Decorative sheet

Abstract

To provide a decorative sheet with reduced degradation of an adhesive layer inside the decorative sheet due to long-term service and reduced formation of delamination (peeling inside the decorative sheet).SOLUTION: A decorative sheet 10 of this embodiment includes, on an original layer 7 containing at least an olefin-based resin, an adhesive layer 5, a transparent resin layer 1, and a surface protective layer 4 in this order, wherein a water vapor permeability W2 of the transparent resin layer 1 is lower than a water vapor permeability W1 of the surface protective layer 4.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a decorative sheet. [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 applications of decorative sheets are expanding beyond indoors to outdoors, making them required to have long-term weather resistance. Until now, peeling of decorative boards or sheets from wood substrates over long-term use has been prevented, for example, by attaching a moisture-proof sheet to the back surface of the decorative board or sheet (see Patent Document 2), or by forming a surface protective layer from an ionizing radiation-curable resin composition to reduce the moisture permeability of the entire decorative sheet (see Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2-128843 [Patent Document 2] JP 2003-340966 A [Patent Document 3] International Publication No. 2021 / 065620 Summary of the Invention [Problem to be solved by the invention]

[0004] As described above, it is possible to prevent the decorative board or sheet from peeling off from the wood substrate after long-term use by reducing the moisture permeability of the entire decorative sheet or by preventing moisture penetration from the back surface of the decorative board or sheet. However, decorative sheets relating to conventional technology cannot adequately prevent moisture penetration from the surface of the decorative sheet, and with long-term use, the adhesive layer (adhesive layer) inside the decorative sheet can deteriorate, causing delamination (peel within the decorative sheet).

[0005] The present disclosure has been made in consideration of the above circumstances, and aims to provide a decorative sheet that can reduce deterioration of the adhesive layer inside the decorative sheet due to long-term use and reduce the occurrence of interlayer delamination (peelation within the decorative sheet). [Means for solving the problem]

[0006] In order to solve the above problems, a decorative sheet according to one embodiment of the present disclosure is a decorative sheet comprising, in that order, an adhesive layer, a transparent resin layer, and a surface protective layer on a base sheet containing at least an olefin-based resin, and is characterized in that the moisture permeability W2 of the transparent resin layer is lower than the moisture permeability W1 of the surface protective layer. Effect of the Invention

[0007] According to one aspect of the present disclosure, a decorative sheet can be provided that can reduce the deterioration of the adhesive layer inside the decorative sheet caused by long-term use and reduce the occurrence of delamination (delamination within the decorative sheet). More specifically, according to one aspect of the present disclosure, a decorative sheet with good weather resistance (i.e., no delamination over time) can be provided by suppressing moisture transmission (particularly water vapor transmission) from the surface of the decorative sheet. [Brief description of the drawings]

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

[0009] Hereinafter, the decorative sheet and decorative member according to the embodiment of the present disclosure will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. are different from the actual ones. As long as it is within the scope of the present disclosure, it is not necessary to stack in the order shown in the drawings. In addition, layers not shown in the drawings may be added. In addition, the embodiments shown below are examples of configurations for embodying the technical idea of ​​the present disclosure, and the technical idea of ​​the present disclosure is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present disclosure can be modified in various ways within the technical scope defined by the claims described in the claims. In addition, the directions of "left and right" and "up and down" in the following description are merely defined for the convenience of explanation and do not limit the technical ideas of the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left".

[0010] As a result of intensive research, the present inventors have found that by making the moisture permeability W2 of the transparent resin layer lower than the moisture permeability W1 of the surface protective layer in a decorative sheet, it is possible to prevent deterioration (e.g., hydrolysis) of the adhesive layer in the decorative sheet, and delamination can be prevented. As a result, the present inventors have invented a decorative sheet that can reduce deterioration of the adhesive layer inside the decorative sheet caused by long-term use, and reduce the occurrence of delamination (peel within the decorative sheet).

[0011] In other words, the present disclosure proposes and provides a new design concept for preventing delamination in decorative sheets. This point will be described below. In conventional design concepts, in order to prevent delamination in decorative sheets, as described above, attention has been focused on and adjustments have been made to the moisture permeability (degree) from the back side of the decorative sheet and the moisture permeability (degree) of the entire decorative sheet. In response to this, the present inventors have newly discovered that in order to prevent delamination in a decorative sheet, it is important not only to prevent moisture penetration from the back side of the decorative sheet, but also to prevent moisture penetration from the front side.

[0012] Thus, the design concept in this disclosure is significantly different from conventional design concepts, and focuses on and adjusts the moisture permeability (degree) of each of the transparent resin layer and surface protective layer that make up the decorative sheet in order to prevent delamination in the decorative sheet. By adjusting the moisture permeability of each of the transparent resin layer and surface protective layer that make up the decorative sheet, i.e., by limiting moisture permeation from the surface side of the decorative sheet, it becomes possible to prevent deterioration (e.g., hydrolysis) of the adhesive layer that makes up the decorative sheet, and prevents delamination in 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] (Measurement of moisture permeability W) First, the "moisture permeability W" defined in this embodiment will be described. The moisture permeability W in this embodiment is a value measured using a method in accordance with JIS Z 0208, and is a value measured under measurement conditions of a temperature of 40° C. and a relative humidity of 90%. In this embodiment, the moisture permeability W is measured for each of the transparent resin layer and the surface protective layer, and for a two-layer sheet in which the surface protective layer is laminated on the transparent resin layer. Hereinafter, with regard to the moisture permeability W, the value obtained by measuring the transparent resin layer is referred to as the moisture permeability W2, the value obtained by measuring the surface protective layer is referred to as the moisture permeability W1, and the value obtained by measuring the two-layer sheet having a surface protective layer laminated on top of a transparent resin layer is referred to as the moisture permeability W3.

[0014] In this embodiment, the moisture permeability W2 of the transparent resin layer is lower than the moisture permeability W1 of the surface protective layer. The moisture permeability W2 of the transparent resin layer is 15 g / m 2 -24 hours or less is preferable. In addition, the moisture permeability W3 of a two-layer sheet in which a surface protective layer is laminated on a transparent resin layer is 15 g / m 2 -24 hours or less is preferable. Furthermore, it is preferable that the rate of change in moisture permeability W3 before and after the weather resistance test for a two-layer sheet having a surface protective layer laminated on a transparent resin layer is within ±20%. It should be noted that a higher value of the moisture permeability W means a lower gas barrier property, and a lower value of the moisture permeability W means a higher gas barrier property.

[0015] (Composition of decorative sheet) Hereinafter, each component of the decorative sheet (one example of a laminate) of the present embodiment will be described. Note that in the present embodiment, the transparent resin layer (transparent resin layer) will be described as a single layer. The decorative sheet 10 shown in Fig. 1 is a laminate comprising multiple layers, and comprises, from the top of the drawing, a surface protective layer 4, a transparent resin layer 1, an adhesive layer 5 (heat-sensitive adhesive layer, anchor coat layer, dry lamination adhesive layer), a picture print layer 6, a concealing layer 3, a base fabric layer 7, and an easy-adhesion layer 8. The base fabric layer 7 is a layer that serves as the base material for the decorative sheet 10, and is also referred to as a base material sheet or base material layer.

[0016] 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. That is, the decorative sheet 10 is a laminate, and may be any decorative sheet 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 sheet having a two-layer structure) composed of the transparent resin layer 1 and the surface protective layer 4 will be referred to as a "two-layer sheet 50" for the sake of convenience. In order to improve the design, an embossed pattern may be appropriately provided on the surface of the transparent resin layer 1 on the side of the surface protective layer 4 .

[0017] The total thickness of the decorative sheet 10 is preferably in the range of 60 μm to 250 μm. If the total thickness is less than 60 μm, there is a concern that the required performance of the decorative sheet may be reduced in terms of concealment (ability to hide the base of the decorative substrate) and scratch resistance. If the total thickness is more than 250 μm, there is a concern that the cost may increase and that the processability may decrease when bonding the decorative sheet to the decorative substrate. Moreover, the decorative sheet of the present embodiment preferably does not contain vinyl chloride resin. By using a decorative sheet that uses a non-vinyl chloride resin, concerns about the generation of toxic gases and the like during incineration can be reduced. Hereinafter, each layer constituting the decorative sheet of this embodiment will be described in detail.

[0018] (Original layer) When the decorative sheet is to be given design, scratch resistance and post-processing resistance, the raw cloth layer (raw cloth) 7 may be appropriately selected from, for example, paper such as tissue paper, titanium paper, and resin-impregnated paper, synthetic resins such as polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic, or foams of these synthetic resins, rubbers such as ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane, organic or inorganic nonwoven fabrics, synthetic paper, and metal foils such as aluminum, iron, gold, and silver. The raw cloth layer 7 may also be a sheet made of the same resin composition as the transparent resin layer 1. Among the above, it is preferable to use polyolefin-based materials such as polypropylene and polyethylene. In other words, the raw cloth layer 7 is preferably a layer containing at least an olefin-based resin.

[0019] Examples of the polyolefin resin contained in the raw fabric layer 7 include polypropylene, polyethylene, polybutene, and the like, as well as α-olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl These include homopolymers or copolymers of two or more types of α-olefins (e.g., 1-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) as well as copolymers of ethylene or α-olefins with other monomers, such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.

[0020] When a substrate having an inactive surface such as a polyolefin-based material is used as the raw fabric layer 7, it is preferable to perform, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, etc. on the front and back sides of the raw fabric layer 7. Furthermore, a primer layer (not shown) may be provided between the raw fabric layer 7 and the picture print layer 6 to ensure adhesion.

[0021] When it is desired to provide the decorative sheet with a concealing property, a concealing colored sheet may be used for the original fabric layer 7, or as shown in FIG. 1, a concealing layer 3 may be provided on the original fabric layer 7 and below the pattern printed layer 6. The concealing layer 3 will be described later. When a colored sheet is used as the original fabric layer 7, a coloring agent may be added to the resin material constituting the original fabric layer 7 to color it. As the coloring agent, for example, inorganic pigments (titanium oxide, carbon black, etc.) and organic pigments (phthalocyanine blue, etc.) as well as dyes can be used. The coloring agent of this embodiment can be selected from one or more known or commercially available coloring agents, and the amount added can be adjusted so as to obtain the desired concealing property and design. If necessary, various additives such as fillers, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, crystal nucleating agents, UV absorbers, light stabilizers, heat stabilizers, colorants, and matting agents may be added to the raw fabric layer 7. The thickness of the raw fabric layer 7 is preferably within the range of 20 μm to 150 μm, taking into consideration printing workability, costs, and the like.

[0022] (Pattern printing layer) The pattern printed layer 6 may be formed on the base layer 7 or the transparent resin layer 1 by, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, or the like. When ink is used to form the picture print layer 6, the binder contained in the ink may be appropriately selected from, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., either alone or modified. These may be water-based, solvent-based, or emulsion type, and may be any one-component type or two-component type using a hardener. Furthermore, the ink can be cured by irradiation with ultraviolet light, electron beams, etc. Among these, the preferred method is to use a urethane-based ink and cure it with isocyanate. That is, in the decorative sheet 10 according to this embodiment, the picture-printed layer 6 preferably contains a urethane-based resin as a binder.

[0023] The urethane resin used in the pattern printing layer 6 is not particularly limited, and may be either one-component curing type or two-component curing type. For example, one-component ester polyurethane resin may be suitably used as the one-component curing type urethane resin. In addition, as the two-component curing type urethane resin, for example, one containing a polyol component having an OH group as a main agent and an isocyanate component as a curing agent component may be adopted. Examples of the polyol component having an OH group include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, the pattern printing layer 6 may be suitably used with a polyester urethane resin using a polyester polyol as a main agent.

[0024] In addition to the binder, the picture-printed layer 6 may contain pigments, colorants such as dyes, extender pigments, solvents, and various additives that are contained in normal inks. Particularly commonly used pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica. In addition to applying ink, it is also possible to apply designs by deposition or sputtering of various metals.

[0025] The thickness of the pattern-printed layer 6 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 3 μm. By making the pattern-printed layer 6 sufficiently thick, it is possible to improve the interlayer adhesion (e.g., adhesion between the base fabric layer 7, the concealing layer 3, and the adhesive layer 5) in the decorative sheet 10. On the other hand, if the pattern-printed layer 6 is too thick, post-processability (e.g., bending processability) may be reduced. Therefore, by setting the thickness of the picture-printed layer 6 within the range of 1 μm or more and 10 μm or less as described above, it is possible to improve the adhesion between layers and the post-processing properties.

[0026] (Hidden layer) The concealing layer 3 can be provided on the original fabric layer 7 or on the pattern-printed layer 6 formed on the transparent resin layer 1 by the same printing method as that for the pattern-printed layer 6. The concealing layer 3 may be formed as necessary, and may be omitted, for example, when a concealing colored sheet is used for the original fabric layer 7. When applying the concealing layer 3, for example, a comma coater, a knife coater, a lip coater, metal vapor deposition, or a sputtering method may be used. The concealing layer 3 is generally provided as an upper layer of the original fabric layer 7 and as a lower layer of the pattern-printed layer 6.

[0027] The material used for the concealing layer 3 may basically be the same as that for the pattern printed layer 6. Since the concealing layer 3 needs to have a concealing property as its purpose, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide, etc. as a pigment. In addition, it is also possible to add metals such as gold, silver, copper, and aluminum to improve the concealing property. Generally, flake-shaped aluminum is often added. If the coating thickness, i.e., the thickness of the concealing layer 3, is less than 2 μm, it is difficult to impart concealing property, and if it exceeds 10 μm, the cohesive force of the resin layer tends to be weak. For this reason, the thickness of the concealing layer 3 is preferably in the range of 2 μm to 10 μm.

[0028] (adhesive layer) Any material can be selected for the adhesive layer 5, and examples of adhesion methods using the adhesive layer 5 include heat lamination, extrusion lamination, dry lamination, etc. The adhesive contained in the adhesive layer 5 can be selected from, for example, acrylic, polyester, polyurethane, phthalic acid (alkoxy acid)-based materials, etc. The adhesive contained in the adhesive layer 5 is usually desirably a two-liquid curing type adhesive due to its high cohesive strength, and it is particularly desirably a urethane-based material obtained by reaction with a polyol using an isocyanate due to its workability, cost, and high cohesive strength. In other words, the adhesive layer 5 preferably contains a urethane resin.

[0029] The urethane resin used in the adhesive layer 5 is not particularly limited, and may be either a one-component curing type or a two-component curing type. For example, a one-component ester polyurethane resin may be suitably used as the one-component curing type urethane resin. In addition, a two-component curing type urethane resin may be used that contains, for example, a polyol component having an OH group as a main agent and an isocyanate component as a curing agent component. Examples of the polyol component having an OH group include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, a polyester urethane resin using a polyester polyol as a main agent may be suitably used for the adhesive layer 5.

[0030] The thickness of the adhesive layer 5 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 5 μm. By making the thickness of the adhesive layer 5 sufficiently thick, it is possible to improve the interlayer adhesion (e.g., adhesion between the base layer 7, the concealing layer 3, and the transparent resin layer 1) in the decorative sheet 10. On the other hand, if the thickness of the adhesive layer 5 is too thick, post-processability (e.g., bending processability) may be reduced. Therefore, by setting the thickness of the adhesive layer 5 within the range of 1 μm or more and 10 μm or less as described above, it is possible to improve the adhesion between the layers and the post-processability.

[0031] (Transparent resin layer) The transparent resin layer 1 is formed on the adhesive layer 5. The transparent resin layer 1 may be a sheet formed by film formation, or may be a laminate of already formed sheets. The transparent resin layer 1 is preferably formed using a polyolefin resin. Specifically, it is preferable to use a polypropylene resin as the transparent resin layer 1. The transparent resin layer 1 is formed, for example, of a highly crystalline polypropylene resin. Furthermore, one or both surfaces of the transparent resin layer 1 may be activated, for example, by corona treatment, plasma treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, or the like, as necessary.

[0032] When the transparent resin layer 1 is formed from a sheet by film formation, for example, a method using an extruder is generally used. When the transparent resin layer 1 is laminated and formed, there is no particular restriction, and for example, a method using heat and pressure, an extrusion lamination method, a dry lamination method, etc. are generally used. In addition, when the embossed pattern 1a is applied, there is a method of embossing a sheet that has been once laminated by various methods, for example, by heat and pressure, or a method of providing an uneven pattern on a cooling roll and embossing the sheet at the same time as extrusion lamination using the cooling roll. More specifically, the embossed pattern 1a is directly applied to the transparent resin layer 1, for example, a highly crystalline polypropylene sheet, and the method includes a method of providing an embossed pattern on the sheet formed by film formation using an embossing plate having an uneven pattern by heat and pressure, and a method of providing an embossment at the same time as cooling using a cooling roll having an uneven pattern when forming a film using an extruder. Here, it is also possible to embed ink in the embossed pattern 1a as the embossed part to further improve the design. The embossed pattern 1a may be provided if necessary, but may not be provided if unnecessary.

[0033] The thickness of the transparent resin layer 1 is preferably in the range of 40 μm or more and 170 μm or less. If the thickness of the transparent resin layer 1 is less than 40 μm, the weather resistance and scratch resistance may decrease. If the thickness of the transparent resin layer 1 exceeds 170 μm, the manufacturing cost may increase and the post-processing property may decrease. If necessary, various additives such as heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, catalyst scavengers, and, as long as the characteristics of this embodiment are not impaired, colorants, light scattering agents, and gloss adjusters may also be added to the transparent resin layer 1.

[0034] More specifically, in this embodiment, one or more types of ultraviolet absorbing agents (UVA) may be added to the transparent resin layer 1, or a light stabilizer (HALS) may be added to the transparent resin layer 1. Moreover, both an ultraviolet absorbing agent (UVA) and a light stabilizer (HALS) may be added to the transparent resin layer 1. The content of the ultraviolet absorbing agent (UVA) is preferably within the range of 0.1 parts by mass 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 absorbing agent (UVA) is added.

[0035] The content of the light stabilizer (HALS) is preferably within the range of 0.1 parts by mass 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) and a light stabilizer (HALS) to the transparent resin layer 1, it is possible to suppress oxidation deterioration caused by light (exposure light) during weather resistance tests such as the Super Xenon test, and to prevent appearance changes such as cracks and breaks. As a result, an increase in the moisture permeability W2 of the transparent resin layer 1 is suppressed, and interlayer delamination can be further suppressed.

[0036] It is common to add, in any combination, heat stabilizers such as phenols, sulfurs, phosphorus, and hydrazines, flame retardants such as aluminum hydroxide and magnesium hydroxide, ultraviolet absorbers such as benzotriazoles, benzoates, benzophenones, and triazines, and light stabilizers such as hindered amines (HALS). In particular, when used for this purpose, weather resistance must be considered. In that case, an ultraviolet absorber and a light stabilizer may be added to the transparent resin layer 1, and the appropriate amount of each is within the range of 0.1% by mass to 2.0% by mass, with the transparent resin layer 1 being 100% by mass. The transparent resin layer 1 may also contain a crystal nucleating agent (nano-sized nucleating agent) that has been subjected to vesicle treatment by supercritical reverse phase evaporation.

[0037] 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.

[0038] Examples of triazine-based ultraviolet absorbers that can be used include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, as well as mixtures, modified products, polymers, and derivatives thereof. Furthermore, as the benzophenone-based ultraviolet absorbing agent, for example, octabenzone, its modified product, polymer, and derivative can be used.

[0039] Furthermore, 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]], dimethyl succinate·1-(2hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine polycondensate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and mixtures, modified products, polymers, and derivatives thereof.

[0040] In addition, the crystalline polypropylene resin forming the transparent resin layer 1 can be appropriately selected and designed from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, lock polypropylene, and mixtures thereof, each having a different pentad fraction. More preferably, it is important that the crystalline polypropylene resin is a propylene homopolymer, i.e., a highly crystalline homopolypropylene resin, which is a homopolymer, having an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. In addition, resins other than the crystalline polypropylene constituting the transparent resin layer 1 can be appropriately selected depending on the purpose of the blending, as long as they do not significantly adversely affect the physical properties of the crystalline polypropylene. However, in order to maintain the V-groove bending processability, it is preferable that the resin has good compatibility with the crystalline polypropylene resin constituting the transparent resin layer 1. The material of the transparent resin layer 1 is not limited to this, and a highly flexible polyolefin resin such as a random polypropylene resin containing an ethylene content or a polyolefin thermoplastic elastomer can be used.

[0041] The terms used in the above description of the transparent resin layer 1 will be briefly explained below. A nucleating agent is added to promote the generation of crystal nuclei during the crystallization of a resin, or to make the nucleating agent itself a crystal nucleus. Nucleating agents include melting agents that melt into the resin of the base material when added and precipitate again to generate crystal nuclei, and non-melting agents that do not melt when added to the base material and become crystal nuclei with the same particle size. Examples of nucleating agents for polypropylene resin include metal phosphate salts, metal benzoate salts, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in this embodiment, in order to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoate salts, metal pimelate salts, and metal rosin salts that are non-melting and can be expected to have good transparency, but if the nano-processing can make the material transparent, colored quinacridone, cyanine blue, talc, etc. can also be used. In addition, melting benzylidene sorbitol may be appropriately mixed with the non-melting nucleating agent.

[0042] The isotactic pentad fraction (mmmm fraction) is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating the resin material constituting the transparent resin layer 1 at a predetermined resonance frequency by 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclear species) with a mass number of 13, and specifies the atomic arrangement, electronic structure, and molecular microstructure in the resin material. The isotactic pentad fraction of a polypropylene resin is the ratio of five propylene units lined up as determined by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. Such an isotactic pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface, and basically, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, and therefore the better the scratch resistance.

[0043] [Moisture permeability W2 of transparent resin layer 1] In this embodiment, the moisture permeability W2 of the transparent resin layer 1 only needs to be lower than the moisture permeability W1 of the surface protective layer 4. This makes it possible to prevent moisture permeation from the surface side of the decorative sheet 10, and to provide a decorative sheet in which deterioration (e.g., hydrolysis) of the adhesive layer 5 is reduced and interlayer delamination is prevented. This point will be described in detail below. The resin constituting the surface protective layer 4 formed on the transparent resin layer 1 can be various resins as described below. When imparting good scratch resistance, contamination resistance, etc. to the surface protective layer 4, the surface protective layer 4 may be formed using, for example, a thermosetting resin such as a urethane-based resin or an ionizing radiation curing resin such as a urethane acrylate-based resin. Resins widely used in forming the surface protection layer 4, such as thermosetting resins such as urethane-based resins and ionizing radiation curable resins such as urethane acrylate-based resins, provide good scratch resistance and contamination resistance as described above, but are generally known to tend to have higher moisture permeability than other resins.

[0044] In this embodiment, the transparent resin layer 1 is made of an olefin resin or the like, which has a relatively low moisture permeability compared to the resin constituting the surface protective layer 4, i.e., the moisture permeability W2 of the transparent resin layer 1 is made lower than the moisture permeability W1 of the surface protective layer 4, thereby suppressing interlayer delamination in the decorative sheet 10. Specifically, the moisture permeability W2 of the transparent resin layer 1 measured by a method conforming to JIS Z 0208 (temperature 40°C, relative humidity 90%) should be lower than the moisture permeability W1 of the surface protective layer 4 measured by the same method, and should be 15 g / m 2 - 24 hours or less is preferable, 10g / m 2 24 hours or less is even better.

[0045] By setting the moisture permeability W2 of the transparent resin layer 1 within the above numerical range, it becomes possible for the transparent resin layer 1 to effectively prevent moisture permeation (particularly water vapor permeation) from the surface side of the decorative sheet 10, thereby reducing deterioration (hydrolysis) of the adhesive layer 5. As a result, interlayer delamination in the decorative sheet 10 can be effectively suppressed. The moisture permeability W2 of the transparent resin layer 1 can be controlled, for example, by selecting the material constituting the transparent resin layer 1 and the forming conditions (adjusting the curing method and crystallinity) of the transparent resin layer 1. For example, the moisture permeability W2 can be increased by blending a resin having different physical properties with the resin constituting the transparent resin layer 1.

[0046] (Surface protective layer) As shown in Fig. 1, the surface protective layer 4 is formed on a transparent resin layer 1. That is, in the decorative sheet 10, the surface protective layer 4, which serves as the outermost layer, is laminated on the transparent resin layer 1. The surface protective layer 4 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 10. The surface protective layer 4 may contain various additives, such as an ultraviolet absorbing agent, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst trap, a colorant, a light scattering agent, and a gloss adjusting agent, if necessary.

[0047] For example, a curable resin composition can be used as a material for forming the surface protective layer 4. In this embodiment, the surface protective layer 4 may contain a cured product of the curable resin composition. More specifically, the curable resin composition constituting the surface protective layer 4 is preferably formed containing at least one of a resin that is cured by heat, i.e., a thermosetting resin, and a resin that is cured by ultraviolet light or electron beam irradiation, i.e., an ionizing radiation curable resin. In other words, the surface protective layer 4 may be formed containing only a thermosetting resin as the curable resin composition, or may be formed containing only an ionizing radiation curable resin. Furthermore, the surface protective layer 4 may be formed containing both a thermosetting resin and an ionizing radiation curable resin, i.e., a mixed composition of a thermosetting resin and an ionizing radiation curable resin.

[0048] The thermosetting resin used for the surface protective layer 4 can be appropriately selected from, for example, polyurethane, acrylic, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, etc. The form can be any of water-based, emulsion, and solvent-based, and the curing can be either a one-liquid type or a two-liquid type using a curing agent. Among them, a urethane-based top coat using an isocyanate reaction is preferable from the viewpoints of workability, cost, cohesive strength of the resin itself, etc. Specifically, it is preferable to use an acrylic urethane resin in which an acrylic polyol is combined with an isocyanate curing agent as the thermosetting resin used for the surface protective layer 4. In other words, it is preferable that the thermosetting resin constituting the surface protective layer 4 is composed of an acrylic polyol (an acrylic polyol compound) and an isocyanate curing agent.

[0049] 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.

[0050] The ionizing radiation curable resin used in the surface protective layer 4 can be appropriately selected from, for example, polyester acrylate, epoxy acrylate, urethane acrylate, acrylic acrylate, etc., but it is particularly preferable to use urethane acrylate and acrylic acrylate resins, which have good weather (light) resistance. As a curing method for the ionizing radiation curable resin, curing with active energy rays such as ultraviolet rays and electron beams is preferable from the viewpoint of workability. As an electron beam source, for example, light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, etc. can be used. The wavelength of the ultraviolet rays is preferably within the range of 180 nm to 400 nm.

[0051] It is more preferable to use, for example, a mixture of a urethane-based resin obtained by reacting an acrylic polyol with an isocyanate as the thermosetting resin and a urethane acrylate-based resin as the ionizing radiation curable resin as the mixture of thermosetting resin and ionizing radiation curable resin for the surface protective layer 4. By using a mixture of a thermosetting resin and an ionizing radiation curable resin, it is possible to improve the surface hardness and at least one of the suppression of cure shrinkage and the adhesion of inorganic fine particles (inorganic filler).

[0052] Moreover, the ionizing radiation curable resin constituting the surface protective layer 4 is preferably an ultraviolet curable resin that is cured by ultraviolet rays. The ultraviolet curing resin constituting the surface protective layer 4 preferably has 4 or more functional groups and contains one or more components with a mass average molecular weight of 500 or more. More preferably, the ultraviolet curing resin has 4 or more functional groups and contains one or more components with a mass average molecular weight in the range of 500 to 5,000. If the ultraviolet curing resin has less than 4 functional groups, the crosslinking density is low and the scratch resistance is significantly reduced, which is not preferable. If the ultraviolet curing resin has a mass average molecular weight of less than 500, the surface condition during coating is significantly deteriorated, which is not preferable. If the ultraviolet curing resin has a mass average molecular weight of more than 5,000, the viscosity of the coating liquid increases and the coating suitability is significantly reduced, which is not preferable.

[0053] The amount of the photoinitiator added is not particularly limited, and is preferably about 0.1 to 15 parts by mass with respect to 100 parts by mass of the base resin. The type of photoinitiator is not particularly limited. In the case of a resin system having a radical polymerizable unsaturated group, at least one of the following photoinitiators can be selected: acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, isopropyl-N,N dimethylaminobenzoate, etc. In addition, it is desirable to design a combination of multiple types according to the light source and production environment. In the case of a resin system having a cationic polymerizable functional group, the photoinitiator can be selected from at least one of, for example, aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, and furyloxysulfoxonium diallyliodosyl salts.

[0054] The method for forming the surface protective layer 4 is not particularly limited, and the surface protective layer 4 may be formed by coating the above-mentioned material in a coating liquid form using a conventional method such as gravure coating, microgravure coating, comma coating, knife coating, or die coating, and then curing the liquid using a method suitable for the resin material, such as thermal curing or ultraviolet curing. This surface protective layer 4 may be provided on the transparent resin layer 1 after bonding the pattern printed layer 6 provided on the original fabric layer 7 to the transparent resin layer 1 via the adhesive layer 5, or it may be provided on the transparent resin layer 1 before bonding the transparent resin layer 1 to the original fabric layer 7.

[0055] In order to further improve weather resistance, an ultraviolet absorbing agent may be added to the surface protective layer 4. The ultraviolet absorbing agent may be, for example, an ultraviolet absorbing agent selected from a benzotriazole-based ultraviolet absorbing agent, a triazine-based ultraviolet absorbing agent, and a benzophenone-based ultraviolet absorbing agent. In addition to the ultraviolet absorbing agent, a light stabilizer may be added to the surface protective layer 4 as appropriate. In this manner, in this embodiment, one or more types of ultraviolet absorbing agents (UVA) may be added to the surface protective layer 4, or a light stabilizer (HALS) may be added to the surface protective layer 4. In addition, both an ultraviolet absorbing agent (UVA) and a light stabilizer (HALS) may be added to the surface protective layer 4.

[0056] The content of the ultraviolet absorbing agent (UVA) is preferably within the range of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin constituting the layer (surface protective layer 4) to which the ultraviolet absorbing agent (UVA) is added. The content of the light stabilizer (HALS) is preferably within the range of 0.1 parts by mass to 10 parts by mass with respect 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 an ultraviolet absorbing agent (UVA) and a light stabilizer (HALS) to the surface protective layer 4, it is possible to suppress oxidation deterioration caused by light (exposure light) during weather resistance tests such as the Super Xenon test, and to prevent appearance changes such as cracks and breaks. As a result, an increase in the moisture permeability W1 of the surface protective layer 4 is suppressed, and interlayer delamination can be further suppressed.

[0057] 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.

[0058] Examples of triazine-based ultraviolet absorbers that can be used include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, as well as mixtures, modified products, polymers, and derivatives thereof.

[0059] Furthermore, as the benzophenone-based ultraviolet absorbing agent, for example, octabenzone, its modified product, polymer, and derivative can be used. As the light stabilizer, for example, a hindered amine light stabilizer (HALS) can be used. Examples of the hindered amine light stabilizer (HALS) include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. In order to improve the scratch resistance of the surface or to adjust the luster (luster) associated with imparting design properties, it is desirable to add an inorganic filler as a luster adjuster to the surface protective layer 4 .

[0060] Examples of inorganic fillers to be added to the surface protective layer 4 include alumina, silica, boehmite, iron oxide, magnesium oxide, aluminosilicate, diamond, silicon nitride, silicon carbide, glass beads, calcium titanate, barium titanate, magnesium pyroporate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, and glass fibers. As the inorganic filler, inorganic fine particles having an average particle size of 1 μm or more and 30 μm or less can be used, and inorganic fine particles having an average particle size of 1 μm or more and 10 μm or less are particularly suitable. When the average particle size of the inorganic filler is less than 1 μm, it tends to be difficult to obtain a matte effect. This is because, in order to achieve a matte effect, it is ideal for the particle size to be equal to or larger than the thickness of the film (layer) to which the inorganic filler is added. When the average particle size of the inorganic filler exceeds 30 μm, or more reliably, 10 μm, the inorganic filler is likely to fall off from the surface protective layer 4 under high load conditions, and the luster tends to change and the surface tends to look worse.

[0061] For example, when gravure printing is selected as the method for forming the surface protective layer 4, the coating thickness for one layer is appropriately in the range of 4 μm to 21 μm. In this case, as described above, it is preferable to select an inorganic filler having an average particle size of about the same size as the thickness that can be coated at one time. The content of the inorganic filler in the surface protective layer 4 is preferably within a range of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin constituting the surface protective layer 4. If the content of the inorganic filler is less than 1 part by mass, scratch resistance may decrease. If the content of the inorganic filler exceeds 20 parts by mass, the surface gloss may decrease significantly, which may impair the design and decrease weather resistance and stain resistance.

[0062] It is desirable to perform a surface treatment on the inorganic filler contained in the surface protective layer 4. By performing a surface treatment on the inorganic filler, it is possible to strengthen the bond with the surface protective layer 4. Note that the surface protective layer 4 may contain inorganic fillers whose surfaces are not treated. In addition, when carrying out the surface treatment, it is desirable that the inorganic filler has a functional group that hydrophobicizes the surface of the inorganic filler and imparts reactivity with the surface protective layer 4. In other words, it is desirable that the surface treatment agent used to treat the surface of the inorganic filler has a reactive group that reacts with the main resin constituting the surface protective layer 4. When carrying out the surface treatment of the inorganic filler, the method is not particularly limited, and a known method can be selected.

[0063] The surface treatment agent used for the surface treatment of the inorganic filler may be at least one of a surfactant, a fatty acid metal salt, a silane coupling agent, silicone, wax, and a modified resin. The surface treatment agent of this embodiment may be, for example, a silicone oil type, an alkylsilazane type, a trimethylsilylating agent, an alkoxysilane type, a siloxane, a silane coupling agent, a titanium coupling agent, a phosphoric acid type, or a fatty acid type surfactant, and may be one type or a combination of multiple types.

[0064] Examples of silicone oil-based treatment agents that can be selected include straight silicone oils (dimethyl silicone oil, methylphenyl silicone oil, etc.) and modified silicone oils (amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, one-end reactive modified, heterogeneous functional group-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, specially hydrophilic modified, higher alkoxy-modified, higher fatty acid-containing modified, fluorine-modified silicone oil, etc.).

[0065] 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.

[0066] As the trimethylsilylation agent, an alkoxysilane compound among silane coupling agents can be selected. Examples of titanate coupling agents that can be selected include isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(ditridecyl) phosphite titanate, and bis(dioctyl pyrophosphate) oxyacetate titanate. As the aluminate-based coupling agent, for example, acetoalkoxyaluminum diisopropylate can be selected.

[0067] When an embossed pattern 1a is applied to the surface of the transparent resin layer 1 on the side of the surface protective layer 4, the ink forming the surface protective layer 4 can be embedded into this embossed pattern by wiping processing to improve the design. From the viewpoint of weather resistance, in order to protect the transparent resin layer 1 as the base material, there is a method of imparting weather resistance to the surface protective layer 4 and the transparent resin layer 1 as described above. In addition, there is also a method of adding an ultraviolet absorber and a light stabilizer 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 side of the surface protection layer 4. This can further improve the design.

[0068] Further, in FIG. 1, an example in which the surface protective layer 4 is a single layer has been described, but the surface protective layer 4 in the decorative sheet 10 according to this embodiment is not limited to a single layer. The surface protective layer 4 may be a single layer or a multi-layer structure. In other words, the surface protective layer 4 may be composed of one or more layers. Therefore, the surface protective layer 4 may have a total thickness in the range of 4 μm to 21 μm. Furthermore, when the surface protective layer 4 has a multi-layer structure, it may include layers formed from different resins. Furthermore, when the surface protective layer 4 has a multi-layer structure, the gloss control agent may be contained in at least one layer of the multi-layer structure. Furthermore, when the surface protective layer 4 is a multi-layer structure, it is sufficient that at least the uppermost layer is configured to include a cured product of a curable resin composition, and layers formed from different types of resin materials may be included.

[0069] [Moisture permeability W1 of surface protective layer 4] In this embodiment, the moisture permeability W1 of the surface protective layer 4 is not particularly limited. The moisture permeability W1 of the surface protective layer 4 can be controlled, for example, by selecting the material and forming conditions (adjusting the curing method and hardness) of the surface protective layer 4. The degree of curing of the surface protective layer 4 may also be controlled by the temperature history until the decorative sheet (laminate) is in its final form.

[0070] [Moisture permeability W3 of 2-layer sheet 50] In this embodiment, the moisture permeability W3 of the two-layer sheet 50, which is a laminate consisting of only the transparent resin layer 1 and the surface protective layer 4, is 15 g / m 2 - 24 hours or less is preferable, 10g / m 2 24 hours or less is even better. Setting the moisture permeability W3 of the two-layer sheet 50 within the above range makes it possible to prevent moisture from penetrating from the front side of the decorative sheet 10, thereby reducing deterioration (hydrolysis) of the adhesive layer 5. As a result, delamination in the decorative sheet 10 can be effectively suppressed. The moisture permeability W3 of the two-layer sheet 50, like the moisture permeability W2 of the transparent resin layer 1 and the moisture permeability W1 of the surface protective layer 4, is a value measured according to a method conforming to JIS Z 0208 (temperature 40° C., relative humidity 90%). Furthermore, the moisture permeability W3 of the two-layer sheet 50 can be controlled by, for example, selecting the materials for the transparent resin layer 1 and the surface protection layer 4 and combining the formation conditions (adjustment of the curing method and hardness).

[0071] [Change in moisture permeability W3 of two-layer sheet 50 before and after weather resistance test] The moisture permeability W3 of the two-layer sheet 50, which is a laminate composed of the transparent resin layer 1 and the surface protective layer 4, is 15 g / m 2 By setting the time to 24 hours or less, the rate of change in the moisture permeability W3 of the two-layer sheet 50 before and after the weather resistance test can be kept to ±20% or less. If the rate of change in moisture permeability W3 of the two-layer sheet 50 before and after the weather resistance test is within the above numerical range, even when the decorative sheet 10 is used outdoors for a long period of time, it is possible to prevent moisture permeation from the front side of the decorative sheet 10, thereby reducing deterioration (hydrolysis) of the adhesive layer 5. As a result, the interlayer adhesion of the adhesive layer 5 can be maintained, so that delamination in the decorative sheet 10 used outdoors for a long period of time can be effectively suppressed. In this embodiment, the rate of change in moisture permeability W3 before and after the weather resistance test is a value calculated from the moisture permeability W3 before and after the super xenon test, and is a value measured under measurement conditions with an exposure time (test time) of 1750 hours.

[0072] (Easy adhesion layer) The adhesive layer 8 is a layer for bonding the adherend of the decorative sheet 10 (for example, a substrate for a decorative material) and the original fabric layer 7, and is also called a primer layer. The material used for the easy adhesion layer 8 may basically be the same as that for the picture print layer 6 and the concealing layer 3. In addition, considering that the easy adhesion layer 8 is applied to the back surface of the decorative sheet and is wound in a web form, inorganic fillers such as silica, alumina, magnesia, titanium oxide, barium sulfate, etc. may be added to the easy adhesion layer 8 to avoid blocking and improve adhesion with the adhesive. The coating thickness, i.e., the thickness of the easy adhesion layer 8 (primer layer) is intended to ensure adhesion with the base material layer 7, so that it is appropriate to be in the range of 0.1 μm to 10.0 μm, more preferably in the range of 0.1 μm to 3.0 μm. The easy-adhesion layer 8 is necessary when the surface of the base layer 7 is inactive, such as when the layer is made of an olefin-based material, but is not particularly necessary when the surface is active.

[0073] <First Modification> A first modified example of the decorative sheet according to the first embodiment will be described with reference to Fig. 2. Fig. 2 is a schematic cross-sectional view for explaining one configuration example of a decorative sheet 20 according to a first modified example of the first embodiment. The decorative sheet 20 according to this modified example differs from the decorative sheet 10 according to the above-mentioned first embodiment in that the transparent resin layer is not a single layer but a multi-layer. The decorative sheet shown in Fig. 2 comprises, in order from the top of the drawing, a surface protective layer 4, a transparent resin layer 11, an adhesive layer 5 (heat-sensitive adhesive layer, anchor coat layer, dry lamination adhesive layer), a picture print layer 6, a concealing layer 3, a base fabric layer 7, and an easy-adhesion layer 8. As will be described in detail later, the transparent resin layer 11 has a multilayer structure and comprises a transparent resin layer 1 and a transparent resin layer 2.

[0074] 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. That is, the decorative sheet 20 is 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, 2), and a surface protective layer 4 in this order. In addition, in the decorative sheet 20 according to this embodiment, the laminate (a sheet having a three-layer structure) composed of the transparent resin layer 11 and the surface protective layer 4 will be referred to as a "three-layer sheet 51" for the sake of convenience.

[0075] Below, a detailed description will be given of the transparent resin layer 11, which is a configuration of the decorative sheet 20 that differs from that of the decorative sheet 10. Note that the configuration of the decorative sheet 20 other than the transparent resin layer 11 is the same as that of the decorative sheet 10. For this reason, the same reference numerals as those in the decorative sheet 10 are used and detailed description will be omitted. In this modified example, it is also sufficient that the moisture permeability W2 of at least one of the transparent resin layer 1 and the transparent resin layer 2 is lower than the moisture permeability W1 of the surface protective layer 4. As a result, in the decorative sheet 20 according to this modified example, deterioration (hydrolysis) of the adhesive layer 5 can be reduced, and delamination in the decorative sheet 10 can be effectively suppressed.

[0076] Furthermore, in this modified example, the moisture permeability W may be decreased in the order of transparent resin layer 2, transparent resin layer 1, and surface protective layer 4. As a result, in the decorative sheet 20 according to this modified example, deterioration (hydrolysis) of adhesive layer 5 can also be reduced, and interlayer delamination in the decorative sheet 10 can be effectively suppressed. Furthermore, in this modified example, the moisture permeability W may be decreased in the order of transparent resin layer 1, transparent resin layer 2, and surface protective layer 4. As a result, in the decorative sheet 20 according to this modified example, deterioration (hydrolysis) of adhesive layer 5 can also be reduced, and interlayer delamination in the decorative sheet 10 can be effectively suppressed.

[0077] In this modified example, the moisture permeability W2 of the transparent resin layer 11 (transparent resin layers 1 and 2) is 15 g / m 2 - 24 hours or less is preferable, 10g / m 2 It is even more preferable that the storage time is 24 hours or less. As a result, the decorative sheet 20 according to this modified example can also reduce deterioration (hydrolysis) of the adhesive layer 5, and can effectively prevent delamination in the decorative sheet 20. In this modified example, the moisture permeability W3 of the three-layer sheet 51 in which the surface protective layer 4 is laminated on the transparent resin layer 11 (transparent resin layers 1 and 2) is 15 g / m 2 - 24 hours or less is preferable, 10g / m 2 It is even more preferable that the storage time is 24 hours or less. As a result, the decorative sheet 20 according to this modified example can also reduce deterioration (hydrolysis) of the adhesive layer 5, and can effectively prevent delamination in the decorative sheet 20. In this modified example, the three-layer sheet 51 in which the surface protective layer 4 is laminated on the transparent resin layer 11 (transparent resin layers 1 and 2) preferably has a change rate of moisture permeability W3 of ±20% or less before and after the weather resistance test, and is preferably 10 g / m 2 It is even more preferable that the storage time is 24 hours or less. As a result, the decorative sheet 20 according to this modified example can also reduce deterioration (hydrolysis) of the adhesive layer 5, and can effectively prevent delamination in the decorative sheet 20.

[0078] (Transparent resin layer) 2, the decorative sheet 20 includes a transparent resin layer 11. The transparent resin layer 11 is a multi-layer (two layers in this example) structure including a transparent resin layer 1 and a transparent resin layer 2. More specifically, the transparent resin layer 11 is a multi-layer structure including the transparent resin layer 1 that serves as a first transparent resin layer, and the transparent resin layer 2 that serves as a second transparent resin layer located between the transparent resin layer 1 and the adhesive layer 5.

[0079] [First transparent resin layer] 2, transparent resin layer 1, which is the first transparent resin layer of transparent resin layer 11 in this modified example, is in contact with surface protective layer 4 and is located above transparent resin layer 2. Transparent resin layer 1, which is the first transparent resin layer of transparent resin layer 11, has the same configuration as transparent resin layer 1 of decorative sheet 10 according to the first embodiment described above, and therefore is given the same reference numeral and detailed description thereof is omitted.

[0080] [Second transparent resin layer] 2, in the decorative sheet 20 according to this modification, the transparent resin layer 2, which is the second transparent resin layer, is provided between the transparent resin layer 1, which is 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 the extrusion lamination method.

[0081] In general, the transparent resin layer 1 and the transparent resin layer 2 in the transparent resin layer 11 are laminated and formed by a co-extrusion method. The resin contained in the transparent resin layer 2 is preferably, for example, an acid-modified resin such as polypropylene, polyethylene, or an acrylic resin. For the purpose of improving adhesive strength, the thickness of the transparent resin layer 2 is desirably 2 μm or more. If the thickness of the transparent resin layer 2 is less than 2 μm, it tends to be difficult to obtain sufficient adhesive strength.

[0082] Moreover, the thickness of the transparent resin layer 2 is desirably 20 μm or less. If the thickness of the transparent resin layer 2 exceeds 20 μm, the transparent resin layer 2 tends to deteriorate during long-term use, causing cohesive failure and making the layer more susceptible to peeling. In other words, the thickness of the transparent resin layer 2 is preferably within the range of 2 μm or more and 20 μm or less. In addition, in the transparent resin layer 11, the sum of the thickness of the transparent resin layer 1 and the thickness of the transparent resin layer 2 is preferably 40 μm or more and 170 μm or less. In other words, the total thickness of the transparent resin layer 11 is preferably 40 μm or more and 170 μm or less. This makes it possible to suppress an increase in manufacturing costs and a decrease in post-processing properties while improving weather resistance and scratch resistance.

[0083] <Second Modification> The decorative material according to the second modified example of this embodiment will be described with reference to Fig. 3. The decorative sheet according to this embodiment can be suitably used for the purpose of producing a decorative material by laminating it with a base material for a decorative material. Fig. 3 is a cross-sectional view for explaining one configuration example of the decorative material 100 according to the second modified example of this embodiment. 3, the decorative material 100 according to this modification is obtained by laminating the decorative sheet 10 according to this embodiment on a substrate 16 for a decorative material so that the surface protective layer 4 of the decorative sheet 10 is the outermost layer. That is, the decorative material 100 differs from the decorative sheet 10 according to the first embodiment in that it includes an adhesive 15 and a substrate 16 for a decorative material.

[0084] (Decorative materials) 3, in the decorative material 100, a concealing layer 3, a pattern printed layer 6, an adhesive layer 5, a transparent resin layer 1, and a surface protective layer 4 are laminated in this order on one surface of an original fabric layer 7 in a decorative sheet 10, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 are provided on the other surface of the original fabric layer 7. In other words, the decorative material 100 comprises the decorative material substrate 16 and the decorative sheet 10, which is a laminate bonded to the decorative material substrate 16. As a result, the decorative material 100 can provide a decorative material that reduces the deterioration of the adhesive layer 5 inside the decorative sheet 10 caused by long-term use and reduces the occurrence of delamination.

[0085] (Base material for cosmetic materials) The decorative material substrate 16 may be a wood substrate or a metal substrate. The wooden substrate may be, for example, a wood veneer, a wood plywood, a laminated lumber, a particle board, a medium density fiberboard, a hard fiberboard, or a chipboard. The metal substrate may be, for example, a steel plate or an aluminum plate. The decorative material substrate 16 may be a resin such as plastic, or a composite material thereof. When the decorative material substrate 16 is a resin substrate, for example, a polyvinyl chloride resin may be used.

[0086] The decorative material substrate 16 may be made of, for example, a non-combustible steel plate or a non-combustible material as specified by Notification No. 1400 of the Ministry of Construction. The shape of the base material 16 for decorative material is not particularly limited, but may be, for example, a flat plate. An adhesive 15 may be used to bond the base material 16 for decorative material and the decorative sheet 10. The adhesive 15 is the same as the adhesive 15 in the second modified example of the first embodiment, and therefore the same reference numeral is used and a description thereof is omitted.

[0087] When bonding the decorative material substrate 16 and the decorative sheet 10 together, a bonding device such as a cold press, a hot press, a roll press, a laminator, a wrapping machine, an edge bonding machine, or a vacuum press can be used. After bonding the decorative material substrate 16 and the decorative sheet 10, depending on the characteristics of the final product, it may be possible to perform processes such as cutting, tongue and groove processing using a tenon, V-shaped groove processing, and chamfering of the four sides (e.g., C-chamfering).

[0088] The decorative material 100 according to this modification may be provided with grooves and / or chamfers extending from the decorative sheet 10 side to the base material 16 for the decorative material, and the grooves and chamfers may be painted with a colored paint. The colored paint for painting the grooves and chamfers can be, for example, an ink made by dissolving or dispersing a colorant (organic pigment, inorganic pigment) that can also be used in the adhesive layer 5 in a vehicle. Specific examples of colorants are the same as those described above. Examples of vehicles include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyesters, polyurethanes made of isocyanates and polyols, polyacrylics, polyvinyl acetates, polyvinyl chlorides, vinyl chloride-vinyl acetate copolymers, cellulose-based resins, polyamide-based resins, and the like. These vehicles can be used alone or in combination of two or more. As described above, it is preferable to use a colored paint containing a curing agent such as isocyanate that chemically bonds with the silanol groups of the modified resin layer. In addition, solvents, auxiliary agents, and the like can be added as necessary.

[0089] The decorative material 100 according to this modification has been described above. Note that FIG. 3 illustrates an example in which the decorative material 100 is constructed using the decorative sheet 10 according to the first embodiment, but the present disclosure is not limited thereto. The decorative material 100 may be constructed using the decorative sheet 20 according to the first modification of this embodiment, as shown in FIG. 4. For example, the decorative material 100 may have a concealing layer 3, a picture print layer 6, an adhesive layer 5, a transparent resin layer 2, a transparent resin layer 11, and a surface protection layer 4 laminated in this order on one surface side of the original fabric layer 7 in the decorative sheet 20, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 provided on the other surface side of the original fabric layer 7. That is, the decorative material 100 may be configured to include a base material 16 for a decorative material and a decorative sheet 20 that is a laminate bonded to the base material 16 for a decorative material. This makes it possible for the decorative material 100 to provide a decorative material that reduces deterioration of the adhesive layer 5 inside the decorative sheet 20 caused by long-term use and reduces the occurrence of delamination.

[0090] (Effects of this embodiment) The decorative sheet and decorative material according to this embodiment have the following effects. (1) The decorative sheet (decorative sheets 10, 20) of this embodiment comprises an adhesive layer 5, a transparent resin layer (transparent resin layer 1, 11) and a surface protective layer 4, in that order, on an original fabric layer 7 containing at least an olefin-based resin, and the moisture permeability W2 of the transparent resin layer (transparent resin layer 1, 11) is lower than the moisture permeability W1 of the surface protective layer 4. According to this configuration, it is possible to provide a decorative sheet that can reduce deterioration of the adhesive layer 5 inside the decorative sheet (decorative sheets 10, 20) and reduce the occurrence of delamination. (2) In the decorative sheets (decorative sheets 10, 20), the moisture permeability W2 of the transparent resin layers (transparent resin layers 1, 11) is 15 g / m 2 It may be less than 24 hours. According to this configuration, it is possible to provide a decorative sheet that can reduce deterioration of the adhesive layer 5 inside the decorative sheet (decorative sheets 10, 20) and reduce the occurrence of delamination. (3) In the decorative sheets (decorative sheets 10, 20), the moisture permeability W3 of the sheet (two-layer sheet 50, three-layer sheet 51) in which the surface protective layer 4 is laminated on the transparent resin layer (transparent resin layer 1, 11) is 15 g / m 2 It may be less than 24 hours. According to this configuration, it is possible to provide a decorative sheet that can reduce deterioration of the adhesive layer 5 inside the decorative sheet (decorative sheets 10, 20) and reduce the occurrence of delamination.

[0091] (4) In the decorative sheet (decorative sheets 10, 20) according to this embodiment, the rate of change in moisture permeability W3 before and after weather resistance testing of a sheet (two-layer sheet 50, three-layer sheet 51) in which a surface protective layer 4 is laminated on a transparent resin layer (transparent resin layer 1, 11) may be ±20% or less. According to this configuration, a decorative sheet can be provided that reduces deterioration of the adhesive layer 5 inside the decorative sheet (decorative sheets 10, 20) even after long-term use, and reduces the occurrence of delamination. (5) In the decorative sheets (decorative sheets 10, 20) according to this embodiment, one or more types of ultraviolet absorbents (UVA) may be added to either the surface protective layer 4 or the transparent resin layer (transparent resin layer 1, 11). According to this configuration, a decorative sheet can be provided that reduces deterioration of the adhesive layer 5 inside the decorative sheet (decorative sheets 10, 20) even after long-term use, and reduces the occurrence of delamination. (6) In the decorative sheets (decorative sheets 10, 20) according to this embodiment, one or more types of light stabilizers (HALS) may be added to either the surface protective layer 4 or the transparent resin layer (transparent resin layer 1, 11). According to this configuration, a decorative sheet can be provided that reduces deterioration of the adhesive layer 5 inside the decorative sheet (decorative sheets 10, 20) even after long-term use, and reduces the occurrence of delamination.

[0092] (Example) The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the examples. In this example, the transparent resin layer 1 was formed using the following polypropylene resin.

[0093] [Polypropylene resin A] Random polypropylene resin "F219DA" (Prime Polymer Co., Ltd.), MFR 8.0g / 10Min.) Extrusion temperature: 200℃ Cooling roll water temperature during film formation: 25~50℃ [Polypropylene resin B] Highly crystalline homopolypropylene resin "F109V" (Prime Polymer Co., Ltd., MFR 30.0g / 10Min.) Extrusion temperature: 200~230℃ Cooling roll water temperature during film formation: 25 to 65°C

[0094] <Example 1> A wood grain pattern was gravure printed on a polyethylene base film (thickness 70 μm) with concealability to form a base film layer 7 using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to form a picture pattern layer 6 (thickness 3 μm). Further, 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) to form an adhesive layer 5. The transparent resin layer 1 was formed from a resin material in which various additives were blended with polypropylene resin A. More specifically, a resin material in which 0.5 parts by mass of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF) and 0.5 parts by mass of a NOR-type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) were blended with 100 parts by mass of polypropylene resin A was extruded using a melt extruder to form a transparent resin sheet (protective film) having a thickness of 75 μm to be used as the transparent resin layer 1. The moisture permeability W2 of the transparent resin layer 1 thus formed was 6.0 g / m 2 ·day. The conditions for forming the transparent resin layer 1 (film formation conditions) were as follows: the extrusion temperature of the polypropylene resin A was 200°C, and the cooling roll water temperature during film formation was 25°C.

[0095] Next, a two-component cured polyurethane resin layer consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate) was applied (layer thickness 9 μm) onto the transparent resin layer 1 (the above-mentioned protective film) as a surface protective layer 4, thereby obtaining the decorative sheet 10 of Example 1 in which the transparent resin layer 1 is a single layer.

[0096] <Example 2> A transparent resin layer 1 (transparent resin sheet) was formed in the same manner as in Example 1, except that polypropylene resin B was used as the polypropylene resin. The moisture permeability W2 of the formed transparent resin layer 1 was 3.5 g / m 2 ·day. The conditions for forming the transparent resin layer 1 (film formation conditions) were as follows: the extrusion temperature of the polypropylene resin B was 230°C, and the cooling roll water temperature during film formation was 65°C. In this way, the decorative sheet 10 of Example 2 was obtained.

[0097] <Example 3> A transparent resin layer 1 (transparent resin sheet) was formed in the same manner as in Example 1, except that 30 parts by mass of a softener (L-MODU S901 (Idemitsu Kosan Co., Ltd.)) was added to 100 parts by mass of polypropylene resin B constituting the transparent resin layer 1. The moisture permeability W2 of the formed transparent resin layer 1 was 9.5 g / m 2 ·day. The conditions for forming the transparent resin layer 1 (film-forming conditions) were as follows: the extrusion temperature of the polypropylene resin B was 200°C, and the cooling roll water temperature during film formation was 25°C. In this way, the decorative sheet 10 of Example 3 was obtained.

[0098] <Example 4> A transparent resin layer 1 (transparent resin sheet) was formed in the same manner as in Example 1, except that 0.5 parts by mass of UVA (CYASORB UV-1164; manufactured by SUNCHEM) was added to 100 parts by mass of polypropylene resin A constituting the transparent resin layer 1. The moisture permeability W2 of the formed transparent resin layer 1 was 6.5 g / m 2 ·day. The conditions for forming the transparent resin layer 1 (film formation conditions) were as follows: the extrusion temperature of the polypropylene resin A was 200°C, and the cooling roll water temperature during film formation was 25°C. In this way, the decorative sheet 10 of Example 4 was obtained.

[0099] <Example 5> A surface protective layer 4 was formed in the same manner as in Example 4, except that 5 parts by mass of UVA (Tinuvin 479 (manufactured by BASF)) and 5 parts by mass of a light stabilizer (Tinuvin 123 (manufactured by BASF)) were added to 100 parts by mass of the polyurethane resin constituting the surface protective layer 4. The moisture permeability W1 of the formed surface protective layer 4 was 600 g / m 2 ·day. In this way, the decorative sheet 10 of Example 5 was obtained.

[0100] <Example 6> A surface protective layer 4 was formed in the same manner as in Example 4, except that 5 parts by mass of UVA (Tinuvin 479 (manufactured by BASF)) was added to 100 parts by mass of the polyurethane resin constituting the surface protective layer 4. The moisture permeability W1 of the formed surface protective layer 4 was 600 g / m 2 ·day. In this way, the decorative sheet 10 of Example 6 was obtained.

[0101] <Example 7> A surface protective layer 4 was formed in the same manner as in Example 4, except that 5 parts by mass of a light stabilizer (Tinuvin 123 (manufactured by BASF)) was added to 100 parts by mass of the polyurethane resin constituting the surface protective layer 4. The moisture permeability W1 of the formed surface protective layer 4 was 600 g / m 2 ·day. In this way, the decorative sheet 10 of Example 7 was obtained.

[0102] <Example 8> A decorative sheet 10 was obtained in the same manner as in Example 5, except that the film thickness of the transparent resin layer 1 was 30 μm. The moisture permeability W2 of the formed transparent resin layer 1 was 16.5 g / m 2 ·day. In this way, the decorative sheet 10 of Example 8 was obtained.

[0103] <Example 9> A transparent resin layer 1 (transparent resin sheet) was formed in the same manner as in Example 1, except that 0.5 parts by mass of UVA (CYASORB UV-1164; manufactured by SUNCHEM) was added to 100 parts by mass of polypropylene resin A constituting the transparent resin layer 1, and HALS was not added. The moisture permeability W2 of the formed transparent resin layer 1 was 6.0 g / m 2 ·day. In this way, the decorative sheet 10 of Example 9 was obtained.

[0104] <Comparative Example 1> A transparent resin layer 1 (transparent resin sheet) was formed in the same manner as in Example 4, except that a PMMA resin film (HBA007P manufactured by Mitsubishi Chemical) was used as the transparent resin layer 1. The moisture permeability W2 of the formed transparent resin layer 1 was 270 g / m 2 The surface protective layer 4 was formed in the same manner as in Example 4, except that the thickness of the surface protective layer 4 was 25 μm. The moisture permeability W1 of the formed surface protective layer 4 was 235 g / m 2 ·day. In this manner, the decorative sheet 10 of Comparative Example 1 was obtained.

[0105] <Comparative Example 2> The surface protection layer 4 is a resin film (5 μm, moisture permeability 85 g / m) made of a mixture of PVDF (polyvinylidene fluoride) resin and PMMA resin. 2 1 day) and a PMMA resin film (45 μm, moisture permeability 350 g / m 2 A surface protective layer 4 and a transparent resin layer 1 were formed in the same manner as in Comparative Example 1, except that a film co-extruded with 1,000,000 sintered materials (polyethylene glycol) and 1,000,000 sintered materials (polyethylene glycol) were used. In this manner, the decorative sheet 10 of Comparative Example 2 was obtained.

[0106] The moisture permeability (moisture permeability W1, moisture permeability W2) measured for each of the decorative sheets 10 in Examples 1 to 9 and Comparative Examples 1 and 2 is shown in Table 1. Table 1 also shows the moisture permeability (moisture permeability W3, moisture permeability W4) measured for the two-layer sheet obtained by laminating the transparent resin layer 1 and the surface protective layer 4 that constitute each of the decorative sheets 10 of Examples 1 to 9 and Comparative Examples 1 to 2. The moisture permeability W3 indicates the moisture permeability of the two-layered sheet before the weather resistance test, and the moisture permeability W4 indicates the moisture permeability of the two-layered sheet after the weather resistance test.

[0107] [Table 1]

[0108] The weather resistance (interlayer adhesion) evaluation and scratch resistance evaluation carried out on each of the decorative sheets 10 of Examples 1 to 9 and Comparative Examples 1 and 2 will be described below.

[0109] <Evaluation method> Weather resistance (interlayer adhesion) evaluation After testing for 1,750 hours with a super xenon testing machine, we made cuts in the film with a cutter blade and checked whether it could be peeled off with tweezers. ○: Cannot be peeled off △: Partial peeling ×: Peelable In addition, a rating of "○" or above is deemed to be a practical level and is therefore considered to be "passed."

[0110] Scratch resistance rating The Hoffman scratch test was selected as the method for evaluating scratch resistance. The Hoffman scratch test was performed using a Hoffman scratch hardness tester (manufactured by BYK-Gardner) by scratching the surface of the decorative material using the decorative sheets of each Example and Comparative Example at a constant speed with loads of 200g to 2000g, with a test length of 5cm per 200g, and the load at which damage occurred to the surface of the decorative sheet was recorded. 〇: Hoffman Scratch 1200g or more △: Hoffman Scratch 600g or more but less than 1200g ×: Hoffman scratch less than 600g In addition, a rating of "△" or above is deemed to be at a practical level and is therefore rated as "pass."

[0111] As shown in Table 1, if the moisture permeability W2 of the transparent resin layer 1 is lower than the moisture permeability W1 of the surface protective layer 4, the occurrence of interlayer peeling (peel-off within the decorative sheet) can be reduced. Moreover, with each of the decorative sheets 10 of Examples 1 to 9 described above, it is possible to improve scratch resistance.

[0112] Moreover, for example, this embodiment can have the following configuration. (1) A decorative sheet comprising, in this order, an adhesive layer, a transparent resin layer, and a surface protective layer on a substrate sheet containing at least an olefin-based resin, A decorative sheet, characterized in that the moisture permeability W2 of said transparent resin layer is lower than the moisture permeability W1 of said surface protective layer. (2) The moisture permeability W2 of the transparent resin layer is 15 g / m 2 The decorative sheet according to (1) above, characterized in that the shelf life is 24 hours or less. (3) The moisture permeability W3 of the two-layer sheet in which the surface protective layer is laminated on the transparent resin layer is 15 g / m 2 The decorative sheet according to (1) or (2) above, characterized in that the shelf life is 24 hours or less. (4) A decorative sheet according to any one of (1) to (3) above, characterized in that the rate of change in moisture permeability W3 before and after weather resistance testing of a two-layer sheet having the surface protective layer laminated on top of the transparent resin layer is ±20% or less. (5) The decorative sheet according to any one of (1) to (4) above, characterized in that one or more types of ultraviolet absorbents are added to at least one of the surface protective layer and the transparent resin layer. (6) The decorative sheet according to any one of (1) to (5) above, characterized in that at least one type of light stabilizer is added to at least one of the surface protective layer and the transparent resin layer. [Explanation of symbols]

[0113] 1, 2 Transparent resin layer 1a Embossed pattern 3. Hidden Layer 4 Surface protective layer 5 Adhesive layer 6. Pattern printing layer 7 Original layer 8 Easy adhesive layer 10, 20 Decorative sheet 100 Cosmetic materials

Claims

1. A decorative sheet comprising, in this order, an adhesive layer, a transparent resin layer, and a surface protective layer on a substrate sheet containing at least an olefin-based resin, The moisture permeability W of the transparent resin layer ２ is the moisture permeability W of the surface protective layer １ The decorative sheet is characterized in that the thickness is lower than that of the decorative sheet.

2. The moisture permeability W of the transparent resin layer ２ is 15 g / m ２ The decorative sheet according to claim 1, characterized in that the durability is 24 hours or less.

3. The moisture permeability W of the two-layer sheet having the surface protective layer laminated on the transparent resin layer ３ is 15 g / m ２ The decorative sheet according to claim 1, characterized in that the durability is 24 hours or less.

4. The moisture permeability W of a two-layer sheet having the surface protective layer laminated on the transparent resin layer before and after a weather resistance test ３ 2. The decorative sheet according to claim 1, wherein the rate of change is ±20% or less.

5. 2. The decorative sheet according to claim 1, wherein at least one type of ultraviolet absorbing agent is added to at least one of said surface protective layer and said transparent resin layer.

6. 6. The decorative sheet according to claim 5, wherein at least one type of light stabilizer is added to at least one of said surface protective layer and said transparent resin layer.

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