Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material capable of suppressing deterioration of adhesion under a high temperature environment even when formed by using a plant-derived material.SOLUTION: The decorative sheet is formed by laminating a coloring base material layer 2, a pattern layer 3, an adhesive resin layer 4, and a transparent resin layer 5 in this order, and the coloring base material layer 2 and the transparent resin layer 5 are each formed using a resin composition containing a plant-derived polyolefin resin. Furthermore, the Martens hardness HM in the cross-sectional direction of the adhesive layer 4 is in the range of 5N / mm2 or more and 20N / mm2 or less. By adjusting the Martens hardness of the adhesive resin layer 4, it is possible to suppress a decrease in the adhesion of the adhesive resin layer 4 in a high temperature environment.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet and a decorative material. [Background technology]

[0002] As an alternative to decorative sheets made of polyvinyl chloride, decorative sheets using olefin resins have been proposed, as disclosed in Patent Document 1, for example. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-188941 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, due to environmental concerns, biomass plastics have been attracting attention as an alternative. In the field of decorative sheets, there is a desire to reduce the amount of fossil fuel used by replacing conventional petroleum-derived materials with biomass-derived raw materials. Biomass polyethylene is one example of a plant-derived material that can be used for decorative sheets. However, this biomass polyethylene has poorer heat resistance than polypropylene, which has traditionally been used as a material for decorative sheets. As a result, there is concern that the adhesiveness of the decorative sheet will decrease as it deteriorates in high-temperature environments.

[0005] The present invention has been made in consideration of these points, and aims to provide a decorative sheet and decorative material that can suppress a decrease in adhesion in high-temperature environments, even when formed using a plant-derived polyolefin resin. [Means for solving the problem]

[0006] According to one aspect of the present invention, a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin, and the adhesive resin layer has a Martens hardness HM of 5 N / mm in the cross-sectional direction. 2 More than 20N / mm 2 Decorative sheets are provided that fall within the following ranges:

[0007] According to another aspect of the present invention, there is provided a decorative material comprising a substrate and the decorative sheet of the above aspect laminated on at least one surface of the substrate. [Effects of the Invention]

[0008] According to one embodiment of the present invention, it is possible to provide decorative sheets and decorative materials that are capable of suppressing a decrease in adhesion in high-temperature environments, even when formed by including a plant-derived polyolefin resin. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a decorative sheet according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present technology will be described with reference to the drawings. In the drawings, identical or similar parts are denoted by the same or similar reference numerals, and redundant explanations are omitted. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., may differ from the actual ones. The layers do not necessarily need to be stacked in the order shown in the drawings, as long as they fall within the scope of the present disclosure. Layers not shown in the drawings may also be added. Furthermore, the embodiments shown below are illustrative of configurations that embody the technical concept of the present disclosure, and the material, shape, structure, etc. of the components are not limited to those described below. The technical concept of the present disclosure may be modified in various ways within the technical scope defined by the claims.

[0011] Furthermore, the directions of "left and right" and "up and down" in the following explanation are merely definitions for the convenience of explanation and do not limit the technical idea of ​​the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left." The structure of the decorative material 10 will be described below with reference to FIG.

[0012] As shown in Figure 1, the decorative material 10 comprises a decorative sheet 1 and a substrate 9. The specific configuration of the decorative sheet 1 will be described later. The base material 9 is formed into a plate shape using, for example, a wood board, an inorganic board, a metal plate, or the like, and has a decorative sheet 1 laminated on one surface (the upper surface in FIG. 1) thereof. That is, the decorative material 10 comprises the base material 9 and the decorative sheet 1 laminated on one surface of the base material 9.

[0013] (Composition of decorative sheet) As shown in Figure 1, the decorative sheet 1 comprises a colored base layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive resin layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protective layer 6, an uneven portion 7, and a primer layer 8.

[0014] <Colored base material layer> The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is formed using a resin composition containing a biomass-derived (plant-derived) polyolefin resin. Specifically, it is a colored resin layer formed from a resin composition containing, for example, biomass-derived (plant-derived) polyethylene, fossil fuel-derived ethylene, and fossil fuel-derived polyethylene obtained by polymerizing a monomer containing at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin. In the present specification, "biomass-derived" means "plant-derived".

[0015] The composition of the colored substrate layer 2 will be described in detail below. (Biomass-derived polyethylene) Biomass-derived polyethylene is produced by polymerizing a monomer containing biomass-derived ethylene. The biomass-derived ethylene is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyethylene is biomass-derived. The raw material monomer for polyethylene does not necessarily contain 100% by mass of biomass-derived ethylene.

[0016] The monomers that are raw materials for biomass-derived polyethylene may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefins, or may further contain biomass-derived α-olefins.

[0017] The number of carbon atoms in the α-olefin is not particularly limited, but those having 3 to 20 carbon atoms can usually be used, and butylene, hexene, or octene is preferred. This is because butylene, hexene, or octene can be produced by polymerizing ethylene, a raw material derived from biomass. Furthermore, by including such an α-olefin, the polyethylene obtained by polymerization has alkyl groups as a branched structure, and can therefore be more flexible than a simple linear polyethylene. By using ethylene, a raw material derived from biomass, it is theoretically possible to produce polyethylene using components derived 100% from biomass.

[0018] The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as "biomass content") is a value obtained by measuring the biomass-derived carbon content through radiocarbon (C14) analysis. Atmospheric carbon dioxide contains a certain proportion of C14 (105.5 pMC), and it is known that the C14 content in plants that grow by absorbing atmospheric carbon dioxide, such as corn, is also approximately 105.5 pMC. It is also known that fossil fuels contain very little C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 in the total carbon atoms in the polyethylene. In this embodiment, when the C14 content in the polyethylene is PC14, the biomass-derived carbon content Pbio can be determined as follows.

[0019] Pbio(%) = PC14 / 105.5 × 100

[0020] In the present embodiment, theoretically, if all biomass-derived ethylene is used as a raw material for polyethylene, the concentration of biomass-derived ethylene is 100%, and the biomass degree of biomass-derived polyethylene is 100. Furthermore, the concentration of biomass-derived ethylene in fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of fossil fuel-derived polyethylene is 0.

[0021] In this embodiment, the biomass-derived polyethylene or the decorative sheet comprising this polyethylene does not necessarily have a biomass degree of 100. In this embodiment, the method for polymerizing the ethylene-containing monomer derived from biomass is not particularly limited, and can be carried out by a conventionally known method. The polymerization temperature and polymerization pressure may be adjusted appropriately depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of the method for polymerizing the ethylene-containing monomer will be described below.

[0022] The polymerization method for ethylene polymers or ethylene / α-olefin copolymers can be appropriately selected depending on the type of polyethylene desired, for example, differences in density and branching, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), etc. For example, it is preferable to use a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as the polymerization catalyst, and to carry out the polymerization in one stage or two or more stages by any of gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0023] Furthermore, as the biomass-derived polyethylene, ethylene polymers and copolymers of ethylene and α-olefins may be used alone or in combination of two or more.

[0024] (Resin composition containing biomass-derived polyethylene) In this embodiment, the resin composition contains the above-mentioned polyethylene as a main component. The resin composition may contain two or more polyethylenes with different biomass contents, as long as the concentration of biomass-derived ethylene in the resin composition as a whole is within the above range.

[0025] (Ethylene derived from fossil fuels, polyethylene derived from fossil fuels) The colored substrate layer 2 contains biomass-derived polyethylene made from the resin composition, and further contains fossil fuel-derived ethylene and fossil fuel-derived polyethylene obtained by polymerizing a monomer containing at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin. That is, in this embodiment, the resin composition is a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and mixing can be performed by a conventionally known method. For example, dry blending or melt blending may be used.

[0026] According to this embodiment, the resin composition forming the colored substrate layer 2 preferably contains 5 to 90 mass %, more preferably 25 to 75 mass %, of biomass-derived polyethylene and preferably 10 to 95 mass %, more preferably 25 to 75 mass % of fossil fuel-derived polyethylene. Even when a resin composition is used that is a mixture containing biomass-derived polyethylene, fossil fuel-derived ethylene, and fossil fuel-derived polyethylene obtained by polymerizing a monomer containing at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, it is sufficient that the concentration of biomass-derived ethylene in the resin composition as a whole is within the above range.

[0027] In addition to polyethylene, which is the main component, various additives may be added to the resin composition produced in the above-mentioned resin composition production process, as long as the properties of the composition are not impaired. Examples of additives that can be added include plasticizers, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather resistance agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, and color pigments. These additives are preferably added in an amount of 1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the resin composition.

[0028] As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass, based on the entire colored substrate layer 2. If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and a carbon-neutral decorative sheet can be achieved.

[0029] The colored substrate layer 2 has a density of 0.92 [g / cm 3 ] or more than 1.16[g / cm 3 ] or less, preferably 0.98 [g / cm 3 ] or more 1.10[g / cm 3 The density of the colored substrate layer 2 is a value measured according to the method specified in Method A of JIS K7112-1980 after annealing as specified in JIS K6760-1995. When the density of the colored substrate layer 2 is 0.92 [g / cm 3 ] or more, the rigidity of the colored substrate layer 2 can be increased. 3 ] or less, the transparency and mechanical strength of the colored substrate layer 2 can be improved.

[0030] The colored substrate layer 2 may contain, as the biomass-derived polyethylene, a biomass-derived high-density polyethylene and a biomass-derived low-density polyethylene, a biomass-derived high-density polyethylene and a fossil fuel-derived low-density polyethylene, or a fossil fuel-derived high-density polyethylene and a biomass-derived low-density polyethylene.

[0031] The biomass ratio of the entire colored substrate layer 2 may be within the range of 10% or more and 90% or less. Biomass-derived high-density polyethylene has a density of 0.94 g / cm 3 ]. Biomass-derived low-density polyethylene refers to polyethylene with a density of 0.94 [g / cm 3 ] refers to the following polyethylene.

[0032] The biomass-derived polyethylene for the colored substrate layer 2 is preferably a blend of biomass-derived high-density polyethylene and low-density polyethylene (which may be biomass-derived or fossil fuel-derived) in a ratio of 95:5 to 70:30. If the content of low-density polyethylene is low, film formation stability is poor, while if the content of low-density polyethylene is high, the film becomes too soft. The method for producing the colored substrate layer 2 is not particularly limited, and the layer can be produced by a conventionally known method. In this embodiment, the layer is preferably formed by calender molding.

[0033] Furthermore, as described above, the colored substrate layer 2 may contain, if necessary, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters.

[0034] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 200 μm, more preferably 51 μm to 120 μm, and even more preferably 55 μm to 100 μm. This is because, when the thickness of the colored substrate layer 2 made of biomass-derived polyethylene is 40 μm or more, it can absorb unevenness and steps in the underlying flooring material, etc., thereby improving the application finish of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 200 μm or less, it is not necessary to form the colored substrate layer 2 thicker than necessary, which reduces the manufacturing cost of the decorative sheet 1.

[0035] In this embodiment, biomass-derived polyethylene has been described as the biomass-derived resin constituting the colored substrate layer 2, but the present invention is not limited to this. For example, biomass-derived polypropylene or biomass-derived polybutylene may be used instead of the biomass-derived polyethylene described above. In other words, in this embodiment, a wide variety of biomass-derived polyolefins can be used as the biomass-derived resin constituting the colored substrate layer 2.

[0036] <Picture layer> The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored substrate layer 2, and is a layer for adding a pattern to impart design properties. The design layer 3 is formed using printing ink, paint, etc. The printing ink, paint, etc. that forms the design layer 3 is formed, for example, by dissolving or dispersing a colorant such as a dye or pigment together with an appropriate binder resin in an appropriate dilution solvent.

[0037] The printing ink or paint that forms the design layer 3 is applied by using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating. The design layer 3 is formed by containing the above-mentioned colorant and binder resin. The binder resin used in the design layer 3 in this embodiment will be described below.

[0038] [Binder resin] The binder resin contained in the design layer 3 includes a biourethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy(meth)acrylate. In the design layer 3, at least one of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate constituting the biourethane (meth)acrylate preferably contains a biomass-derived component. In the following description, a urethane (meth)acrylate containing a biomass-derived component is also referred to as a biourethane (meth)acrylate.

[0039] That is, the design layer 3 is a resin layer containing the above-mentioned colorant and biourethane (meth)acrylate. That is, the design layer 3 contains a colorant and a biomass-derived component.

[0040] Biourethane (meth)acrylates are obtained, for example, by reacting a polyol and an isocyanate with a hydroxy(meth)acrylate. In the biourethane (meth)acrylates, a plant-derived polyol can be used as the polyol, a plant-derived isocyanate can be used as the isocyanate, or both the polyol and the isocyanate can be plant-derived.

[0041] The polyol may be a polyester polyol, which is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, a polyether polyol, which is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate, or a polycarbonate polyol, which is a reaction product of a polyfunctional alcohol and a carbonate. Each of these polyols preferably contains a biomass-derived component. Each polyol will be described below.

[0042] <Polyester polyol> When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains a biomass-derived component. Examples of polyester polyols containing a biomass-derived component include the following. Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional carboxylic acids Reaction products of polyfunctional alcohols derived from fossil fuels and polyfunctional carboxylic acids derived from biomass Reaction products of biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional carboxylic acids Examples of biomass-derived polyfunctional alcohols that can be used include aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugarcane, cassava, and sago palm. Examples of biomass-derived aliphatic polyfunctional alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), and hexamethylene glycol, all of which can be obtained from plant materials by the following methods. These may be used alone or in combination.

[0043] Biomass-derived polypropylene glycol is produced by a fermentation method in which glucose is obtained by decomposing plant raw materials, via 3-hydroxypropylaldehyde (HPA) from glycerol. Compared to polypropylene glycol produced by the EO production method, polypropylene glycol produced by a biomethod such as the fermentation method is preferable in terms of safety, as useful by-products such as lactic acid can be obtained, and production costs can be kept low.

[0044] Biomass-derived butylene glycol can be produced by producing glycol from plant raw materials, fermenting the glycol, obtaining succinic acid, and then hydrogenating the resulting succinic acid. Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

[0045] The fossil fuel-derived polyfunctional alcohol may be a compound having two or more, preferably two to eight, hydroxyl groups per molecule. Specifically, the fossil fuel-derived polyfunctional alcohol is not particularly limited and may be any conventionally known alcohol. Examples of such alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), and hexamethylene glycol, as well as triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl-1,5-pentanediol, polyether polyol, polycarbonate polyol, polyolefin polyol, and acrylic polyol. These may be used alone or in combination of two or more.

[0046] Examples of biomass-derived polyfunctional carboxylic acids include aliphatic polyfunctional carboxylic acids obtained from plant materials, such as renewable plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, as well as regenerated oils derived from recycled waste cooking oils containing these oils as a primary component. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced by alkaline pyrolysis of ricinoleic acid obtained from castor oil, with heptyl alcohol as a by-product. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid. These may be used alone or in combination of two or more.

[0047] The fossil fuel-derived polyfunctional carboxylic acid may be an aliphatic polyfunctional carboxylic acid or an aromatic polyfunctional carboxylic acid. The fossil fuel-derived aliphatic polyfunctional carboxylic acid is not particularly limited and may be any conventionally known substance, such as adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, and ester compounds thereof. The fossil fuel-derived aromatic polyfunctional carboxylic acid is not particularly limited and may be any conventionally known substance, such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, and ester compounds thereof. These may be used alone or in combination of two or more.

[0048] <Polyether polyol> When the polyether polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains a biomass-derived component. Examples of polyether polyols containing a biomass-derived component include the following. Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional isocyanate ·Reaction products of fossil fuel-derived polyfunctional alcohols with biomass-derived polyfunctional isocyanates ·Reaction products of biomass-derived polyfunctional alcohols with fossil fuel-derived polyfunctional isocyanates As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described above in connection with the polyester polyol can be used.

[0049] Biomass-derived polyfunctional isocyanates can be obtained by converting plant-derived dicarboxylic acids into terminal amino groups through acid amidation and reduction, and then reacting the amidated dicarboxylic acids with phosgene to convert the amino groups into isocyanate groups. Examples of biomass-derived polyfunctional isocyanates include biomass-derived diisocyanates. Examples of biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. Plant-derived diisocyanates can also be obtained by using plant-derived amino acids as raw materials and converting their amino groups into isocyanate groups. For example, lysine diisocyanate (LDI) can be obtained by methyl esterifying the carboxyl groups of lysine and then converting the amino groups into isocyanate groups. 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl groups of lysine and then converting the amino groups into isocyanate groups.

[0050] Other methods for synthesizing 1,5-pentamethylene diisocyanate include the phosgenation method and the carbamate method. More specifically, the phosgenation method involves directly reacting 1,5-pentamethylene diamine or a salt thereof with phosgene, or suspending pentamethylene diamine hydrochloride in an inert solvent and reacting it with phosgene to synthesize 1,5-pentamethylene diisocyanate. The carbamate method involves first carbamatizing 1,5-pentamethylene diamine or a salt thereof to generate pentamethylene dicarbamate (PDC), which is then thermally decomposed to synthesize 1,5-pentamethylene diisocyanate. A polyisocyanate that can be suitably used in the present invention is 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

[0051] The fossil fuel-derived polyfunctional isocyanate is not particularly limited and conventionally known substances can be used, for example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis (phenylene isocyanate) (MDI), jurylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanate dibenzyl and other aromatic diisocyanates. Other examples include aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; and alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI. These may be used alone or in combination of two or more.

[0052] <Polycarbonate polyol> When the polycarbonate polyol contains a biomass-derived component, the polycarbonate polyol can be a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate derived from a fossil fuel. Alternatively, the polycarbonate polyol can be a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component. Examples of carbonates include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate. These can be used alone or in combination of two or more.

[0053] As the biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohols described above in connection with the polyester polyol can be used.

[0054] <Isocyanate compounds> Next, the isocyanate compound will be described. As the isocyanate compound containing a biomass-derived component, the biomass-derived polyfunctional isocyanate described in the polyether polyol can be used.

[0055] <Hydroxy (meth)acrylate> Next, hydroxy(meth)acrylates will be described. Examples of hydroxy(meth)acrylates include hydroxy(meth)acrylates having one (meth)acryloyl group, such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, and 2-hydroxy-3-phenoxypropyl(meth)acrylate; and hydroxy(meth)acrylates having two or more (meth)acryloyl groups, such as glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and sorbitol penta(meth)acrylate. These may be used alone or in combination of two or more.

[0056] The binder resin of the design layer 3 may be formed to contain nitrocellulose in addition to the above-mentioned biourethane (meth)acrylate. That is, the design layer 3 may contain the above-mentioned biourethane (meth)acrylate, or may contain nitrocellulose in addition to the biourethane (meth)acrylate.

[0057] <Nitrocellulose> Nitrocellulose is a nitro-substituted cellulose resin in which some of the hydroxyl groups in the cellulose skeleton are nitrated. The cellulose skeleton of nitrocellulose resin is a biomass material. While ordinary nitrocellulose can be used without any problems, it is particularly preferable to use nitrocellulose in which an average of 1.3 to 2.7 nitro groups are substituted per glucose unit constituting the cellulose skeleton.

[0058] Nitrocellulose is classified into L type and H type depending on the molecular weight. From the viewpoint of solubility in organic solvents, it is preferable to use L type. The design layer 3 preferably has a biomass ratio of 5% or more, more preferably 5% to 50%, and even more preferably 10% to 50%. If the biomass ratio is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the design layer 3 after drying is preferably 0.1 [g / m 2 ] or more than 15[g / m 2 ] or less, more preferably 3 [g / m 2 ] or more than 10[g / m 2 ] or less, more preferably 6 [g / m 2 ] or more than 9 [g / m 2 The design layer 3 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 5 μm or less, and even more preferably 0.7 μm or more and 3 μm or less. Note that a plurality of design layers 3 having such weights and thicknesses may be provided.

[0059] Regarding the "biomass ratio," in the case of biourethane (meth)acrylate, for example, as described above, it is determined as a value measured by measuring the amount of carbon derived from biomass using radiocarbon (C14) measurement.

[0060] Regarding "biomass content," in the case of nitrocellulose, for example, there are three hydroxyl groups per glucose unit (formula weight = 172) that makes up the cellulose skeleton (the starting material), and one to three of these hydroxyl groups can be converted to nitrate esters (the hydrogen is replaced by a nitro group (non-biomass material, formula weight = 46)). If the original cellulose skeleton is made up of 100% biomass material by weight, and the average number of nitro groups replaced per glucose unit is n, then the proportion (by weight) of biomass material in the entire nitrocellulose molecule can be calculated as (172-n) x 100 / (172-n + 46n).

[0061] The proportion of biomass material in the entire nitrocellulose molecule is approximately 78.8% by weight when each glucose unit constituting the cellulose skeleton is substituted with an average of one nitro group, approximately 64.9% by weight when each glucose unit is substituted with two nitro groups, and approximately 55.0% by weight when each glucose unit is substituted with three nitro groups (values ​​calculated using the above formula).

[0062] Furthermore, when the thickness of the design layer 3 is 10 μm or less, the printing workability during the production of the decorative sheet 1 is improved, and the production costs can be reduced. In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the pattern layer 3 to impart various functions.

[0063] Any pattern can be used as the pattern of the pattern layer 3, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, letters, symbols, solid colors, or combinations thereof. In order to improve the hiding power of the decorative sheet 1, a hiding layer may be provided between the pattern layer 3 and the colored substrate layer 2. The hiding layer is formed using, for example, an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0064] In addition, the pattern layer 3 may be configured to have, for example, a solid colored base layer to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer to add a pattern to impart design features.

[0065] <Adhesive resin layer> The adhesive resin layer 4 is laminated on the surface of the design layer 3 opposite the colored substrate layer 2 (the upper surface in Figure 1), and is a layer used to adhere the design layer 3 and the transparent resin layer 5 together.

[0066] The adhesive resin layer 4 may be made of either a polypropylene-based or polyethylene-based material, but because the transparent resin layer 5 is formed of a resin composition containing biomass-derived (plant-derived) polyethylene as described below, it is preferable to use an adhesive resin made of a polyethylene-based material for the adhesive resin layer 4. By forming the adhesive resin layer 4 from a polyethylene-based material, thickness unevenness and quality variation can be suppressed when the decorative sheet 1 is manufactured.

[0067] As the adhesive resin, a resin derived from a fossil fuel is preferred, and resins such as maleic anhydride modified polyethylene resin, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, and polyester-based resins can be used. The adhesive resin layer 4 has a Martens hardness HM of 5 N / mm 2 More than 20N / mm 2 Preferably, it is less than 8N / mm 2 More than 12N / mm 2 It is more preferable that the Martens hardness HM of the adhesive resin layer 4 is within the following range (temperature 23°C, humidity 50% RH): 2 If it is smaller, the adhesive resin layer 4 may not be able to absorb the deformation stress during peeling, which may lead to a decrease in adhesive strength. 2 If it is larger, the adhesive resin layer 4 cannot absorb the deformation stress during peeling, and the adhesive resin layer 4 may break, leading to a decrease in adhesive strength.

[0068] Martens hardness is a type of index that indicates the hardness of a material. It is defined as the quotient of the indentation force calculated from the load and the surface area of ​​the indentation calculated from the indentation depth, which is obtained by applying a load to an indenter and pressing the indenter into the surface of a sample, and measuring the depth of the indentation (indentation) formed in the sample. Martens hardness is measured from the cross section of the decorative sheet 1 to avoid the influence of resin layers laminated other than the adhesive resin layer 4. Specifically, a sample of the decorative sheet 1 is embedded in a resin such as a cold-curing epoxy resin or a UV-curing resin and allowed to fully harden, then cut so that the cross section of the decorative sheet 1 is exposed, and the cut surface is mechanically polished to obtain a measurement surface. An indenter is then pressed into the adhesive resin layer 4, and the Martens hardness is calculated from the pressing depth and load. More specifically, the measurement method is specified in "ISO 14577."

[0069] Methods for adjusting the Martens hardness include, for example, adjusting the extrusion temperature when forming the adhesive resin layer 4, or adding a nucleating agent to the resin that constitutes the adhesive resin layer 4 to adjust the crystallinity of the resin. The adhesive resin layer 4 preferably has a restoration power ηIT in the range of 50% to 75%, more preferably 55% to 70%. If the restoration power ηIT is less than 50%, the elastic deformation during peeling will be small, and the stress change during deformation may not be fully absorbed, resulting in a decrease in adhesion. If the restoration power ηIT is greater than 75%, the elastic deformation during peeling will be excessively large, resulting in a decrease in adhesion.

[0070] Methods for adjusting the restoration power include adjusting the extrusion temperature during film formation of the resin that will become the adhesive resin layer 4, or adding a nucleating agent to the resin that makes up the adhesive resin layer 4 as described above to adjust the crystallinity of the resin.

[0071] Here, the recovery power ηIT is measured, for example, using a Martens hardness tester (Fisherscope HM2000; Fisher Instruments, Inc.) conforming to ISO 14577. The recovery power may also be measured from the cross section of the substrate to avoid the influence of the core layer of the laminated substrate other than the adhesive resin layer 4 during measurement. Specifically, the decorative sheet may be embedded in a resin such as a cold-curing epoxy resin or a UV-curing resin, and then fully cured. The measurement surface may then be obtained by cutting the decorative sheet so that its cross section is exposed and mechanically polishing it. A specific measurement method involves pressing an indenter into the measurement surface of the adhesive resin layer, deriving Wplast (plastic deformation work) and Welast (elastic deformation work) from the area enclosed by the curve of the indentation depth displacement versus load, and then deriving the recovery power (ηIT) from the ratio of the elastic deformation work to Wtotal (total deformation work) using the following equations (1) and (2). The measurement conditions are, for example, a test force of 10 mN, a test force application time of 10 seconds, and a test force holding time of 5 seconds.

[0072] Wtotal = Wplast + Welast …(1) ηIT=Welast / Wtotal …(2)

[0073] In order to improve the adhesion between the design layer 3 and the transparent resin layer 5, an adhesive layer (not shown) may be further provided between the design layer 3 and the adhesive resin layer 4. Examples of materials that can be used for the adhesive layer include urethane adhesives, polyester resins, polyisocyanate resins, and polyester polyol resins.

[0074] <Transparent resin layer> The transparent resin layer 5 is laminated on the surface of the adhesive resin layer 4 opposite to the pattern layer 3 (the upper surface in FIG. 1 ), and is a transparent resin layer formed from a resin composition containing the biomass-derived (plant-derived) polyethylene described above. More specifically, the transparent resin layer 5 is a resin layer formed from a resin composition containing biomass-derived polyethylene obtained by polymerizing a monomer containing the biomass-derived ethylene described above, and fossil fuel-derived polyethylene obtained by polymerizing fossil fuel-derived ethylene and a monomer containing at least one of fossil fuel-derived ethylene and an α-olefin. In other words, the transparent resin layer 5 may use a resin composition containing biomass-derived polyethylene used in the colored substrate layer 2.

[0075] The transparent resin layer 5 may contain the above-mentioned biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass, based on the entire transparent resin layer 5. If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and a carbon-neutral decorative sheet can be achieved.

[0076] The density of the transparent resin layer 5 is 0.92 [g / cm 3 ] or more 0.99[g / cm 3 ] or less, preferably 0.94 [g / cm 3 ] or more 0.98[g / cm 3 ] or less, more preferably 0.95 [g / cm 3 ] or more 0.97[g / cm 3 The density of the transparent resin layer 5 is a value measured according to the method specified in Method A of JIS K7112-1980 after annealing as specified in JIS K6760-1995. 3 ] or more, the rigidity of the transparent resin layer 5 can be increased. 3 ] or less, the transparency and mechanical strength of the transparent resin layer 5 can be improved.

[0077] The transparent resin layer 5 has a thickness of 55 to 150 μm, preferably 55 to 100 μm, and more preferably 60 to 80 μm. The transparent resin layer 5 may contain biomass-derived high-density polyethylene as the biomass-derived polyethylene.

[0078] Furthermore, the transparent resin layer 5 may contain, as the biomass-derived polyethylene, polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in the range of 100:0 to 20:80. Furthermore, the biomass ratio of the entire transparent resin layer 5 may be within the range of 10% to 90%.

[0079] The method for producing the transparent resin layer 5 is not particularly limited, and the layer can be produced by a conventionally known method. In this embodiment, the layer is preferably formed by extrusion molding, and more preferably, the extrusion molding is performed by a T-die method or an inflation method.

[0080] In this embodiment, it is preferable that the transparent resin layer 5 and the colored substrate layer 2 satisfy the following specific relationships with respect to density, thickness, and biomass content (concentration of ethylene derived from biomass). In the present embodiment, it is preferable that the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 satisfy d2>d1. This is because shapeability is required to function as the transparent resin layer 5, and productivity is required to function as the colored substrate layer 2.

[0081] The ratio (d2 / d1) of the density d1 of the transparent resin layer 5 to the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, more preferably in the range of 1.1 to 1.3, and even more preferably in the range of 1.1 to 1.2. When the density ratio of the transparent resin layer to the colored substrate layer is in this range, the extrusion suitability and bending suitability required for a decorative sheet can be achieved even when biomass-derived polyethylene is used.

[0082] In the present embodiment, it is preferable that the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored substrate layer 2 satisfy the relationship t1≧t2. This is because a thickness is required to function as the transparent resin layer 5, but a thickness as large as that of the transparent resin layer 5 is not required to function as the colored substrate layer 2. The ratio (t1 / t2) of the thickness t1 of the transparent resin layer 5 to the thickness t2 of the colored substrate layer 2 is preferably in the range of 1.1 or more and 3 or less, more preferably in the range of 1.1 or more and 2 or less, and even more preferably in the range of 1.1 or more and 1.5 or less.

[0083] In the present embodiment, it is preferable that the concentration C1 of biomass-derived ethylene in the transparent resin layer 5 and the concentration C2 of biomass-derived ethylene in the colored substrate layer 2 satisfy the relationship C1>C2. This is because the transparent resin layer 5 needs to be thick and use a large amount of ethylene to function properly, and therefore increasing the biomass content of the transparent resin layer 5 can further reduce the amount of fossil fuel used.

[0084] The biomass-derived polyethylene forming the transparent resin layer 5 may contain a nucleating agent (for example, "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd.). The nucleating agent is preferably added to the polyethylene in an amount of 500 ppm to 2000 ppm, more preferably 1500 ppm to 2000 ppm, based on the mass of the polyethylene. Adding a nucleating agent to the transparent resin layer 5 can improve extrusion stability during production and also achieve good haze.

[0085] If necessary, the transparent resin layer 5 may contain one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters. The transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1.

[0086] In this embodiment, biomass-derived polyethylene has been described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited to this. For example, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used instead of the biomass-derived polyethylene described above. In other words, in this embodiment, a wide variety of biomass-derived polyolefins can be used as the biomass-derived resin constituting the transparent resin layer 5.

[0087] <Surface protective layer> The surface protective layer 6 is laminated on the opposite side of the transparent resin layer 5 from the adhesive resin layer 4 (the upper side in Figure 1), and is a layer provided to impart functions such as weather resistance, scratch resistance, contamination resistance, and design properties to the decorative sheet 1. The surface protection layer 6 can be made of a thermosetting resin or an ionizing radiation curable resin, and is formed using, for example, an acrylic resin composition.

[0088] The surface protective layer 6 may contain various additives, such as weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters, as needed. The surface protective layer 6 may also contain functional additives, such as antibacterial agents and antifungal agents, as needed.

[0089] <Uneven part> The uneven portion 7 is formed by recesses provided at a plurality of locations from the surface protection layer 6 side to the transparent resin layer 5. The uneven portion 7 does not necessarily have to be provided. <Primer layer> The primer layer 8 is a base layer for improving the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .

[0090] The primer layer 8 is laminated on the surface of the colored substrate layer 2 opposite to the pattern layer 3 (the lower surface in FIG. 1). Furthermore, the primer layer 8 is formed using, for example, a polyester resin, an organic additive, a pigment, and the like. The primer layer 8 may contain an anti-rust pigment in order to improve corrosion resistance.

[0091] The thickness of the primer layer 8 is, for example, in the range of 1 μm to 10 μm. The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even in forms other than this embodiment, as long as they do not deviate from the technical idea of ​​the present invention.

[0092] (Effects of this embodiment) The decorative sheet 1 of this embodiment can achieve the effects described below.

[0093] (1) In the decorative sheet 1 in which a colored substrate layer 2, a design layer 3, an adhesive resin layer 4, and a transparent resin layer 5 are laminated in this order, the colored substrate layer 2 and the transparent resin layer 5 are each a resin layer formed using a resin composition containing a biomass-derived polyolefin resin, and the adhesive resin layer 4 has a Martens hardness HM of 5 N / mm in the cross-sectional direction. 2 More than 20N / mm 2 It is within the following range:

[0094] Biomass-derived polyethylene has inferior heat resistance compared to biomass-derived polypropylene. Therefore, when the decorative sheet 1 is used at high temperatures, deterioration of the transparent resin layer 5 may result in a decrease in adhesion between the transparent resin layer 5 and the pattern layer 3, which is bonded to the transparent resin layer 5 via the adhesive resin layer 4. As described above, adjusting the Martens hardness of the adhesive resin layer 4 can improve heat resistance, thereby preventing a decrease in adhesion between the transparent resin layer 5 and the pattern layer 3 and reducing problems associated with poor interlayer adhesion. In other words, using biomass-derived materials for the colored substrate layer 2 and the transparent resin layer 5 can reduce the amount of fossil fuel used, prevent a decrease in adhesion in high-temperature environments, improve weather-resistant adhesion strength, and maintain the physical properties of the decorative sheet and its long-term quality. Similarly, when the pattern layer 3 is not provided and the colored substrate layer 2 and the transparent resin layer 5 are bonded via the adhesive resin layer 4, a decrease in adhesion between the colored substrate layer 2 and the transparent resin layer 5 can be prevented.

[0095] (2) The adhesive resin layer 4 has a recovery power ηIT in the range of 50% to 75% in an indentation test using a Martens hardness tester. Therefore, adjusting the recovery power ηIT can also improve the heat resistance of the adhesive resin layer 4 and prevent a decrease in adhesion between the adhesive resin layer 4 and a resin layer in contact with it.

[0096] (3) A pattern layer 3 is provided between a colored substrate layer 2 and an adhesive resin layer 4, and each of the colored substrate layer 2 and the transparent resin layer 5 is a resin layer formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene, fossil fuel-derived ethylene, and fossil fuel-derived polyethylene obtained by polymerizing a monomer containing at least one of fossil fuel-derived ethylene and α-olefin, and the colored substrate layer 2 contains 5% by mass or more of biomass-derived ethylene and has a density of 0.92 g / cm 3 More than 1.16g / cm 3 The transparent resin layer 5 has a density within the following range, and contains 5 mass % or more of biomass-derived ethylene and has a density of 0.92 g / cm3 More than 0.99g / cm 3 The density is within the following range, and the pattern layer 3 is a resin layer containing a colorant and a biourethane (meth)acrylate, and the biourethane (meth)acrylate is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy(meth)acrylate, and at least one of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a biomass-derived component.

[0097] Therefore, even when the structure is made of biomass-derived polyethylene, which is a biomass-derived material, it is possible to form a colored substrate layer 2 and a transparent resin layer 5 that have high hardness equivalent to that of a structure made of, for example, polypropylene. Furthermore, by using materials derived from biomass, it is possible to provide a decorative sheet that reliably reduces the amount of fossil fuel used and reliably maintains physical properties suitable for use as a decorative sheet.

[0098] (4) The polyol, which is a constituent element of the biourethane (meth)acrylate contained in the design layer 3, is a polyether polyol or a polycarbonate polyol containing a biomass-derived component. This makes it possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuel used by using biomass-derived materials and more reliably maintain the physical properties suitable for use as a decorative sheet.

[0099] (5) Of the polyols that are components of the biourethane (meth)acrylate contained in the pattern layer 3, the polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional carboxylic acid containing a biomass-derived component. This makes it possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuel used by using biomass-derived materials and more reliably maintain the physical properties suitable for use as a decorative sheet.

[0100] (6) Among the polyols that are components of the biourethane (meth)acrylate contained in the pattern layer 3, the polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional isocyanate containing a biomass-derived component. This makes it possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuel used by using biomass-derived materials and more reliably maintain the physical properties suitable for use as a decorative sheet. (7) Among the polyols that are components of the biourethane (meth)acrylate contained in the pattern layer 3, the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component. This makes it possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuel used by using biomass-derived materials and more reliably maintain the physical properties suitable for use as a decorative sheet.

[0101] (8) The isocyanate compound, which is a constituent element of the biourethane (meth)acrylate contained in the design layer 3, is an isocyanate compound containing a biomass-derived component. This makes it possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuel used by using plant-derived materials and that can more reliably maintain physical properties suitable for use as a decorative sheet.

[0102] (9) The device comprises a substrate 9 and a decorative sheet 1 laminated on at least one surface of the substrate 9. As a result, even when a decorative sheet 1 made from biomass-derived polyethylene resin is used, a decorative material 10 can be provided that can suppress a decrease in the adhesion of the decorative sheet 1 at high temperatures. [Example]

[0103] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0104] Example 1 After corona discharge treatment was performed on one side of a 60 μm-thick colored substrate layer made of biomass-derived polyethylene resin, a design layer made of urethane-based printing ink, a layer made of urethane-based adhesive, an adhesive resin layer, a transparent resin layer made of biomass-derived polyethylene resin, and a surface protection layer primarily composed of an acrylic resin composition were laminated on one side of the colored substrate layer in this order to obtain the decorative sheet of Example 1. The biomass-derived polyethylene resin and adhesive resin that constitute the transparent resin layer, and the maleic anhydride-modified polyethylene that constitutes the adhesive resin layer, were co-extruded onto the design layer after the urethane adhesive had been applied, thereby laminating the adhesive resin layer and transparent resin layer on top of the design layer. The transparent resin layer had a thickness of 70 μm. The adhesive resin layer has a Martens hardness of 5N / mm 2 , the restoration power is 40%, the content of plant-derived ethylene in the colored substrate layer is 3 mass% with respect to the entire colored substrate layer, and the density is 1.5 g / cm 3 The transparent resin layer has a plant-derived ethylene content of 3% by mass relative to the entire transparent resin layer and a density of 1.3 g / cm 3 The design layer was a resin layer containing a colorant and urethane acrylate that did not contain any plant-derived components.

[0105] Example 2 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1. Example 3 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 20 N / mm 2 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1.

[0106] Example 4 A decorative sheet having the same properties as in Example 1 was obtained in the same manner as in Example 1, except that the restoration power of the adhesive resin layer in the decorative sheet of Example 1 was 50%. Example 5 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 A decorative sheet having the same properties as in Example 1 was obtained in the same manner as in Example 1, except that the restoration power was 60%.

[0107] Example 6 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 20 N / mm 2 A decorative sheet having the same properties as in Example 1 was obtained in the same manner as in Example 1, except that the restoration power was 75%. Example 7 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer was 5 mass%.

[0108] Example 8 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 A decorative sheet having the same properties as in Example 1 was obtained in the same manner as in Example 1, except that the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer was 10 mass%. Example 9 In the decorative sheet of Example 1, the density of the colored substrate layer is 0.92 g / cm 3 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1.

[0109] Example 10 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 , the density of the colored substrate layer is 1 g / cm3 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1. Example 11 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 20 N / mm 2 , the density of the colored substrate layer is 1.16 g / cm 3 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1.

[0110] Example 12 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer was 5 mass%. Example 13 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 A decorative sheet having the same properties as in Example 1 was obtained using the same procedures as in Example 1, except that the content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer was 10 mass %.

[0111] Example 14 In the decorative sheet of Example 1, the density of the transparent resin layer is 0.92 g / cm 3 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1. (Example 15) In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 , the density of the transparent resin layer is 0.95 g / cm 3 A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1.

[0112] Example 16 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 20 N / mm 2 , the density of the transparent resin layer is 0.99 g / cm 3A decorative sheet having the same properties as in Example 1 except for the above was obtained in the same manner as in Example 1. Example 17 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the design layer was a resin layer containing a colorant and a biourethane (meth)acrylate containing plant-derived components.

[0113] Example 18 In the decorative sheet of Example 1, the restoration power of the adhesive resin layer is 50%, the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer is 5 mass%, and the density of the colored substrate layer is 0.95 g / cm 3 The content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer is 5 mass %, and the density of the transparent resin layer is 0.92 g / cm 3 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the design layer was a resin layer containing a colorant and a biourethane (meth)acrylate containing plant-derived components. Example 19 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 10 N / mm 2 , the recovery power of the adhesive resin layer is 60%, the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer is 10 mass%, and the density of the colored substrate layer is 1 g / cm 3 The content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer is 10 mass %, and the density of the transparent resin layer is 0.95 g / cm 3 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the design layer was a resin layer containing a colorant and a biourethane (meth)acrylate containing plant-derived components.

[0114] Example 20 In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 20 N / mm 2, the recovery power of the adhesive resin layer is 75%, the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer is 15 mass%, and the density of the colored substrate layer is 1.16 g / cm 3 The content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer is 15 mass %, and the density of the transparent resin layer is 0.99 g / cm 3 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the design layer was a resin layer containing a colorant and a biourethane (meth)acrylate containing plant-derived components.

[0115] (Comparative Example 1) In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 2 N / mm 2 , the recovery power of the adhesive resin layer is 60%, the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer is 10 mass%, and the density of the colored substrate layer is 1 g / cm 3 The content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer is 10 mass %, and the density of the transparent resin layer is 0.95 g / cm 3 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the design layer was a resin layer containing a colorant and a biourethane (meth)acrylate containing plant-derived components.

[0116] (Comparative Example 2) In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 25 N / mm 2 , the recovery power of the adhesive resin layer is 80%, the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer is 10 mass%, and the density of the colored substrate layer is 1 g / cm 3 The content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer is 10 mass %, and the density of the transparent resin layer is 0.95 g / cm 3 A decorative sheet having the same properties as in Example 1 was obtained using the same procedure as in Example 1, except that the design layer was a resin layer containing a colorant and a biourethane (meth)acrylate containing plant-derived components.

[0117] (Comparative Example 3) In the decorative sheet of Example 1, the Martens hardness of the adhesive resin layer was 25 N / mm 2 , the recovery power of the adhesive resin layer is 60%, the content of plant-derived ethylene in the colored substrate layer relative to the entire colored substrate layer is 10 mass%, and the density of the colored substrate layer is 1 g / cm 3 The content of plant-derived ethylene in the transparent resin layer relative to the entire transparent resin layer is 10 mass %, and the density of the transparent resin layer is 0.95 g / cm 3 A decorative sheet having the same properties as in Example 1 was obtained in the same manner as in Example 1, except that the design layer was a resin layer containing a colorant and urethane acrylate that did not contain plant-derived components.

[0118] (evaluation) The decorative sheets of Examples 1 to 20 and the decorative sheets of Comparative Examples 1 to 3 were each evaluated for "environmental friendliness," "adhesion improvement," surface strength, and impact resistance. The evaluation methods used were as follows. The evaluation results are shown in Table 1.

[0119] <Environmental friendliness> The dependency on fossil fuels in creating decorative sheets was evaluated relatively. Dependence was assessed based on the amount of fossil fuel-derived materials used. The greater the amount used, the higher the dependency, and the less the amount used, the lower the dependency. Evaluation criteria Highly addictive: × Moderately addictive: Yes Low dependency: ◎

[0120] <Improved adhesion> After preparing the decorative sheets of each example and comparative example, the samples were stored at room temperature for 24 hours, and the T-peel strength between the transparent resin layer, adhesive resin layer, and colored substrate layer was measured (sample width: 25 mm, pulling speed: 50 mm / min). Evaluation criteria ◎: The substrate breaks without forming a peeling interface ○: Deformation occurs in the base layer and peeling occurs △: No deformation in the base layer and peeling surface ×: Peeling occurred during sample handling, making measurement impossible Here, a rating of ⊚ or ◯ was considered a pass. <Surface strength> The surface strength was evaluated by a pencil hardness test. The decorative sheets of each example and comparative example were subjected to a test for scratch hardness (pencil method) in accordance with JIS K5600-5-4. A pencil was slid across each decorative sheet with a load applied, and the formation of dents (scratches) in the surface protective layer was observed to evaluate whether the decorative sheet had sufficient scratch resistance or poor scratch resistance. Evaluation criteria ⊚: Damage occurred on the surface after the pencil hardness test was carried out using a pencil with a hardness of 2B or more. ◯: Damage occurred on the surface after the pencil hardness test was repeated using a pencil with a hardness of 3B or 4B. ×: Damage occurred on the surface after a pencil hardness test was conducted using a pencil with a hardness of 5B or less. In this example, "◯" was considered to be acceptable.

[0121] <Impact resistance> A DuPont impact test was carried out in accordance with JIS K5600-5-3. Specifically, a DuPont impact tester was used to drop a 500g weight from a height of 50cm onto the surface protective layer side of the decorative sheets of Examples 1 to 23 and Comparative Examples 1 to 3. (This was carried out at 500g-30cm, 500g-50cm, and 1000g-50cm with the back surface attached to plywood.) The decorative sheet was deformed by dropping a weight, and the sheet cracks and the depth of the dents were observed. Evaluation criteria ◎: No cracks, and the performance is the same as or better than the current product in terms of dents. ○: There are some cracks, but they are the same as the current product specifications. There are no problems with production. △: There are cracks and dents, and it is slightly inferior to the current product, but there is no problem in production. ×: Both cracks and dents are at a level that makes production and use difficult. This is an NG evaluation product.

[0122] [Table 1] As shown in Table 1, the colored substrate layer and the transparent resin layer were formed using a resin composition containing a biomass-derived polyethylene resin, and the Martens hardness HM in the cross-sectional direction of the adhesive resin layer was 5 N / mm 2 More than 20N / mm 2 It was confirmed that good adhesion performance could be obtained by adjusting the thickness within the following ranges. It was also confirmed that good results could be obtained with respect to surface strength and impact resistance.

[0123] The present invention can have the following configurations, for example. (1) a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer laminated in this order; the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin, The adhesive resin layer has a Martens hardness HM of 5 N / mm in the cross-sectional direction. 2 More than 20N / mm 2 A decorative sheet characterized by being within the following range.

[0124] (2) The decorative sheet according to (1) above, wherein the adhesive resin layer has a recovery power ηIT in the range of 50% to 75% in an indentation test using a Martens hardness tester. (3) a pattern layer is provided between the colored thermoplastic resin layer and the adhesive resin layer, each of the colored thermoplastic resin layer and the transparent thermoplastic resin layer is a resin layer formed of a resin composition containing: plant-derived polyethylene obtained by polymerizing a monomer containing plant-derived ethylene; fossil fuel-derived ethylene; and fossil fuel-derived polyethylene obtained by polymerizing a monomer containing at least one of fossil fuel-derived ethylene and an α-olefin; The colored thermoplastic resin layer contains the plant-derived ethylene in an amount of 5% by mass or more based on the entire colored thermoplastic resin layer, and the amount of the plant-derived ethylene is 0.92 g / cm 3 More than 1.16g / cm3 having a density within the following range: The transparent thermoplastic resin layer contains the plant-derived ethylene in an amount of 5% by mass or more based on the entire transparent thermoplastic resin layer, and the amount of the plant-derived ethylene is 0.92 g / cm 3 More than 0.99g / cm 3 having a density within the following range: the design layer is a resin layer containing a colorant and a biourethane (meth)acrylate, the biourethane (meth)acrylate being a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate; The decorative sheet according to (1) or (2) above, wherein at least one component of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a plant-derived component.

[0125] (4) The decorative sheet according to (3) above, wherein the polyol is a polyester polyol containing a plant-derived component, a polyether polyol containing a plant-derived component, or a polycarbonate polyol containing a plant-derived component. (5) The decorative sheet according to (4) above, characterized in that the polyester polyol is a reaction product of a polyfunctional alcohol containing a plant-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional carboxylic acid containing a plant-derived component.

[0126] (6) The decorative sheet according to (4) above, characterized in that the polyether polyol is a reaction product of a polyfunctional alcohol containing a plant-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional isocyanate containing a plant-derived component.

[0127] (7) The decorative sheet according to (4) above, characterized in that the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a plant-derived component and a carbonate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a plant-derived component.

[0128] (8) The decorative sheet according to any one of (3) to (7) above, wherein the isocyanate compound is an isocyanate compound containing a plant-derived component. (9) A decorative sheet according to any one of (1) to (8) above, characterized in that it comprises a primer layer laminated on the surface of the colored thermoplastic resin layer opposite to the adhesive resin layer.

[0129] (10) A substrate; The decorative sheet according to any one of (1) to (9) above, laminated on at least one surface of the substrate; A decorative material comprising: [Explanation of symbols]

[0130] 1 decorative sheet 2 Colored base material layer (colored thermoplastic resin layer) 3. Picture layer 4 Adhesive resin layer 5 Transparent resin layer (transparent thermoplastic resin layer) 6 Surface protective layer 7 Uneven part 8 Primer layer 9 Base material 10 Cosmetic materials

Claims

1. a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer laminated in this order; the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each formed using a resin composition containing a plant-derived polyolefin resin, The adhesive resin layer has a Martens hardness HM of 5 N / mm in the cross-sectional direction. ２ 20N / mm or more ２ A decorative sheet characterized by being within the following range.

2. 2. The decorative sheet according to claim 1, wherein the adhesive resin layer has a recovery power ηIT in the range of 50% to 75% in an indentation test using a Martens hardness tester.

3. a pattern layer is provided between the colored thermoplastic resin layer and the adhesive resin layer, each of the colored thermoplastic resin layer and the transparent thermoplastic resin layer is a resin layer formed of a resin composition containing: plant-derived polyethylene obtained by polymerizing a monomer containing plant-derived ethylene; fossil fuel-derived ethylene; and fossil fuel-derived polyethylene obtained by polymerizing a monomer containing at least one of fossil fuel-derived ethylene and an α-olefin; The colored thermoplastic resin layer contains 5% by mass or more of the plant-derived ethylene relative to the entire colored thermoplastic resin layer, and has a density of 0.92 g / cm ３ 1.16g / cm or more ３ having a density within the following range: The transparent thermoplastic resin layer contains 5% by mass or more of the plant-derived ethylene relative to the entire transparent thermoplastic resin layer, and has a density of 0.92 g / cm ３ 0.99g / cm or more ３ having a density within the following range: the design layer is a resin layer containing a colorant and a biourethane (meth)acrylate, the biourethane (meth)acrylate being a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate; 3. The decorative sheet according to claim 1, wherein at least one component of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a plant-derived component.

4. 4. The decorative sheet according to claim 3, wherein the polyol is a polyester polyol containing a plant-derived component, a polyether polyol containing a plant-derived component, or a polycarbonate polyol containing a plant-derived component.

5. The decorative sheet according to claim 4, characterized in that the polyester polyol is a reaction product of a polyfunctional alcohol containing a plant-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional carboxylic acid containing a plant-derived component.

6. The decorative sheet according to claim 4, characterized in that the polyether polyol is a reaction product of a polyfunctional alcohol containing a plant-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional isocyanate containing a plant-derived component.

7. The decorative sheet according to claim 4, wherein the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a plant-derived component and a carbonate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a plant-derived component.

8. 4. The decorative sheet according to claim 3, wherein the isocyanate compound is an isocyanate compound containing a plant-derived component.

9. 3. The decorative sheet according to claim 1, further comprising a primer layer laminated on the surface of the colored thermoplastic resin layer opposite to the adhesive resin layer.

10. A substrate; The decorative sheet according to claim 1 or 2 laminated on at least one surface of the substrate; A decorative material comprising:

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