35% or less. (3) The laminate according to (1) or (2) above, wherein the surface protective layer contains at least one of a thermosetting resin and an ionizing radiation curable resin. (4) The laminate according to any one of (1) to (3) above, wherein the surface protective layer contains at least one of an ultraviolet absorber and a light stabilizer. (5) The laminate according to any one of (1) to (4) above, wherein the transparent resin layer contains at least one of an ultraviolet absorber and a light stabilizer. [Explanation of symbols]

[0125] 1, 2 Transparent resin layer 1a Embossed pattern 3 Hidden Layer 4 Surface protective layer 5 Adhesive layer 6. Picture printing layer 7. Original layer 8 Easy adhesive layer 10, 20 Decorative sheet (laminate) 50 Oxygen barrier laminate 100 Cosmetic Materials

Claims

1. a transparent resin layer and a surface protective layer provided in this order on a substrate sheet containing at least an olefin-based resin; Before the weather resistance test, the oxygen barrier laminate consisting of the transparent resin layer and the surface protective layer had an oxygen permeability of 1500 cc / (m ２ .times.day.atm) or less.

2. 2. The laminate according to claim 1, wherein the oxygen barrier laminate has a rate of change in oxygen permeability of 35% or less before and after a weather resistance test (super xenon test for 1000 hours).

3. 2. The laminate according to claim 1, wherein the surface protection layer contains at least one of a thermosetting resin and an ionizing radiation curable resin.

4. The laminate according to claim 1 , wherein the surface protective layer contains at least one of an ultraviolet absorber and a light stabilizer.

5. 5. The laminate according to claim 1, wherein the transparent resin layer contains at least one of an ultraviolet absorber and a light stabilizer.

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