Decorative sheets and decorative materials

Abstract

To provide a decorative sheet and a decorative material which reduce a used amount of fossil fuel by using a plant-derived material, and can maintain physical property suitable for application as the decorative sheet.SOLUTION: A decorative sheet 1 includes a colored base material layer 2, a pattern layer 3, an adhesive resin layer 4, a transparent resin layer 5, and a surface protective layer 6 in this order, where the colored base material layer 2 and the transparent resin layer 5 are each a resin layer formed of a resin composition containing biomass-derived polyolefin polymerized with a monomer containing biomass-derived olefin, the transparent resin layer 5 contains 5 mass% or more of the biomass-derived olefin, and has density of 0.92 g / cm3 or more and 0.99 g / cm3 or less, the colored base material layer 2 contains 5 mass% or more of the biomass-derived olefin, and has density of 0.92 g / cm3 or more and 1.12 g / cm3 or less, the pattern layer 3 contains a coloring agent and a biomass-derived component, and the surface protective layer 6 contains a biomass-derived component.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to decorative sheets and decorative materials. [Background technology]

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

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-188941 [Overview of the initiative] [Problems that the invention aims to solve]

[0004] In recent years, due to environmental concerns, there has been a demand to reduce carbon dioxide emissions and contribute to an environmentally friendly and sustainable society by replacing the materials used in decorative sheets from conventional petroleum-derived materials to plant-derived materials. However, when using biomass polyethylene as a plant-derived material that can be used in decorative sheets, there has been a challenge in maintaining the physical properties suitable for use in decorative sheets.

[0005] In view of the above-mentioned problems, the present invention aims to provide a decorative sheet and decorative material that can reduce the amount of fossil fuels used by using plant-derived materials, while maintaining physical properties suitable for use as a decorative sheet. [Means for solving the problem]

[0006] To solve the above problems, one aspect of the present invention comprises, in this order, a colored thermoplastic resin layer, a pattern layer, an adhesive resin layer, a transparent thermoplastic resin layer, and a surface protective layer, wherein the colored thermoplastic resin layer and the transparent thermoplastic resin layer are resin layers formed from a resin composition containing a biomass-derived polyolefin obtained by polymerizing monomers containing biomass-derived olefins, and the transparent thermoplastic resin layer contains 5% by mass or more of the biomass-derived olefin, at a concentration of 0.92 g / cm³. 3 More than 0.99g / cm 3 The density is within the following range, and the colored thermoplastic resin layer contains 5% by mass or more of the biomass-derived olefin, with a density of 0.92 g / cm³. 3 More than 1.12g / cm 3 The decorative sheet has a density within the following range, the pattern layer contains a coloring agent and a biomass-derived component, and the surface protective layer contains a biomass-derived component.

[0007] Furthermore, in order to solve the above problems, another aspect of the present invention is a decorative material comprising a base material and a decorative sheet laminated on at least one surface of the base material. [Effects of the Invention]

[0008] According to one aspect of the present invention, it is possible to provide decorative sheets and decorative materials that reduce the amount of fossil fuels used by using plant-derived materials, while maintaining physical properties suitable for use as decorative sheets. [Brief explanation of the drawing]

[0009] [Figure 1] This is a cross-sectional view showing the configuration of the decorative sheet and decorative material in an embodiment of the present invention. [Modes for carrying out the invention]

[0010] Hereinafter, embodiments of the present technology will be described with reference to the drawings. In the description of the drawings, the same or similar parts are denoted by the same or similar reference numerals, and duplicate explanations are omitted. Each drawing is schematic and may differ from the actual one. The embodiments shown below exemplify apparatuses and methods for embodying the technical idea of the present technology, and the technical idea of the present technology is not limited to the apparatuses and methods exemplified in the following embodiments. The technical idea of the present technology can be variously modified within the technical scope described in the claims. Also, the directions of "left and right" and "up and down" in the following description are merely definitions for convenience of explanation and do not limit the technical idea of the present invention. Therefore, for example, if the paper surface is rotated 90 degrees, "left and right" and "up and down" are read in exchange, and if the paper surface is rotated 180 degrees, it is a matter of course that "left" becomes "right" and "right" becomes "left".

[0011] Hereinafter, the configuration of the cosmetic material 10 will be described with reference to FIG. 1. As shown in FIG. 1, the cosmetic material 10 includes a cosmetic sheet 1 and a base material 9. The specific configuration of the cosmetic sheet 1 will be described later. The base material 9 is formed in a plate shape using, for example, wood boards, inorganic boards, metal plates, etc., and the cosmetic sheet 1 is laminated on one surface (the upper surface in FIG. 1). That is, the cosmetic material 10 includes the base material 9 and the cosmetic sheet 1 laminated on one surface of the base material 9.

[0012] (Configuration of the cosmetic sheet) As shown in FIG. 1, the cosmetic sheet 1 includes a colored base material 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 protection layer 6, an uneven portion 7, and a primer layer 8.

[0013] <Colored base material layer> The colored base material layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed of a resin composition containing biomass-derived (plant-derived) polyethylene. Hereinafter, the composition of the colored base material layer 2 will be described in detail. (Biomass-derived polyethylene) In this embodiment, biomass-derived polyethylene is obtained by polymerizing monomers containing biomass-derived ethylene. The biomass-derived ethylene is not particularly limited, and ethylene produced by conventionally known methods can be used. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyethylene is biomass-derived. Furthermore, the raw material monomer for polyethylene does not necessarily have to contain 100% by mass of biomass-derived ethylene.

[0014] The monomers used as raw materials for biomass-derived polyethylene may further include at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, or may further include α-olefins derived from biomass.

[0015] The above-mentioned α-olefin is not particularly limited in terms of the number of carbon atoms, but typically those with 3 to 20 carbon atoms can be used, and butylene, hexene, or octene are preferred. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a biomass-derived raw material. Furthermore, by including such an α-olefin, the polymerized polyethylene has alkyl groups as branched structures, making it more flexible than simple linear polyethylene.

[0016] By using ethylene, a biomass-derived raw material, it is theoretically possible to manufacture the product using 100% biomass-derived components.

[0017] The biomass-derived ethylene concentration in the polyethylene mentioned above (hereinafter sometimes referred to as "biomass content") is a value measured by radiocarbon (C14) measurement of the carbon content derived from biomass. Since atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14, it is known that the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in the total carbon atoms in polyethylene, the proportion of carbon derived from biomass can be calculated. In this embodiment, the C14 content in polyethylene is P C14 In that case, the carbon content P from biomass bio This can be calculated as follows: P bio (%)=P C14 / 105.5×100

[0018] In this embodiment, theoretically, if all ethylene derived from biomass is used as the raw material for polyethylene, the concentration of biomass-derived ethylene will be 100%, and the biomass degree of biomass-derived polyethylene will be 100. Furthermore, the concentration of biomass-derived ethylene in fossil fuel-derived polyethylene produced solely from fossil fuel-derived raw materials will be 0%, and the biomass degree of fossil fuel-derived polyethylene will be 0.

[0019] In this embodiment, the biomass-derived polyethylene and the decorative sheet composed of that polyethylene do not need to have a biomass content of 100%.

[0020] In this embodiment, the polymerization method for monomers containing biomass-derived ethylene is not particularly limited and can be carried out by conventionally known methods. The polymerization temperature and polymerization pressure should be adjusted as appropriate depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited and can be conventionally known apparatus. An example of a polymerization method for monomers containing ethylene is described below.

[0021] The polymerization method for ethylene polymers and copolymers of ethylene and α-olefins can be appropriately selected depending on the type of polyethylene to be polymerized, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE), depending on differences in density and branching. 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 or more stages using one of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, or high-pressure ionic polymerization.

[0022] Furthermore, as the biomass-derived polyethylene, ethylene polymers or copolymers of ethylene and α-olefins may be used individually or in combination of two or more types.

[0023] (Resin composition containing biomass-derived polyethylene) In this embodiment, the resin composition mainly contains the above-mentioned polyethylene. The resin composition contains biomass-derived ethylene at a concentration of 5% by mass or more, preferably 5 to 95% by mass, and more preferably 25 to 75% by mass, relative to the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral decorative sheet can be realized.

[0024] The above resin composition may contain two or more types of polyethylene with different biomass concentrations, and the concentration of biomass-derived ethylene in the resin composition as a whole should be within the above range.

[0025] The above resin composition may further contain fossil fuel-derived polyethylene, which is obtained by polymerizing ethylene derived from fossil fuels with monomers containing at least one of fossil fuel-derived ethylene and α-olefin. In other words, in this embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited and can be mixed by conventionally known methods. For example, it may be a dry blend or a melt blend.

[0026] According to this embodiment, the resin composition preferably contains 5 to 90% by mass, more preferably 25 to 75% by mass, of biomass-derived polyethylene and preferably 10 to 95% by mass, more preferably 25 to 75% by mass, of fossil fuel-derived polyethylene. Even when using such a mixed resin composition, the concentration of biomass-derived ethylene in the resin composition as a whole only needs to be within the above range.

[0027] In the resin composition manufactured in the above manufacturing process, various additives may be added to the resin composition in addition to the main component polyethylene, to the extent that its properties are not impaired. Examples of additives include plasticizers, UV stabilizers, color inhibitors, matting agents, deodorizers, flame retardants, weather-resistant agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, and coloring pigments. These additives are added to the entire resin composition in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass.

[0028] As described above, the colored base material layer 2 contains biomass-derived ethylene at a concentration 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, relative to the entire colored base material layer 2. If the concentration of biomass-derived ethylene in the colored base material layer 2 is 5% by mass or more, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral decorative sheet can be realized.

[0029] The colored substrate layer 2 contains 0.92 to 1.12 g / cm³.3 Preferably, it has a density of 0.98 to 1.10 g / cm 3 The density of the colored base material layer 2 is a value measured according to the method specified in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. If the density of the colored base material layer 2 is 0.92 g / cm 3 or more, the rigidity of the colored base material layer 2 can be increased. Also, if the density of the colored base material layer 2 is 1.12 g / cm 3 or less, the transparency and mechanical strength of the colored base material layer 2 can be increased.

[0030] The colored base material layer 2 may be any of those containing biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as biomass-derived polyethylene, those containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene, and those containing biomass-derived low-density polyethylene in fossil fuel-derived high-density polyethylene. The biomass content of the entire colored base material layer 2 may be within the range of 10% or more and 90% or less. Note that biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. Also, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less. The colored base material layer 2 is preferably a blend of biomass-derived high-density polyethylene and low-density polyethylene (which may be either biomass-derived or fossil fuel-derived) within the range of 95:5 to 70:30 as biomass-derived polyethylene. If the content of low-density polyethylene is too low, the film-forming stability is poor, and if the content of low-density polyethylene is too high, there is a problem that it becomes too soft.

[0031] The manufacturing method of the colored base material layer 2 is not particularly limited and can be manufactured by a conventionally known method. In this embodiment, it is preferably formed by calendering.

[0032] Furthermore, 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, friction reducers, light scattering agents, and gloss adjusters. The thickness of the colored base material 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 base material layer 2, which is made of biomass-derived polyethylene, is 40 μm or more, it is possible to absorb unevenness and steps in the underlying flooring material, etc., and improve the finish of the decorative sheet 1. Also, when the thickness of the colored base material layer 2 is 200 μm or less, it is possible to reduce the manufacturing cost of the decorative sheet 1 by not forming the colored base material layer 2 to be unnecessarily thick.

[0033] In this embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the colored base material layer 2, but the present invention is not limited thereto. 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 range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the colored base material layer 2.

[0034] <Pattern layer> The pattern layer 3 is laminated on one side of the colored substrate layer 2 (the upper side in Figure 1) and is a layer for adding a pattern to enhance the design. Furthermore, the pattern layer 3 is formed using printing ink or paint. The printing ink or paint that forms the pattern layer 3 is formed, for example, by dissolving or dispersing a coloring agent such as a dye or pigment together with a suitable binder resin in a suitable diluent solvent.

[0035] The printing ink or coating that forms the pattern layer 3 is applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.

[0036] The pattern layer 3 is formed by including the above-mentioned coloring agent and binder resin. The binder resin used in the pattern layer 3 in this embodiment will be described below.

[0037] [Binder resin] The binder resin contained in the pattern layer 3 includes a urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy(meth)acrylate. Furthermore, in the pattern layer 3, at least one component of the polyol, isocyanate compound, or hydroxy(meth)acrylate constituting the urethane(meth)acrylate described above contains a biomass-derived component. At least one of the polyol, isocyanate compound, or hydroxy(meth)acrylate may or may not contain a biomass-derived component. In the following description, urethane(meth)acrylate containing a biomass-derived component will also be referred to as biourethane(meth)acrylate. In other words, pattern layer 3 is a resin layer containing the aforementioned coloring agent and biourethane (meth)acrylate. That is, pattern layer 3 contains a coloring agent and biomass-derived components.

[0038] Urethane (meth)acrylates are obtained, for example, by the reaction of polyols and isocyanates with hydroxy(meth)acrylate. In biourethane (meth)acrylates, plant-derived polyols can be used as the polyol, plant-derived isocyanates can be used as the isocyanate, or both the polyol and isocyanate can be plant-derived.

[0039] As polyols, polyester polyols, which are reaction products of polyfunctional alcohols and polyfunctional carboxylic acids, polyether polyols, which are reaction products of polyfunctional alcohols and polyfunctional isocyanates, or polycarbonate polyols, which are reaction products of polyfunctional alcohols and carbonates can be used. Each polyol will be described below.

[0040] <Polyester Polyol> When a polyester polyol contains biomass-derived components, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains biomass-derived components. Examples of polyester polyols containing biomass-derived components are listed below. • Reaction product of a biomass-derived polyfunctional alcohol and a biomass-derived polyfunctional carboxylic acid • Reaction product of polyfunctional alcohol derived from fossil fuels and polyfunctional carboxylic acid derived from biomass • Reaction product of polyfunctional alcohol derived from biomass and polyfunctional carboxylic acid derived from fossil fuels

[0041] As biomass-derived polyfunctional alcohols, aliphatic polyfunctional alcohols obtained from plant raw materials such as corn, sugarcane, cassava, and sago palm can be used. 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 raw materials by the methods described below. These may be used individually or in combination.

[0042] Biomass-derived polypropylene glycol is produced by a fermentation method that breaks down plant materials to obtain glucose, via glycerol to 3-hydroxypropyl aldehyde (HPA). Compared to polypropylene glycol produced by the fermentation method described above, polypropylene glycol produced by bio-methods such as fermentation is preferable in terms of safety, yields useful by-products such as lactic acid, and can also be produced at a lower cost. Biomass-derived butylene glycol can be produced by manufacturing glycol from plant materials, obtaining succinic acid through fermentation, and then hydrogenating it. Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by conventional methods via ethylene.

[0043] As the polyfunctional alcohol derived from fossil fuels, compounds having two or more, preferably two to eight, hydroxyl groups in one molecule can be used. Specifically, the polyfunctional alcohol derived from fossil fuels is not particularly limited and conventionally known compounds can be used. For example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), 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, acrylic polyol, etc. can be used. These may be used individually or in combination of two or more.

[0044] As biomass-derived polyfunctional carboxylic acids, aliphatic polyfunctional carboxylic acids obtained from plant raw materials such as renewable plant-derived oils like soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and recycled oils mainly composed of these, such as waste cooking oil, can be used. 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 as a by-product of heptyl alcohol by alkaline thermal decomposition of ricinoleic acid obtained from castor oil. 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.

[0045] As polyfunctional carboxylic acids derived from fossil fuels, aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used. The aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used, such as adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, and dimer acid, as well as their ester compounds. Furthermore, the aromatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used, such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, as well as their ester compounds. These can be used individually or in combination of two or more.

[0046] <Polyether polyol> When a polyether polyol contains biomass-derived components, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains biomass-derived components. Examples of polyether polyols containing biomass-derived components are listed below. Reaction of biomass-derived polyfunctional alcohols with biomass-derived polyfunctional isocyanates thing • Reaction product of polyfunctional alcohol derived from fossil fuels and polyfunctional isocyanate derived from biomass • Reaction product of polyfunctional alcohol derived from biomass and polyfunctional isocyanate derived from fossil fuels

[0047] As the polyfunctional alcohols derived from biomass and fossil fuels, the polyfunctional alcohols derived from biomass and fossil fuels described above in relation to polyester polyols can be used.

[0048] As a biomass-derived polyfunctional isocyanate, one can be obtained by acid amidating a plant-derived divalent carboxylic acid, reducing it to a terminal amino group, and then reacting it with phosgene to convert the amino group to an isocyanate group. A biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. 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 to isocyanate groups. For example, lysine diisocyanate (LDI) is obtained by methyl esterifying the carboxyl group of lysine and then converting the amino group to an isocyanate group. Also, 1,5-pentamethylene diisocyanate is obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

[0049] Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate. More specifically, the phosgenation method involves directly reacting 1,5-pentamethylenediamine or a salt thereof with phosgene, or suspending the hydrochloride salt of pentamethylenediamine in an inert solvent and reacting it with phosgene to synthesize 1,5-pentamethylenediisocyanate. The carbamate method involves first carbamating 1,5-pentamethylenediamine or a salt thereof to produce pentamethylenedicarbamate (PDC), which is then thermally decomposed to synthesize 1,5-pentamethylenediisocyanate. In the present invention, a suitable polyisocyanate is the 1,5-pentamethylenediisocyanate-based polyisocyanate (trade name: Stavio®) manufactured by Mitsui Chemicals, Inc.

[0050] The polyfunctional isocyanates derived from fossil fuels are not particularly limited and conventionally known ones can be used, for example, aromatic diisocyanates such as toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylenediisocyanate, 4-isopropyl-1,3-phenylenediisocyanate, 4-chlor-1,3-phenylenediisocyanate, 4-butoxy-1,3-phenylenediisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis(phenylene isocyanate) (MDI), juliene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl. 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 individually or in combination of two or more.

[0051] <Polycarbonate polyol> When a polycarbonate polyol contains biomass-derived components, the polycarbonate polyol can be a reaction product of a polyfunctional alcohol containing biomass-derived components and a carbonate derived from fossil fuels. Alternatively, a reaction product of a polyfunctional alcohol containing fossil fuel-derived components and a carbonate containing biomass-derived components can be used. Examples of carbonates include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate. These can be used individually or in combination of two or more.

[0052] As the biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described above in the section on polyester polyols can be used.

[0053] <Isocyanate compounds> Next, isocyanate compounds will be described. As isocyanate compounds containing biomass-derived components, the biomass-derived polyfunctional isocyanates described in the section on polyether polyols can be used.

[0054] <Hydroxy(meth)acrylate> Next, we will explain hydroxy(meth)acrylates. 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 individually or in combination of two or more types.

[0055] Furthermore, the binder resin of the pattern layer 3 may be formed by including nitrocellulose in addition to the biourethane (meth)acrylate described above. In other words, the pattern layer 3 may contain the biourethane (meth)acrylate described above, or it may contain nitrocellulose in addition to the biourethane (meth)acrylate.

[0056] <Nitrocellulose> Nitrocellulose is a cellulosic resin that is a nitro-substituted product in which some of the hydroxyl groups in the cellulose skeleton are esterified with nitrate. The cellulose skeleton of nitrocellulose resin is a biomass material. While general 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.

[0057] Nitrocellulose comes in two types, L-type and H-type, depending on its molecular weight. From the perspective of solubility in organic solvents, it is preferable to use the L-type.

[0058] The pattern layer 3 preferably has a biomass content of 5% or more, more preferably 5% to 50%, and even more preferably 10% to 50%. If the biomass content is within the above range, the amount of fossil fuels used can be reduced, thereby reducing the environmental burden. The dried weight of the pattern layer 3 is preferably 0.1 g / m². 2 More than 15g / m 2 More preferably 3 g / m 2 More than 10g / m 2 More preferably 6 g / m 2 More than 9g / m 2 The following applies: The pattern layer 3 preferably has a thickness of 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm, and even more preferably 0.7 μm to 3 μm. Multiple pattern layers 3 having such weights and thicknesses may be provided. Regarding "biomass content," for example, in the case of biourethane (meth)acrylate, as mentioned above, it is determined by measuring the amount of biomass-derived carbon content using radiocarbon (C14) measurement.

[0059] Furthermore, regarding "biomass content," for example, in the case of nitrocellulose, since there are 3 hydroxyl groups per glucose unit (formula weight = 172) that make up the cellulose skeleton, which is the starting material, 1 to 3 of these hydroxyl groups can be nitrate-esterified (hydrogen is replaced by a nitro group (non-biomass material, formula weight = 46)). If the original cellulose skeleton consists of 100% biomass material by weight, and the average number of substituted nitro groups per glucose unit is n, then the proportion (by weight) of biomass material in the entire nitrocellulose molecule can be calculated as (172-n) × 100 / (172-n + 46n). The proportion of biomass material in the entire nitrocellulose molecule is approximately 78.8% by weight when one nitro group is substituted per glucose unit that makes up the cellulose backbone, approximately 64.9% by weight when two nitro groups are substituted, and approximately 55.0% by weight when three nitro groups are substituted (calculated using the above formula).

[0060] Furthermore, when the thickness of the pattern layer 3 is 10 μm or less, the printability when manufacturing the decorative sheet 1 is improved, and manufacturing costs can be reduced. Furthermore, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the pattern layer 3 to impart various functions.

[0061] Any pattern can be used for the pattern layer 3, such as wood grain, stone pattern, fabric pattern, abstract pattern, geometric pattern, letters, symbols, solid color, or a combination thereof. In addition, to improve the opacity of the decorative sheet 1, an opaque layer may be provided between the pattern layer 3 and the colored base material layer 2. The opaque 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. Furthermore, the pattern layer 3 may have a configuration that includes, for example, a solid-colored base material layer to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer for adding a design to enhance aesthetic appeal.

[0062] <Adhesive resin layer> The adhesive resin layer 4 is laminated on one side of the pattern layer 3 (the upper side in Figure 1) and is used to bond the pattern layer 3 to the transparent resin layer 5. As the material for the adhesive resin layer 4, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin-based, etc., can be used. Polyolefin-based resins are particularly preferred due to their adhesion to the transparent resin layer 5.

[0063] <Transparent resin layer> The transparent resin layer 5 is laminated on one side of the adhesive resin layer 4 (the upper side in Figure 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, which is polymerized from monomers containing biomass-derived ethylene, as described above. In other words, the transparent resin layer 5 may use the same biomass-derived polyethylene-containing resin composition used in the colored substrate layer 2. It may also contain fossil fuel-derived ethylene and fossil fuel-derived polyethylene, which is polymerized from monomers containing at least one of fossil fuel-derived ethylene and α-olefin.

[0064] The transparent resin layer 5 may contain 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, of the biomass-derived ethylene mentioned above, relative to 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, the amount of fossil fuels used can be reduced compared to conventional methods, and a carbon-neutral decorative sheet can be realized.

[0065] The density of the transparent resin layer 5 is 0.92-0.99 g / cm³. 3 Preferably 0.94-0.98 g / cm³ 3 , more preferably 0.95~0.97 g / cm³ 3It has a density of 0.92 g / cm³. The density of the transparent resin layer 5 is the value measured according to the method specified in Method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. 3 If the above is achieved, the rigidity of the transparent resin layer 5 can be increased. Also, if the density of the transparent resin layer 5 is 0.99 g / cm³ 3 The transparency and mechanical strength of the transparent resin layer 5 can be improved if the following conditions are met.

[0066] 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.

[0067] The transparent resin layer 5 may contain biomass-derived high-density polyethylene as biomass-derived polyethylene. Furthermore, the transparent resin layer 5 may also contain polyethylene, as biomass-derived polyethylene, which is a blend of biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. Furthermore, the transparent resin layer 5 may have a biomass content of 10% to 90% of the entire transparent resin layer 5.

[0068] The method for manufacturing the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In this embodiment, it is preferable to form it by extrusion molding, and it is more preferable that the extrusion molding is carried out by the T-die method or the inflation method.

[0069] 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 (ethylene concentration derived from biomass).

[0070] In this 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 for the transparent resin layer 5 to function, and productivity is required for the colored substrate layer 2 to function. Furthermore, the ratio of the density d1 of the transparent resin layer 5 to the density d2 of the colored base material layer 2 (d2 / d1) is preferably within the range of 1.1 to 1.5, more preferably within the range of 1.1 to 1.3, and even more preferably within the range of 1.1 to 1.2. By having the density ratio of the transparent resin layer to the colored base material layer within this range, even when biomass-derived polyethylene is used, the material can have the necessary extrusion suitability and bending suitability as a decorative sheet.

[0071] In this 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 t1 ≥ t2. This is because the transparent resin layer 5 requires a certain thickness to function, while the colored substrate layer 2 does not need to be as thick as the transparent resin layer 5 to function. Furthermore, 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 within the range of 1.1 to 3, more preferably within the range of 1.1 to 2, and even more preferably within the range of 1.1 to 1.5.

[0072] In this embodiment, it is preferable that the biomass-derived ethylene concentration C1 in the transparent resin layer 5 and the biomass-derived ethylene concentration C2 in the colored substrate layer 2 satisfy the condition C1 > C2. This is because, since the transparent resin layer 5 is thick and requires a large amount of ethylene to function, increasing the biomass content of the transparent resin layer 5 can further reduce the amount of fossil fuels used.

[0073] The biomass-derived polyethylene forming the transparent resin layer 5 may have a nucleating agent (for example, "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd.) added to it. The nucleating agent is preferably added to polyethylene in an amount of 500 ppm to 2000 ppm based on the mass of polyethylene, and more preferably in an amount of 1500 ppm to 2000 ppm based on the mass of polyethylene.

[0074] The transparent resin layer 5 may contain, if necessary, one or more additives selected from various sources such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, friction reducers, light scattering agents, and gloss adjusters. Furthermore, it is preferable that the transparent resin layer 5 has a degree of transparency (colorless, colored, or semi-transparent) that allows the pattern of the pattern layer 3 to be seen through to the surface (top surface) of the decorative sheet 1.

[0075] In this embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited thereto. 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 range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the transparent resin layer 5.

[0076] <Surface protective layer> The surface protection layer 6 is laminated on one side of the transparent resin layer 5 (the upper side in Figure 1) and is provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1.

[0077] The surface protection layer 6 can be formed using the same material as the binder resin of the pattern layer 3. Therefore, the structure of the surface protection layer 6 is the same as that of the pattern layer 3, except that it does not contain a coloring agent. The surface protective layer 6 is formed of a urethane (meth)acrylate, i.e., biourethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy(meth)acrylate. Furthermore, in the surface protective layer 6, at least one of the polyol, isocyanate compound, or hydroxy(meth)acrylate components that make up the urethane (meth)acrylate contains a biomass-derived component. In other words, the surface protective layer 6 contains a biomass-derived component.

[0078] Furthermore, the surface protection layer 6 may be formed by adding nitrocellulose in addition to the biourethane (meth)acrylate described above, similar to the binder resin of the pattern layer 3. In other words, the surface protection layer 6 may be formed with the biourethane (meth)acrylate described above, or it may be formed by adding nitrocellulose to the biourethane (meth)acrylate.

[0079] The surface protective layer 6 preferably has a biomass content of 5% or more, more preferably 5% to 50%, and even more preferably 10% to 50%. If the biomass content is within the above range, the amount of fossil fuels used can be reduced, thereby reducing the environmental burden. The dried weight of the surface protective layer 6 is preferably 0.1 g / m². 2 More than 15g / m 2 More preferably 3 g / m 2 More than 10g / m 2 More preferably 6 g / m 2 More than 9g / m 2 The following applies: The surface protective layer 6 preferably has a thickness of 0.1 μm to 10 μm, more preferably 3 μm to 10 μm, and even more preferably 6 μm to 9 μm.

[0080] Furthermore, the surface protective layer 6 may contain various additives as needed, such as weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, UV absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters. In addition, the surface protective layer 6 may contain functional additives as needed, such as antibacterial agents and antifungal agents.

[0081] <Uneven part> The uneven portion 7 is formed by recesses provided in multiple locations on the transparent resin layer 5 and the surface protective layer 6.

[0082] <Primer layer> The primer layer 8 is a base layer that improves the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9. Furthermore, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (the lower side in Figure 1). Furthermore, the primer layer 8 is formed using, for example, a polyester resin, an organic additive, a pigment, etc. Furthermore, the primer layer 8 may contain rust-preventive pigments to improve corrosion resistance. The thickness of the primer layer 8 is, for example, within the range of 1 μm to 10 μm.

[0083] The embodiments described above are merely examples of the present invention, and the present invention is not limited to the embodiments described above. Various modifications can be made to forms other than those described above, as long as they do not depart from the technical spirit of the present invention, depending on the design and other factors.

[0084] (Effects of this embodiment) The decorative sheet 1 of this embodiment can achieve the following effects. (1) The colored base layer 2 and the transparent resin layer 5 are resin layers formed from a resin composition containing biomass-derived polyolefins, which are polymerized monomers containing biomass-derived olefins. The transparent resin layer 5 contains 5% by mass or more of biomass-derived olefins, at a concentration of 0.92 g / cm³. 3 More than 0.99g / cm3 The density is within the following range, and the colored substrate layer 2 contains 5% by mass or more of biomass-derived olefin, with a density of 0.92 g / cm³. 3 More than 1.12g / cm 3 The density is within the following range, the pattern layer 3 contains a coloring agent and biomass-derived components, and the surface protective layer 6 contains biomass-derived components. This makes it possible to provide decorative sheets that reduce the use of fossil fuels by using plant-derived materials, while maintaining physical properties suitable for use as decorative sheets.

[0085] (2) The pattern layer 3 is a resin layer containing urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy(meth)acrylate, and the surface protective layer 6 is a resin layer formed of the urethane (meth)acrylate, and at least one of the polyol, isocyanate compound, and hydroxy(meth)acrylate contained in the urethane (meth)acrylate contains a biomass-derived component. This makes it possible to provide a decorative sheet that reliably reduces the amount of fossil fuels used by utilizing plant-derived materials, while reliably maintaining physical properties suitable for use as a decorative sheet.

[0086] (3) The polyols that are components of the biourethane (meth)acrylate contained in the pattern layer 3 and the surface protective layer 6 are polyester polyols containing biomass-derived components, polyether polyols containing biomass-derived components, or polycarbonate polyols containing biomass-derived components. This makes it possible to provide decorative sheets that more reliably reduce the use of fossil fuels by using plant-derived materials, while more reliably maintaining physical properties suitable for use as decorative sheets.

[0087] (4) Among the polyols that are components of the biourethane (meth)acrylate described above, the polyester polyol is a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional carboxylic acid containing fossil fuel-derived components, or a reaction product of a polyfunctional alcohol containing fossil fuel-derived components and a polyfunctional carboxylic acid containing biomass-derived components. This makes it possible to provide decorative sheets that further reduce the amount of fossil fuels used by utilizing plant-derived materials, while also more reliably maintaining physical properties suitable for use as decorative sheets.

[0088] (5) Among the polyols that are components of the biourethane (meth)acrylate described above, the polyether polyol is a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional isocyanate containing fossil fuel-derived components, or a reaction product of a polyfunctional alcohol containing fossil fuel-derived components and a polyfunctional isocyanate containing biomass-derived components. This makes it possible to provide decorative sheets that further reduce the amount of fossil fuels used by utilizing plant-derived materials, while also more reliably maintaining physical properties suitable for use as decorative sheets.

[0089] (6) Among the polyols that are components of the biourethane (meth)acrylate described above, polycarbonate polyols are reaction products of a polyfunctional alcohol containing biomass-derived components and a carbonate containing fossil fuel-derived components, or reaction products of a polyfunctional alcohol containing fossil fuel-derived components and a carbonate containing biomass-derived components. This makes it possible to provide decorative sheets that further reduce the amount of fossil fuels used by utilizing plant-derived materials, while also more reliably maintaining physical properties suitable for use as decorative sheets.

[0090] (7) The isocyanate compounds that are components of the biourethane (meth)acrylate contained in the pattern layer 3 and the surface protective layer 6 are isocyanate compounds that contain biomass-derived components. This makes it possible to provide decorative sheets that further reduce the amount of fossil fuels used by utilizing plant-derived materials, while also more reliably maintaining physical properties suitable for use as decorative sheets.

[0091] (8) The device comprises a base material 9 and a decorative sheet 1 laminated on at least one surface of the base material 9. This makes it possible to provide a decorative material that reduces the use of fossil fuels by using plant-derived materials, while maintaining physical properties suitable for use as a decorative sheet.

[0092] <Variation> (1) In this embodiment, the decorative material 10 is configured to include a decorative sheet 1 laminated on one side of the base material 9, but it is not limited to this. That is, the decorative material 10 may be configured to include a decorative sheet 1 laminated on the other side of the base material 9 (the lower side in Figure 1) in addition to the one side of the base material 9.

[0093] [Examples] Referring to this embodiment, the decorative materials of Examples 1 to 16 and the decorative materials of Reference Examples 1 to 3 will be described below.

[0094] (Example 1) After corona discharge treatment was applied to one side of the substrate, a pattern layer, a urethane adhesive layer, a maleic anhydride-modified polyethylene resin layer (transparent adhesive resin layer), a transparent resin layer, and a surface protection layer mainly composed of an acrylic resin composition were laminated on that side in this order. Furthermore, after corona discharge treatment was applied to the other side of the substrate, a primer layer (thickness: 1-2 μm) made of polyester urethane resin was formed. In this way, the decorative sheet of Example 1 (total thickness: 135 μm) was obtained. In Example 1, a colored substrate layer (thickness: 55 μm) was used as the base material, formed from a resin composition containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene. The colored substrate layer was obtained by calendering this resin composition. The biomass content of the thus formed colored substrate layer was 80%, and the density of the colored substrate layer was 1.08 g / cm³.3 That is the case. The transparent resin layer used was a transparent resin layer (thickness: 80 μm) formed from a resin composition containing biomass-derived polyethylene ("Biomass Polyethylene" manufactured by Braschem). This biomass-derived polyethylene is a resin blended from biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) in a ratio (high-density polyethylene / low-density polyethylene) of 80 / 20. The transparent resin layer was obtained by laminating this resin. The biomass content of the transparent resin layer thus formed was 94%, and the density of the transparent resin layer was 0.95 g / cm³. 3 That is the case. For the binder resin of the pattern layer, biourethane (meth)acrylate was used, which is a reaction product of a polyester polyol containing biomass-derived components, an isocyanate compound derived from fossil fuels, and a hydroxy(meth)acrylate derived from fossil fuels. As the polyester polyol containing biomass-derived components, a polyester polyol was used, which is a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional carboxylic acid derived from fossil fuels. Furthermore, the surface protective layer was formed using the same biourethane (meth)acrylate as the binder resin for the pattern layer.

[0095] (Example 2) The decorative sheet of Example 2 was obtained in the same manner as in Example 1, except that the polyester polyol used in the biourethane (meth)acrylate forming the surface protective layer was a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional carboxylic acid containing a biomass-derived component.

[0096] (Example 3) The decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that the biourethane (meth)acrylate used to form the surface protective layer was a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing biomass-derived components, and a fossil fuel-derived hydroxy(meth)acrylate.

[0097] (Example 4) The decorative sheet of Example 4 was obtained in the same manner as in Example 1, except that a polyether polyol was used as the polyol in the biourethane (meth)acrylate that forms the surface protective layer. Specifically, a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional isocyanate derived from fossil fuels was used as the polyether polyol.

[0098] (Example 5) The decorative sheet of Example 5 was obtained in the same manner as in Example 4, except that the polyether polyol in the biourethane (meth)acrylate forming the surface protective layer was a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional isocyanate containing a biomass-derived component.

[0099] (Example 6) The decorative sheet of Example 6 was obtained in the same manner as in Example 3, except that a polyether polyol derived from fossil fuels was used as the polyol in the biourethane (meth)acrylate that forms the surface protective layer.

[0100] (Example 7) The decorative sheet of Example 7 was obtained in the same manner as in Example 1, except that a polycarbonate polyol was used as the polyol in the biourethane (meth)acrylate that forms the surface protective layer. Specifically, a reaction product of a polyfunctional alcohol containing biomass-derived components and a carbonate derived from fossil fuels was used as the polycarbonate polyol.

[0101] (Example 8) The decorative sheet of Example 8 was obtained in the same manner as in Example 3, except that a polycarbonate polyol derived from fossil fuels was used as the polyol in the biourethane (meth)acrylate that forms the surface protective layer.

[0102] (Example 9) The decorative sheet of Example 9 was obtained in the same manner as in Example 1, except that the polyester polyol used in the biourethane (meth)acrylate binder resin of the pattern layer was a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional carboxylic acid containing a biomass-derived component.

[0103] (Example 10) A decorative sheet of Example 10 was obtained in the same manner as in Example 1, except that the biourethane (meth)acrylate used as the binder resin for the pattern layer was a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing biomass-derived components, and a fossil fuel-derived hydroxy(meth)acrylate.

[0104] (Example 11) A decorative sheet of Example 11 was obtained in the same manner as in Example 1, except that a polyether polyol was used as the polyol in the biourethane (meth)acrylate binder resin of the pattern layer. Specifically, a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional isocyanate derived from fossil fuels was used as the polyether polyol.

[0105] (Example 12) The decorative sheet of Example 12 was obtained in the same manner as in Example 11, except that the polyether polyol used in the biourethane (meth)acrylate binder resin of the pattern layer was a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional isocyanate containing a biomass-derived component.

[0106] (Example 13) The decorative sheet of Example 13 was obtained in the same manner as in Example 10, except that a polyether polyol derived from fossil fuels was used as the polyol in the biourethane (meth)acrylate, which is the binder resin of the pattern layer.

[0107] (Example 14) A decorative sheet of Example 14 was obtained in the same manner as in Example 1, except that a polycarbonate polyol was used as the polyol in the biourethane (meth)acrylate binder resin of the pattern layer. Specifically, a reaction product of a polyfunctional alcohol containing biomass-derived components and a carbonate derived from fossil fuels was used as the polycarbonate polyol.

[0108] (Example 15) The decorative sheet of Example 15 was obtained in the same manner as in Example 10, except that a polycarbonate polyol derived from fossil fuels was used as the polyol in the biourethane (meth)acrylate binder resin of the pattern layer.

[0109] (Example 16) A decorative sheet of Example 16 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by blending biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) in a ratio (high-density polyethylene / low-density polyethylene) of 100 / 0, and then laminating the resulting resin.

[0110] (Reference example 1) A decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1, except that the pattern layer was formed from a urethane-based printing ink and the surface protective layer was formed from an acrylic resin-based UV-curing resin.

[0111] (Reference example 2) A decorative sheet for Reference Example 2 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by laminating only homopolypropylene resin derived from fossil fuels manufactured by Prime Polymer Co., Ltd.

[0112] (Reference example 3) A decorative sheet for Reference Example 3 was obtained in the same manner as in Example 1, except that a colored substrate layer was obtained using only colored polyethylene resin derived from fossil fuels.

[0113] (Performance evaluation, evaluation results) The decorative sheets of Examples 1 to 16 and the decorative sheets of Reference Examples 1 to 3 were evaluated for "haze (%) of the transparent resin layer," "pencil hardness," "Hoffmann scratch test," "extrusion suitability," and "bending whitening," respectively. The evaluation methods used were as described below.

[0114] <Haze of the transparent resin layer (%)> The haze (%) of the transparent resin layer was measured using a UV-Vis-Near-Infrared spectrophotometer (Manufacturer: Shimadzu Corporation, Model: UV-3600). Resin films were obtained by extruding a resin with the same composition as the transparent resin layer in each example and reference example to a thickness of 70 μm to 80 μm. The haze at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere) and evaluated. A haze of less than 15% was evaluated as "◎", a haze between 15% and 25% was evaluated as "○", and a haze of 25% or more was evaluated as "×". In this example, "◎" and "○" were considered passing grades.

[0115] <Pencil hardness> Pencil hardness was measured using an automatic pencil hardness tester (manufacturer: Yoshimitsu Seiki, model number: C221A). For each example and reference example, a pencil hardness test was conducted on the decorative material, including the decorative sheet, using pencils of different hardness levels. After the test, damage (gouging) that occurred on the surface (surface protective layer) was checked, and the surface hardness was evaluated. When damage occurred on the surface after conducting the pencil hardness test using a pencil with a hardness of 2B or higher, it was evaluated as "◎". When damage occurred on the surface after conducting the pencil hardness test using a pencil with a hardness of 4B or higher, it was evaluated as "○". In addition, when damage occurred on the surface after conducting the pencil hardness test using a pencil with a hardness of 5B or lower, it was evaluated as "×". In this example, "◎" and "○" were considered passing grades.

[0116] <Hoffmann scratch test> The Hoffmann scratch test was performed by setting a scratch blade (a cylindrical blade with a diameter of Φ7) so that it was in contact with the surface of the decorative sheet at a 45-degree angle, and then moving the testing machine over the decorative sheet. The load (weight) was gradually increased (in 200g increments) within the range of 200g to 2000g, and the sample surface was scratched. The load at which scratches occurred (g) was evaluated. If scratches occurred at a load of 800g, "600g" was recorded as the load capacity in the table. In this example, a load capacity of "200g" was deemed unacceptable.

[0117] <Extrusion suitability> The transparent resin layer was extruded and its suitability for production (extrusion suitability) was confirmed. As a result, if the product could be manufactured (molded) without any problems, it was marked with a "○" (pass). On the other hand, if there was a possibility of defects, it was marked with a "△" (fail).

[0118] <Whitening due to folding> We used a decorative sheet (i.e., decorative material) laminated onto MDF to check its suitability for V-cut processing (presence or absence of whitening when bent). As a result, those that did not show any whitening were marked with "○" (pass), those that showed some whitening were marked with "△" (pass), and those that showed any whitening were marked with "×" (fail).

[0119] [Table 1]

[0120] Using the method described above, various performance tests were evaluated, and the decorative sheets of Examples 1 to 16 showed excellent performance equivalent to or better than Reference Examples 1-3 in all evaluation tests. In other words, it was found that the decorative sheets of Examples 1 to 16 can reduce the amount of fossil fuels used by using plant-derived materials while maintaining physical properties suitable for use as decorative sheets. [Explanation of symbols]

[0121] 1…Decorative sheet, 2…Colored base layer, 3…Pattern layer, 4…Adhesive resin layer, 5…Transparent resin layer, 6…Surface protection layer, 7…Rubber part, 8…Primer layer, 9…Base material, 10…Decorative material

Claims

1. The material comprises, in this order, a colored thermoplastic resin layer, a pattern layer, an adhesive resin layer, a transparent thermoplastic resin layer, and a surface protective layer. The colored thermoplastic resin layer and the transparent thermoplastic resin layer are each resin layers formed from a resin composition containing a biomass-derived polyolefin obtained by polymerizing monomers containing biomass-derived olefins. The transparent thermoplastic resin layer contains 5% by mass or more of the biomass-derived olefin, at a concentration of 0.92 g / cm³. ３ 0.99g / cm or more ３ Having a density within the following range: The colored thermoplastic resin layer contains 5% by mass or more of the biomass-derived olefin, at a concentration of 0.92 g / cm³. ３ 1.12g / cm or more ３ Having a density within the following range: The aforementioned pattern layer contains a coloring agent and a binder resin, and its weight after drying is 0.1 g / m². ２ 15g / m or more ２ The following: The binder resin is a resin composition comprising at least a polyol, an isocyanate compound, and hydroxy(meth)acrylate, and includes urethane (meth)acrylate and nitrocellulose. The surface protective layer is a resin layer formed of urethane (meth)acrylate and nitrocellulose. A decorative sheet characterized in that at least one component of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a biomass-derived component.

2. The decorative sheet according to claim 1, characterized in that the polyol is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a polycarbonate polyol containing a biomass-derived component.

3. The decorative sheet according to claim 2, characterized in that the polyester polyol is a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional carboxylic acid containing fossil fuel-derived components, or a reaction product of a polyfunctional alcohol containing fossil fuel-derived components and a polyfunctional carboxylic acid containing biomass-derived components.

4. The aforementioned polyether polyol is a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional isocyanate containing fossil fuel-derived components, or a reaction product of a polyfunctional alcohol containing fossil fuel-derived components and a polyfunctional isocyanate containing biomass-derived components. The decorative sheet according to claim 2, characterized in that it is the same.

5. The decorative sheet according to claim 2, characterized in that the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing biomass-derived components and a carbonate containing fossil fuel-derived components, or a reaction product of a polyfunctional alcohol containing fossil fuel-derived components and a carbonate containing biomass-derived components.

6. The decorative sheet according to any one of claims 1 to 5, characterized in that the isocyanate compound is an isocyanate compound containing a biomass-derived component.

7. Substrate and A decorative material comprising a decorative sheet according to any one of claims 1 to 6, which is laminated on at least one surface of the base material.

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