Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material that reduce petroleum dependence of the material and can maintain or enhance properties appropriate for application as a decorative sheet even when molded from a plant-derived material.SOLUTION: In a decorative sheet 1 of the present embodiment, at least a colored base material layer 2, an adhesive resin layer 4, and a transparent resin layer 5 are laminated sequentially, the colored base material layer 2 being a resin layer formed from a resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin. The tensile modulus of the colored base material layer 2 in both the MD direction, which represents the flow direction of the sheet, and the TD direction, perpendicular to the MD direction, falls within 700 MPa or more to 1000 MPa or less, and the tensile breaking strength of the colored base material layer 2 in both the MD and TD directions falls within 30 MPa or more to 100 MPa or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure 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, 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] Conventional decorative sheets have often been made from materials derived from fossil fuels (petroleum), but in recent years, environmental issues have led to an increased focus on biomass plastics as an alternative. Therefore, it is desirable to reduce the amount of fossil fuel used by using biomass-derived raw materials (plant-derived materials), thereby reducing dependence on petroleum and conserving petroleum resources, thereby reducing carbon dioxide emissions and contributing to an environmentally friendly and sustainable society. On the other hand, decorative sheets are required to have good physical properties such as impact resistance and scratch resistance as part of their environmental friendliness, regardless of their use (exterior use, interior use, etc.). However, decorative sheets made from plant-derived materials may have reduced physical properties compared to conventional decorative sheets made from petroleum-derived materials. For this reason, when plant-derived materials are used in decorative sheets, there is a problem in that it is difficult to maintain the above physical properties, and even to improve them compared to conventional decorative sheets.

[0005] In view of the above-mentioned problems, the present disclosure aims to provide a decorative sheet and decorative material that reduces the dependency on petroleum in the materials and that can maintain or improve physical properties suitable for use as a decorative sheet even when formed using plant-derived materials. [Means for solving the problem]

[0006] In order to solve the above problems, a decorative sheet according to one embodiment of the present disclosure comprises at least a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer laminated in this order, the colored thermoplastic resin layer being a resin layer formed using a resin composition containing a biomass-derived polyolefin formed by polymerizing a monomer containing a biomass-derived olefin, the tensile modulus of the colored thermoplastic resin layer in both the MD direction indicating the flow direction of the sheet and the TD direction perpendicular to the MD direction being within the range of 700 MPa or more and 1000 MPa or less, and the tensile break strength of the colored thermoplastic resin layer in both the MD direction and the TD direction being within the range of 30 MPa or more and 100 MPa or less.

[0007] In order to solve the above-mentioned problems, a decorative material according to another aspect of the present disclosure includes a substrate and the decorative sheet bonded to at least one surface of the substrate. [Effects of the Invention]

[0008] According to one aspect of the present disclosure, dependency on petroleum in materials can be reduced, and even when formed using plant-derived materials, physical properties suitable for use as decorative sheets can be maintained or improved. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view showing the configuration of a decorative sheet and a decorative material according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In the drawings, identical or similar parts are designated by identical or similar reference numerals, and redundant description will be omitted. Each drawing is a schematic diagram and may differ from the actual product. The embodiments described below exemplify devices and methods for embodying the technical ideas of the present disclosure, and the technical ideas of the present disclosure are not limited to the devices and methods exemplified in the following embodiments. The technical ideas of the present disclosure can be modified in various ways within the technical scope described in the claims. Furthermore, the directions of "left and right" and "up and down" in the following description are merely defined for the convenience of explanation and do not limit the technical ideas of the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and of course, if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left."

[0011] The configuration of the decorative material 10 will be described below with reference to FIG. As shown in FIG. 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 side (the upper side in FIG. 1 ). That is, the decorative material 10 comprises the base material 9 and the decorative sheet 1 laminated on one side of the base material 9. The decorative sheet 1 may also be laminated on the other side of the base material 9. That is, in the decorative material 10, the decorative sheet 1 needs to be laminated on at least one side of the base material 9.

[0012] (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. The decorative sheet 1 according to this embodiment may have a configuration in which at least a colored substrate layer 2, an adhesive resin layer 4, and a transparent resin layer 5 are laminated in this order. A design layer 3 is preferably provided between the colored substrate layer 2 and the adhesive resin layer 4. A surface protective layer 6 is more preferably provided on the transparent resin layer 5.

[0013] As will be described in more detail below, the colored substrate layer 2 is a resin layer formed using a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin. Furthermore, in the decorative sheet 1, the tensile modulus of the colored substrate layer 2 in both the MD direction indicating the flow direction of the sheet and the TD direction perpendicular to the MD direction is within the range of 700 MPa or more and 1000 MPa or more, and the tensile breaking strength of the colored substrate layer 2 in both the MD direction and the TD direction is within the range of 30 MPa or more and 100 MPa or less. By having the tensile modulus and tensile breaking strength of the colored substrate layer 2 within the above ranges, the decorative sheet 1 according to this embodiment can reduce dependency on petroleum for its materials, conserve petroleum resources, and contribute to a sustainable society. Furthermore, by limiting the tensile modulus and tensile breaking strength of the colored substrate layer 2 to the above ranges, durability-related physical properties such as impact resistance and surface strength (scratch resistance) can be maintained or improved.

[0014] <Colored base material layer> The colored substrate layer 2 is a resin layer formed using a thermoplastic resin. More specifically, in this embodiment, the colored substrate layer 2 is a resin layer formed using a resin composition containing a biomass-derived (plant-derived) resin material. In this embodiment, the colored substrate layer 2 contains, as the main material of the resin composition, a biomass-derived polyolefin formed by polymerizing a monomer containing a biomass-derived olefin. For example, the colored substrate layer 2 in the decorative sheet 1 according to this embodiment is a colored resin layer formed from a resin composition containing biomass-derived polyethylene as the biomass-derived resin material. The composition of the colored substrate layer 2 will be described in detail below. (Biomass-derived polyethylene) In this embodiment, the biomass-derived polyethylene is obtained 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.

[0015] 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.

[0016] 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.

[0017] 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 ratio") is a value obtained by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement. Carbon dioxide in the atmosphere contains a certain proportion (105.5 pMC) of C14, and it is known that the C14 content in plants that grow by absorbing carbon dioxide from the atmosphere, such as corn, is also about 105.5 pMC. It is also known that fossil fuels contain almost no C14. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of C14 contained in the total carbon atoms in the polyethylene. In this embodiment, the biomass-derived carbon content P when the C14 content in the polyethylene is PC14 is bio can be calculated as follows: P bio (%)=P C14 / 105.5×100

[0019] 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.

[0020] In this embodiment, the biomass-derived polyethylene or the decorative sheet comprising this polyethylene does not necessarily have a biomass degree of 100.

[0021] 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, such as differences in density and branching, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). 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 that forms the colored substrate layer 2, i.e., the colored substrate layer 2, contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5% by mass or more but less than 99% by mass, and more preferably 25% by mass or more but less than 75% by mass, based on the entire resin composition (entire colored substrate layer 2). If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, it is possible to more reliably reduce the amount of fossil fuel used compared to when conventional fossil fuels are used, and a carbon-neutral decorative sheet can be achieved.

[0025] 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.

[0026] The resin composition may further contain 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. That is, in this embodiment, the resin composition forming the colored substrate layer 2 may be a mixture of a biomass-derived polyolefin (e.g., polyethylene) and a fossil fuel-derived polyolefin (e.g., 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.

[0027] According to this embodiment, the resin composition forming the colored substrate layer 2, i.e., the colored substrate layer 2, contains 5% by mass or more, preferably 5 to 90% by mass, and more preferably 25 to 75% by mass of biomass-derived polyethylene when a mixture with fossil fuel-derived polyethylene is used. The resin composition may contain a mixture of biomass-derived polyethylene and, for example, fossil fuel-derived polyethylene. Even when a resin composition of such a mixture is used, it is sufficient that the concentration of biomass-derived ethylene in the resin composition as a whole is 5% by mass or more, preferably 5 to 90% by mass, and more preferably 25 to 75% by mass.

[0028] As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5% by mass or more but less than 99% 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 0.90 g / cm 3 More than 1.50g / cm 3 It is preferable that the density of the porous film is 0.98 to 1.10 g / cm. 3The 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. 3 If the density of the colored substrate layer 2 is 1.50 g / cm or more, the rigidity of the colored substrate layer 2 can be increased. 3 If it is below this, the transparency and mechanical strength of the colored substrate layer 2 can be improved.

[0030] The colored substrate layer 2 may be any of those containing biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, those containing biomass-derived high-density polyethylene and fossil fuel-derived polyethylene, and those containing fossil fuel-derived high-density polyethylene and biomass-derived low-density polyethylene, and the biomass content of the entire colored substrate layer 2 may be within the range of 5% to 90%. Biomass-derived high-density polyethylene refers to polyethylene with a density exceeding 0.94, while biomass-derived low-density polyethylene refers to polyethylene with a density of 0.94 or less. 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.

[0031] 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.

[0032] Furthermore, the colored substrate layer 2 may contain, as needed, 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 thickness of the colored substrate layer 2 is preferably within the range of 10 μm or more and 150 μm or less. This is because, when the thickness of the colored substrate layer 2 is 10 μm or more, it is possible to absorb unevenness and steps in the underlying substrate, etc., thereby improving the application finish of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 150 μm or less, it is possible to reduce the manufacturing cost of the decorative sheet 1 by not forming the colored substrate layer 2 thicker than necessary.

[0033] In this embodiment, biomass-derived polyethylene has been described as the biomass-derived resin constituting the colored substrate layer 2, but the present disclosure 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, or these materials may be used in addition to biomass-derived polyethylene. 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.

[0034] <Pattern 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. As shown in FIG. 1, the pattern layer 3 is provided between the colored substrate layer 2 and the adhesive resin layer 4. Note that the pattern layer 3 can be omitted if the coloring of the colored substrate layer 2 can serve as a substitute. 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. 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 a colorant and a binder resin. The binder resin contained in the design layer 3 will be described below.

[0035] [Binder resin] The binder resin contained in the design layer 3 includes urethane (meth)acrylate. The urethane (meth)acrylate is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate. In addition, in the design layer 3, at least one of the polyol, isocyanate compound, hydroxy(meth)acrylate, polyol, isocyanate compound, and hydroxy(meth)acrylate that constitute the urethane(meth)acrylate preferably contains a plant-derived component. In the following description, a urethane(meth)acrylate containing a plant-derived component may be referred to as a biourethane(meth)acrylate.

[0036] Urethane (meth)acrylates can be obtained, for example, by reacting a polyol, an isocyanate, and a hydroxy (meth)acrylate. In biourethane (meth)acrylates, plant-derived polyols and plant-derived isocyanates can be used, or both the polyol and the isocyanate can be plant-derived.

[0037] The plant-derived polyol is any one of polyester polyol containing a plant-derived component, polyether polyol containing a plant-derived component, and polycarbonate polyol containing a plant-derived component. The polyester polyol containing plant-derived components is a reaction product of a functional alcohol and a polyfunctional carboxylic acid. The polyether polyol containing plant-derived components is a reaction product of a functional alcohol and a polyfunctional isocyanate. The polycarbonate polyol containing plant-derived components is a reaction product of a functional alcohol and a carbonate. Each polyol will be described below.

[0038] <Polyester polyol> When the polyester polyol contains a plant-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains a plant-derived component. Examples of polyester polyols containing a plant-derived component are as follows. Reaction products of polyfunctional alcohols containing plant-derived ingredients with polyfunctional carboxylic acids containing plant-derived ingredients Reaction products of polyfunctional alcohols containing fossil fuel-derived components with polyfunctional carboxylic acids containing plant-derived components Reaction products of polyfunctional alcohols containing plant-derived components with polyfunctional carboxylic acids containing fossil fuel-derived components

[0039] As the plant-derived polyfunctional alcohol, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugarcane, cassava, and sago palm can be used. Examples of plant-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 of two or more.

[0040] Plant-derived polypropylene glycol is produced by a fermentation method in which glucose is obtained by decomposing plant materials, via 3-hydroxypropylaldehyde (HPA) from glycerol. Compared to polypropylene glycol produced by the EO method, biomethods such as fermentation methods in which glucose is obtained by decomposing plant materials are preferable in terms of safety, as useful by-products such as lactic acid are obtained, and production costs can be kept low. Plant-derived butylene glycol can be produced by producing glycol from plant raw materials, fermenting the glycol to obtain succinic acid, and then hydrogenating the succinic acid. Plant-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

[0041] As the fossil fuel-derived polyfunctional alcohol, a compound having two or more, preferably two to eight, hydroxyl groups per molecule can be used. Specifically, the fossil fuel-derived polyfunctional alcohol is not particularly limited and conventionally known substances can be used. For example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, 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 alone or in combination of two or more.

[0042] Plant-derived polyfunctional carboxylic acids can be 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 ingredient. Examples of plant-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 disclosure, plant-derived succinic acid or plant-derived sebacic acid is particularly preferred. These may be used alone or in combination of two or more.

[0043] 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 of the conventionally known compounds, 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 of the conventionally known compounds, such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, and ester compounds thereof. These compounds may be used alone or in combination of two or more.

[0044] <Polyether polyol> When the polyether polyol contains a plant-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains a plant-derived component. Examples of polyether polyols containing a plant-derived component are as follows. Reaction products of polyfunctional alcohols containing plant-derived ingredients with polyfunctional isocyanates containing plant-derived ingredients Reaction products of polyfunctional alcohols containing fossil fuel-derived components with polyfunctional isocyanates containing plant-derived components Reaction products of polyfunctional alcohols containing plant-derived ingredients with polyfunctional isocyanates containing fossil fuel-derived ingredients As the plant-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the plant-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described above in connection with the polyester polyol can be used.

[0045] Plant-derived polyfunctional isocyanates can be obtained by converting plant-derived dicarboxylic acids into terminal amino groups through acid amidation and reduction, and then reacting with phosgene to convert the amino groups into isocyanate groups. Examples of plant-derived polyfunctional isocyanates include plant-derived diisocyanates. Examples of plant-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.

[0046] 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 disclosure is 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

[0047] The fossil fuel-derived polyfunctional isocyanate is not particularly limited, and conventionally known substances can be used, such as aromatic diisocyanates such as 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, 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 alone or in combination of two or more.

[0048] <Polycarbonate polyol> When the polycarbonate polyol contains a plant-derived component, the polycarbonate polyol can be 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. Examples of carbonates include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, diphenyl carbonate, etc. These may be used alone or in combination of two or more. As the plant-derived polyfunctional alcohol, the plant-derived polyfunctional alcohols explained above in connection with the polyester polyol can be used.

[0049] <Isocyanate compounds> The isocyanate compound is an isocyanate compound containing a plant-derived component. As the isocyanate compound containing a plant-derived component, it is possible to use the plant-derived polyfunctional isocyanate described in the polyether polyol.

[0050] <Hydroxy(meth)acrylate> Next, the hydroxy(meth)acrylate 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. 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.

[0051] <Nitrocellulose> Nitrocellulose is a nitro-substituted cellulose-based 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. Nitrocellulose is classified into L type and H type depending on the molecular weight. In terms of solubility in organic solvents, it is preferable to use L type.

[0052] When the design layer 3 contains a biomass-derived material, the biomass content is preferably 5% or more, more preferably 5% to 50%, and even more preferably 10% to 50%. If the biomass content is within the above range, it is possible to reduce the amount of fossil fuel used and reduce the environmental impact. The weight of the pattern layer 3 after drying is preferably 0.1 g / m 2 More than 15g / m 2 within the range of 3 g / m 2 More than 10g / m 2 within the range of 6 g / m 2 More than 9g / m 2 It is within the following range: 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 plant-derived carbon by radiocarbon (C14) measurement.

[0053] Regarding "biomass content," for example, in the case of nitrocellulose, the starting material, there are three hydroxyl groups per glucose unit (formula weight = 172) that makes up the cellulose skeleton. Therefore, one to three of the hydroxyl groups can be converted to nitrate esters (hydrogen is replaced by a nitro group (non-biomass material, formula weight = 46)). If the original cellulose skeleton is 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). The proportion of biomass material in the entire nitrocellulose molecule is approximately 78.8% by weight when substituted with an average of one nitro group per glucose unit that makes up the cellulose backbone, approximately 64.9% by weight when substituted with two nitro groups, and approximately 55.0% by weight when substituted with three nitro groups (calculated using the formula above).

[0054] 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. Furthermore, in order to improve the hiding power of the decorative sheet 1, a hiding layer may be provided between the design layer 3 and the colored substrate layer 2. The hiding layer is formed, for example, using an opaque printing ink or paint that contains a large amount of opaque pigments such as titanium dioxide or iron oxide. 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.

[0055] The thickness of the design layer 3 is set within the range of 1 μm to 10 μm, preferably within the range of 0.1 μm to 10 μm, more preferably within the range of 0.5 μm to 5 μm, and even more preferably within the range of 0.7 μm to 3 μm. This is because when the thickness of the design layer 3 is 1 μm or more, it is possible to make the printing clear. Also, when the thickness of the design layer 3 is 10 μm or less, it is possible to improve the printing workability when producing the decorative sheet 1 and to reduce production costs. It should be noted that the decorative sheet 1 may be provided with a plurality of pattern layers 3 .

[0056] 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. In addition, the pattern layer 3 may be configured to have, for example, a solid colored thermoplastic resin 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.

[0057] <Adhesive resin layer> The adhesive resin layer 4 is laminated on one surface of the design layer 3 (the upper surface in FIG. 1), and is a layer used to bond the design layer 3 to the transparent resin layer 5. The method for joining the transparent resin layer 5 to the colored substrate layer 2 on which the design layer 3 is printed is not particularly limited, and for example, various lamination methods such as thermal lamination, extrusion lamination, dry lamination, and sand lamination via the adhesive resin layer 4 can be used as necessary. The adhesive resin layer 4 may be made of, for example, a urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, or polyolefin-based material.

[0058] The lamination method for the adhesive resin layer 4 is primarily extrusion lamination, as described above, but other methods (e.g., dry lamination) may also be used, and a dry lamination adhesive may be used as the material for the adhesive resin layer 4. For example, a two-component curing urethane adhesive containing a base agent containing a polyol component and a curing agent containing an isocyanate component, and using an isocyanate-based curing agent, may be used. Specifically, the base agent containing a polyol component may be, for example, polyester polyol or polyether polyol, and the curing agent containing an isocyanate component may be any one of tolylene diisocyanate, diphenylmethane diisocyanate, xylylene isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.

[0059] When the adhesive for dry lamination of the adhesive resin layer 4 is used, the coating amount is 3 g / m 2 More than 10g / m 2 The weight should be less than 3g / m 2 If the coating amount is less than 10 g / m, the interlayer strength may not be sufficient and adhesion may be poor. 2 If the amount is more than this, the adhesive resin layer 4 becomes thick, which may cause peeling within the adhesive resin layer and result in poor adhesion.

[0060] <Transparent resin layer> The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1 ) of the adhesive resin layer 4 and is a resin layer formed using a thermoplastic resin. More specifically, in this embodiment, the transparent resin layer 5 may be a resin layer formed using a resin composition containing at least one of a fossil fuel-derived resin material and a biomass-derived (plant-derived) resin material. In this embodiment, the transparent resin layer 5 may contain, as the main material of the resin composition, at least one of a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing a fossil fuel-derived olefin, or a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin.

[0061] That is, in this embodiment, the transparent resin layer 5 may be a resin layer whose resin composition contains only fossil fuel-derived polyolefin, only biomass-derived polyolefin, or both fossil fuel-derived polyolefin and biomass-derived polyolefin. Even when the transparent resin layer 5 is a resin layer containing only fossil fuel-derived polyolefin, the decorative sheet 1 has a colored substrate layer 2 formed from biomass-derived polyolefin, so that it is possible to reduce dependency on petroleum in the materials and conserve petroleum resources compared to conventional decorative sheets made from fossil fuel-derived materials.

[0062] The resin composition forming the transparent resin layer 5 in the decorative sheet 1 according to this embodiment may contain, as a biomass-derived resin material, for example, a biomass-derived polyethylene equivalent to that of the colored substrate layer 2, or may contain biomass-derived polypropylene. The resin composition forming the transparent resin layer 5 may contain, for example, fossil fuel-derived polyethylene as the fossil fuel-derived resin material, or may contain biomass-derived polyethylene as the biomass-derived resin material. Furthermore, the resin composition forming the transparent resin layer 5 may contain, for example, fossil fuel-derived polypropylene as the fossil fuel-derived resin material, or biomass-derived polypropylene as the biomass-derived resin material.

[0063] (Biomass-derived polypropylene) Hereinafter, biomass-derived polypropylene will be described. In this embodiment, the biomass-derived polypropylene is obtained by polymerizing a monomer containing biomass-derived propylene. The biomass-derived propylene is not particularly limited, and propylene produced by a conventionally known method can be used. Since biomass-derived propylene is used as the raw material monomer, the polymerized polypropylene is biomass-derived. By using propylene, a raw material derived from biomass, it is theoretically possible to produce polypropylene from 100% biomass-derived components. The monomers that are the raw material for biomass-derived polypropylene may further include fossil fuel-derived propylene.

[0064] The biomass-derived propylene concentration in the polypropylene (hereinafter sometimes referred to as "biomass degree") is a value obtained by measuring the content of biomass-derived carbon by the radiocarbon (C14) measurement. The percentage of biomass-derived carbon can be calculated by measuring the percentage of C14 contained in the total carbon atoms in the polypropylene. In this embodiment, the biomass-derived carbon content P bio can be calculated as follows: P bio (%)=P C14 / 105.5×100

[0065] In this embodiment, theoretically, if all biomass-derived propylene is used as the raw material for polypropylene, the concentration of biomass-derived propylene is 100%, and the biomass degree of the biomass-derived polypropylene is 100. Furthermore, the concentration of biomass-derived propylene in fossil fuel-derived polypropylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polypropylene is 0.

[0066] In this embodiment, the biomass-derived polypropylene or the decorative sheet comprising this polypropylene does not necessarily have a biomass degree of 100.

[0067] In this embodiment, the polymerization method of the biomass-derived propylene-containing monomer is not particularly limited, and can be carried out by a conventionally known method. The polymerization temperature and polymerization pressure are preferably 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 polymerization method of the propylene-containing monomer will be described below.

[0068] The polymerization method for propylene polymers can be appropriately selected depending on the type of polypropylene desired, such as homopolypropylene, random polypropylene, block polypropylene, 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 in two or more stages by any of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ionic polymerization.

[0069] As the biomass-derived polypropylene, homopolypropylene, random polypropylene, and block polypropylene may be used either alone or in combination of two or more thereof.

[0070] (Resin composition containing biomass-derived polypropylene) In this embodiment, the resin composition contains the above-mentioned polypropylene as a main component. The resin composition that forms the transparent resin layer 5, i.e., the transparent resin layer 5, contains biomass-derived propylene in an amount of 5% by mass or more, preferably 5% by mass or more and less than 99% by mass, and more preferably 25% by mass or more and 75% by mass or less, based on the entire resin composition. If the concentration of biomass-derived propylene in the resin composition is in the range of 5% by mass or more and less than 99% by mass, it is possible to more reliably reduce the amount of fossil fuel used compared to conventional methods, and a carbon-neutral decorative sheet can be achieved. The resin composition may contain two or more polypropylenes with different biomass degrees, as long as the concentration of biomass-derived propylene in the resin composition as a whole is within the above range.

[0071] The resin composition may further contain fossil fuel-derived propylene. That is, in this embodiment, the resin composition may be a mixture of biomass-derived polypropylene and fossil fuel-derived polypropylene. 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.

[0072] According to this embodiment, when the resin composition is a mixture with fossil fuel-derived polypropylene, it contains preferably 5% by mass or more but less than 99% by mass, more preferably 25% by mass or more and 75% by mass or less of biomass-derived polypropylene, and preferably 1% by mass or more and 95% by mass or less, more preferably 25% by mass or more and 75% by mass or less of fossil fuel-derived polypropylene. Even when a resin composition of such a mixture is used, it is sufficient that the concentration of biomass-derived propylene in the resin composition as a whole is within the above range.

[0073] The transparent resin layer 5 has a density of 0.90 g / cm 3 More than 0.96g / cm 3 It is preferred that the density is within the range of 0.90 g / cm 3 More than 0.91g / 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 If the density of the transparent resin layer 5 is 0.96 g / cm or more, the rigidity of the transparent resin layer 5 can be increased. 3 If it is equal to or less than this, the transparency and mechanical strength of the transparent resin layer 5 can be improved.

[0074] 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.

[0075] As described above, the transparent resin layer 5 contains biomass-derived propylene in an amount of 5% by mass or more, preferably 5% by mass or more but less than 99% by mass, and more preferably 25% by mass or more but less than 75% by mass, based on the entire colored substrate layer 2. If the concentration of biomass-derived propylene in the transparent resin layer 5 is 5% by mass or more, it is possible to more reliably reduce the amount of fossil fuel used compared to conventional methods, and a carbon-neutral decorative sheet can be achieved.

[0076] The monomer that is the raw material of the biomass-derived polypropylene that constitutes the transparent resin layer 5 may further contain at least one of fossil fuel-derived propylene and fossil fuel-derived α-olefin, or may further contain biomass-derived α-olefin. The above-mentioned α-olefins have carbon-carbon double bonds. Carbon-carbon double bonds can be broken by ultraviolet light. For this reason, in this embodiment, in order to improve the ultraviolet resistance of the decorative sheet 1, thereby improving weather resistance, and to prevent deterioration of the transparent resin layer 5 and the colored substrate layer 2, the transparent resin layer 5 contains an ultraviolet absorber and a light stabilizer, as described above. Furthermore, as will be described in more detail below, adding an ultraviolet absorber and a light stabilizer to the transparent resin layer 5 can further improve weather resistance.

[0077] The transparent resin layer 5 may have a biomass content in the range of 10% to 90% throughout the entire transparent resin layer 5. The transparent resin layer 5 may also contain polypropylene derived from fossil fuels in addition to biomass-derived polypropylene.

[0078] 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 calendar molding.

[0079] The thickness of the transparent resin layer 5 is preferably in the range of 30 μm to 200 μm, and more preferably in the range of 30 μm to 150 μm. A thickness within the above range provides sufficient practical wear resistance and scratch resistance. In terms of design, the presence of the transparent resin layer 5, in combination with the design layer 3, creates a sense of depth and dimension. Specifically, if the thickness of the transparent resin layer 5 is less than 30 μm, the surface hardness may be reduced, resulting in insufficient wear resistance and scratch resistance. On the other hand, if the thickness of the transparent resin layer 5 exceeds 200 μm, productivity during production may be poor, resulting in cost disadvantages.

[0080] In this embodiment, biomass-derived polypropylene has been described as the biomass-derived resin constituting the transparent resin layer 5, but the present disclosure is not limited thereto. For example, in addition to the biomass-derived polypropylene described above, biomass-derived polyethylene, biomass-derived polybutylene, etc. may be used. Furthermore, biomass-derived polyethylene, biomass-derived polybutylene, etc. may be used instead of biomass-derived polypropylene. 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.

[0081] When biomass-derived polyethylene is used for the transparent resin layer 5, the transparent resin layer 5 is preferably configured as follows. For example, the transparent resin layer 5 preferably contains 5% by mass or more, preferably 5% by mass or more but less than 99% by mass, and more preferably 25% by mass or more but less than 75% by mass, of biomass-derived ethylene relative to the total mass of the resin composition (transparent resin layer 5) forming the transparent resin layer 5. The transparent resin layer 5 containing biomass-derived ethylene has a content of 0.85 g / cm. 3 More than 0.99g / cm 3 It is preferred that the density is within the range of 0.90 g / cm 3 More than 0.98g / cm 3 More preferably, the density is within the range of 0.91 g / cm 3More than 0.97g / cm 3 It is more preferable that the transparent resin layer 5 containing biomass-derived ethylene has a density of 30 μm or more and 200 μm or less, and more preferably a thickness of 30 μm or more and 150 μm or less. This makes it possible to impart excellent physical properties (transparency, mechanical strength, abrasion resistance, scratch resistance, etc.) to the transparent resin layer 5 while reducing dependency on petroleum.

[0082] <Surface protective layer> The surface protective layer 6 is a layer provided to impart functions such as weather resistance, moist heat resistance, scratch resistance, stain resistance, and designability to the decorative sheet 1. The material for the surface protective layer 6 is not particularly limited and may be appropriately selected from, for example, urethane-based, acrylic-based, acrylic silicone-based, fluorine-based, and epoxy-based resin materials, but in the decorative sheet 1 of this embodiment, it is desirable that the surface protective layer 6 contains a water-phobic modified acrylic polyol. This can improve the moist heat resistance performance of the decorative sheet 1, and can impart excellent moist heat resistance to the surface protective layer 6, thereby improving the moist heat resistance of the decorative sheet 1. The method for forming the surface protection layer 6 is not particularly limited, and the surface protection layer 6 is formed by applying a coating liquid made from the above-mentioned material using a conventional method such as gravure coating, microgravure coating, comma coating, knife coating, or die coating, and then curing the liquid using a method suitable for the material, such as heat curing or ultraviolet curing.

[0083] In the decorative sheet 1 of this embodiment, the thickness of the surface protective layer 6 is preferably in the range of 3 μm to 20 μm. If it is within this range, printing workability can be easily improved and manufacturing costs can be reduced. In this embodiment, the surface protective layer 6 may contain weather resistance agents (ultraviolet absorbers, light stabilizers) as additives. That is, in the decorative sheet 1 according to this embodiment, the surface protective layer 6 may contain an ultraviolet absorber and a light stabilizer. This can impart excellent weather resistance to the surface protective layer 6.

[0084] <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 . The primer layer 8 is laminated on the other surface of the colored substrate layer 2 (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. The thickness of the primer layer 8 is, for example, in the range of 1 μm to 10 μm.

[0085] <Physical properties of decorative sheets> Furthermore, the decorative sheet 1 according to this embodiment has the following physical properties. In the decorative sheet 1, the tensile modulus of the colored substrate layer 2 is within the range of 700 MPa or more and 1000 MPa or less in both the MD direction, which indicates the machine direction of the sheet, and the TD direction, which is perpendicular to the MD direction. That is, in the decorative sheet 1, the tensile modulus of the colored substrate layer 2 in the MD direction is within the range of 700 MPa or more and 1000 MPa or less, and the tensile modulus of the colored substrate layer 2 in the TD direction is within the range of 700 MPa or more and 1000 MPa or less. The decorative sheet 1 only needs to have a tensile modulus of elasticity in the colored substrate layer 2 within the above range, and the values ​​may be different in the MD direction and the TD direction. Furthermore, the tensile breaking strength of the colored substrate layer 2 in the decorative sheet 1 is within the range of 30 MPa or more and 100 MPa or less in both the MD direction and the TD direction. That is, in the decorative sheet 1, the tensile breaking strength of the colored substrate layer 2 in the MD direction is within the range of 30 MPa or more and 100 MPa or less, and the tensile breaking strength of the colored substrate layer 2 in the TD direction is within the range of 30 MPa or more and 100 MPa or less. Note that the tensile breaking strength of the colored substrate layer 2 in the decorative sheet 1 may be within the above ranges, and the numerical values ​​may be different in the MD direction and the TD direction.

[0086] By setting the tensile modulus and tensile breaking strength of the colored substrate layer 2 in the MD and TD directions within the above-mentioned ranges, the decorative sheet 1 can suppress a decrease in physical properties such as impact resistance and scratch resistance (surface strength), even when formed using plant-derived materials, and can maintain or improve these physical properties suitable for use as a decorative sheet. In other words, it is possible to provide a decorative sheet that has impact resistance and scratch resistance (surface strength) equal to or better than decorative sheets made from conventional petroleum-derived materials, while reducing the amount of fossil fuel used. In the decorative sheet 1, the tensile modulus and tensile breaking strength of the colored substrate layer 2 are controlled by, for example, the thickness of the colored substrate layer 2, the blending of the resin material, and the like.

[0087] Furthermore, the tensile modulus of elasticity of the colored substrate layer 2 in the decorative sheet 1 is more preferably within the range of 800 MPa or more and 1000 MPa or less in both the MD and TD directions. Furthermore, the tensile breaking strength of the colored substrate layer 2 in the decorative sheet 1 is more preferably within the range of 30 MPa or more and 60 MPa or less in both the MD and TD directions. This more reliably prevents a decrease in the physical properties (impact resistance and scratch resistance), and more reliably maintains or improves these physical properties compared to conventional decorative sheets. The tensile modulus and tensile elongation at break of the colored substrate layer 2 in the decorative sheet 1 are values ​​measured in accordance with JIS K 7161, for example.

[0088] The above-described embodiment is an example of the present disclosure, and the present disclosure is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even in forms other than the above-described embodiment, as long as they do not deviate from the technical concept of the present disclosure.

[0089] (Effects of this embodiment) The decorative sheet 1 according to this embodiment and the above-described modified examples can achieve the effects described below. (1) The decorative sheet 1 of this embodiment comprises at least a colored substrate layer 2, an adhesive resin layer 4, and a transparent resin layer 5 laminated in this order, the colored substrate layer 2 being a resin layer formed using a resin composition containing a biomass-derived polyolefin formed by polymerizing a monomer containing a biomass-derived olefin, the tensile modulus of the colored substrate layer 2 in both the MD direction indicating the flow direction of the sheet and the TD direction perpendicular to the MD direction being within the range of 700 MPa or more and 1000 MPa or less, and the tensile breaking strength of the colored substrate layer 2 in both the MD direction and the TD direction being within the range of 30 MPa or more and 100 MPa or less. According to this configuration, by using biomass-derived polyolefin for at least the colored substrate layer 2, dependency on petroleum in the material can be reduced, and even when formed using plant-derived materials, by limiting the tensile modulus and tensile breaking strength of the colored substrate layer 2 to within the above ranges, physical properties suitable for use as a decorative sheet can be maintained or improved. (2) In the decorative sheet 1, the transparent resin layer 5 may be a resin layer formed using a resin composition containing at least one of a fossil fuel-derived polyolefin and the above-mentioned biomass-derived polyolefin. According to this configuration, by using biomass-derived polyolefin for the transparent resin layer 5, it is possible to further reduce the dependency on petroleum as a material. (3) The resin composition forming the colored substrate layer 2 in the decorative sheet 1 may contain the biomass-derived polyolefin and the fossil fuel-derived polyolefin. This configuration makes it possible to reduce dependence on petroleum compared to conventional methods while using materials derived from fossil fuels. (4) In the decorative sheet 1, the colored substrate layer 2 contains 5% by mass or more of biomass-derived ethylene relative to the total mass of the colored substrate layer 2, and the content is 0.90 g / cm 3 More than 1.50g / cm 3 It may have a density within the following range and a thickness within the range of 10 μm to 150 μm. This configuration makes it possible to reliably reduce the amount of fossil fuel used compared to conventional methods, thereby realizing a carbon-neutral decorative sheet. (5) In the decorative sheet 1, the transparent resin layer 5 contains 5 mass % or more of biomass-derived propylene relative to the total mass of the transparent resin layer 5, and the content is 0.90 g / cm 3 More than 0.96g / cm 3 It may have a density within the following range and a thickness within the range of 30 μm to 200 μm. According to this configuration, the amount of fossil fuel used can be reduced more reliably than before, and a carbon-neutral decorative sheet can be realized. (6) In the decorative sheet 1, the transparent resin layer 5 contains 5 mass % or more of biomass-derived ethylene relative to the total mass of the transparent resin layer 5, and the content is 0.90 g / cm 3 More than 0.98g / cm 3 It may have a density within the following range and a thickness within the range of 30 μm to 200 μm. This configuration can reduce dependency on petroleum and provide the transparent resin layer 5 with excellent physical properties (transparency, mechanical strength, abrasion resistance, scratch resistance, etc.). (7) The decorative sheet 1 has a pattern layer 3 provided between a colored substrate layer 2 and an adhesive resin layer 4, and the pattern layer 3 is a layer containing a colorant and a urethane (meth)acrylate, which is a reaction product of a polyol, an isocyanate compound, and a hydroxy (meth)acrylate, and at least one component of the polyol, the isocyanate compound, and the hydroxy (meth)acrylate may contain a component derived from biomass. This configuration can further reduce dependency on petroleum. (8) The decorative material 10 according to this embodiment comprises a substrate 9 and a decorative sheet 1 attached to at least one surface of the substrate 9. According to this configuration, by using biomass-derived polyolefin for at least the colored substrate layer 2, dependency on petroleum in the material is reduced, and even when formed using plant-derived materials, a decorative material can be provided using a decorative sheet that maintains or improves physical properties suitable for use as a decorative sheet.

[0090] [Example] The decorative materials of each example and comparative example will be described below with reference to this embodiment, but the present disclosure is not limited to the following examples.

[0091] Example 1 The colored substrate layer (colored resin layer) was a colored resin layer made of a thermoplastic resin of biomass-derived (plant-derived) polyethylene. One side of the colored substrate layer was subjected to corona discharge treatment, after which a design layer was printed using plant-derived ink. An adhesive resin layer was then laminated on top of the design layer, and a transparent resin layer made of fossil fuel-derived polypropylene was then laminated using a ruder laminate. After that, the texture was expressed by mechanical embossing, and finally an expression protection layer was formed. The other side of the colored substrate layer (the side opposite the design layer) was subjected to corona discharge treatment, after which a primer layer (thickness 1 to 2 μm) was formed. When the tensile modulus of the colored substrate layer in the decorative sheet according to this example was measured, it was 800 MPa in both the MD and TD directions. Furthermore, when the tensile breaking strength of the colored substrate layer in the decorative sheet according to this example was measured, it was 60 MPa in both the MD and TD directions. The composition of each layer is shown below.

[0092] [Colored base material layer] The material used was biomass-derived polyethylene (green polyethylene manufactured by Braskem). The content of biomass-derived polyethylene in the colored substrate layer was 90% by mass relative to the total mass of the colored substrate layer (resin composition). The thickness was 55 μm. [Picture layer] In Example 1, the binder resin of the design layer was biourethane (meth)acrylate, which is a reaction product of a polyester polyol containing biomass-derived components, an isocyanate compound derived from fossil fuel, and a hydroxy (meth)acrylate derived from fossil fuel, as the binder resin for the plant-derived ink. The polyester polyol containing biomass-derived components was a reaction product of a polyfunctional alcohol containing biomass-derived components and a polyfunctional carboxylic acid derived from fossil fuel.

[0093] [Adhesive resin layer] A two-component urethane adhesive was used. The application amount was 5 g / m. 2 It was decided. [Transparent resin layer] A 70 μm thick transparent resin (fossil fuel-derived polypropylene) was used. [Surface protection layer] The main component was an acrylic resin composition.

[0094] Example 2 The material for the transparent resin layer was the same as for the colored substrate layer, biomass-derived polyethylene (green polyethylene manufactured by Braskem Co., Ltd.) A decorative sheet according to Example 2 was obtained in the same manner as in Example 1. Example 3 The resin material was adjusted so that the measurement results of the tensile breaking strength of the colored substrate layer were 30 MPa in the MD and TD directions, except that the decorative sheet according to Example 3 was obtained in the same manner as in Example 2. Example 4 The resin material was adjusted so that the tensile modulus of the colored substrate layer was 700 MPa in both the MD and TD directions, and the tensile breaking strength was 40 MPa in both the MD and TD directions. Otherwise, a decorative sheet according to Example 4 was obtained in the same manner as in Example 2. Example 5 The resin material was adjusted so that the measured tensile modulus of elasticity of the colored substrate layer was 1000 MPa in both the MD and TD directions, and the measured tensile strength at break was 50 MPa in both the MD and TD directions. Otherwise, a decorative sheet according to Example 5 was obtained in the same manner as in Example 2. Example 6 A decorative sheet according to Example 6 was obtained in the same manner as in Example 5, except that the resin material was adjusted so that the measured tensile breaking strength of the colored substrate layer was 100 MPa in both the MD and TD directions. Example 7 A decorative sheet of Example 7 was obtained in the same manner as in Example 3. Example 8 A decorative sheet according to Example 8 was obtained in the same manner as in Example 5, except that the resin material for the colored substrate layer was adjusted so that the measured tensile breaking strength was 60 MPa in both the MD and TD directions.

[0095] (Comparative Example 1) A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 2, except that polyethylene derived from fossil fuels (petroleum) was used as the material for the colored substrate layer. (Comparative Example 2) The decorative sheet of Comparative Example 2 was obtained in the same manner as Comparative Example 1, except that polyethylene derived from fossil fuels (petroleum) was used as the material for the transparent resin layer. (Comparative Example 3) The resin material was adjusted so that the tensile modulus of the colored substrate layer was 650 MPa in both the MD and TD directions, and the tensile strength at break was 20 MPa in both the MD and TD directions. A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 2. Comparative Example 4 The resin material was adjusted so that the tensile modulus of the colored substrate layer was 600 MPa in both the MD and TD directions, and the tensile strength at break was 25 MPa in both the MD and TD directions. A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 2. (Comparative Example 5) The resin material was adjusted so that the measured tensile modulus of elasticity of the colored substrate layer was 1050 MPa in both the MD and TD directions, and the measured tensile strength at break was 105 MPa in both the MD and TD directions. A decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 2. (Comparative Example 6) The resin material was adjusted so that the tensile modulus of the colored substrate layer was 1000 MPa in the MD direction and 1100 MPa in the TD direction, and the tensile breaking strength was 110 MPa in both the MD and TD directions. A decorative sheet of Comparative Example 6 was obtained in the same manner as in Example 2.

[0096] <Measurement of strength properties> For the decorative sheets produced in each of the Examples and Comparative Examples, tensile tests were carried out at room temperature in accordance with JIS K 7161 to measure the tensile modulus and tensile elongation at break in both the MD and TD directions. The measurement conditions were a pulling speed of 50 mm / min when measuring the tensile modulus and 500 mm / min when measuring the tensile strength at break, a chuck distance of 70 mm, a gauge distance of 40 mm, a test piece thickness of 55 μm, and a test piece width of 10 mm.

[0097] (Performance evaluation, evaluation results) The decorative sheets of each example and comparative example were evaluated for "design," "surface strength," "bending processability," "petroleum dependency," "weather resistance," and "lamination strength." The evaluation methods used were as follows:

[0098] <Design> [Transparency of transparent resin layer] The transparency of the transparent resin layer was visually observed. (Evaluation criteria) ◎: Transparency is better than the current product ○: If the transparency is the same as the current version △: Inferior to the current product but no problems ×: When production is difficult from the viewpoint of productivity of the transparent resin layer In this example, a grade of "good" or better was considered to be acceptable. [Printability] The presence or absence of heat wrinkles during drying, the need for tension adjustment, etc. were observed. (Evaluation criteria) ◎: When the occurrence of heat wrinkles and the need for tension adjustment is better (fewer) than the current product. 〇: When the occurrence of heat wrinkles and the need for tension adjustment is the same as the current product. △: Inferior to the current product but no problems ×: When production is difficult from a productivity standpoint In this example, a grade of "good" or better was considered to be acceptable.

[0099] <Surface strength> [Pencil hardness] The decorative sheets of each example and each comparative example were subjected to a pencil hardness test in accordance with "JIS K5600," and changes in appearance due to scratches were evaluated visually. (Evaluation criteria) ◎: Pencil hardness is better than the current product 〇: When the pencil hardness is the same as the current product △: Inferior to the current product but no problems ×: Inferior to current products and below quality standards In this example, a grade of "good" or better was considered to be acceptable.

[0100] <Impact resistance> The decorative sheets of each Example and Comparative Example were attached to a plywood substrate to prepare decorative materials, and each decorative material was subjected to a DuPont impact test in accordance with the Japanese Industrial Standard "JIS K5600-5-3," in which a weight was dropped to apply impact and the degree of denting was visually confirmed. The weight and drop height of the weight were as follows: (1) A 500g weight was dropped from a height of 30cm. (2) A 500g weight was dropped from a height of 50cm. (3) A 1000g weight was dropped from a height of 50cm. (Evaluation criteria) ◎: No cracks under any of the above conditions (1) to (3), and the dents are better than the current product 〇: There are some cracks, but the product is equivalent to the current product and can be used △: Inferior to the current product but no production problems ×: When cracks and dents make production and use difficult In this example, a grade of "good" or better was considered to be acceptable.

[0101] <Suitable for bending> Each decorative sheet from each Example and Comparative Example was attached to a plywood substrate to prepare a decorative material. Each decorative material was subjected to V-cut processing at room temperature (20°C) and 5°C, and the appearance of the folded top was confirmed. For the V-cut processing, a V-shaped groove was cut from the side of the plywood substrate where the decorative sheet was not attached to the boundary where the plywood substrate and the decorative sheet were attached, so as not to scratch the decorative sheet. Next, the evaluation sheet was folded 90 degrees along the V-shaped groove so that the side where the decorative sheet was attached formed a mountain fold, and the presence of abnormalities such as whitening or cracks (fissures) at the folded top was visually determined. (Evaluation criteria) ◎: Almost no cracks at the corners, better than the current product 〇: Slight cracks are found in the corners, but the product is the same as the current product. △: There is a crack in the corner and it is slightly inferior to the current product. ×: When cracks at the corners are noticeable and production and use are difficult In this example, a grade of "good" or better was considered to be acceptable.

[0102] <Oil dependence> The dependency on fossil fuels when producing the decorative sheets of each Example and Comparative Example was evaluated relatively as "high," "medium," or "low." Evaluations of "medium" or "low" were deemed acceptable. <Weather resistance> The appearance of the decorative sheets of each Example and Comparative Example after the accelerated weathering test was visually evaluated according to the following criteria: The accelerated weathering test was performed using an Eye Super UV Tester (SUV-W161; Iwasaki Electric Co., Ltd.) at a black panel temperature of 63°C and an illuminance of 65 mW / cm², with 30 cycles consisting of 20 hours of UV irradiation + 4 hours of condensation. [Evaluation criteria] 〇: No change in appearance of decorative sheet △: Slight discoloration was observed on the decorative sheet, but there was no problem with the quality. ×: Significant discoloration is observed on the decorative sheet In this example, an evaluation of "good" or "fair" was deemed to be acceptable.

[0103] <Lamination strength> The interlayer adhesion (lamination strength) between the colored substrate layer side and the transparent resin layer side with the adhesive layer sandwiched therebetween was evaluated. (Evaluation criteria) ◎: When the laminate strength is equivalent to that of the current product. ○: Inferior to the current product but no problems. △: Inferior to current products and below quality standards. ×: Not applicable as interlayer lamination strength of decorative sheet. In this example, an evaluation of "◎" or "◯" was deemed to be a pass.

[0104] The results of evaluating various performances using the methods described above are shown in Table 1, along with the compositions of the decorative sheets of each example and comparative example.

[0105] [Table 1]

[0106] As shown in Table 1, all of the decorative sheets of Examples 1 to 8 passed the evaluations of surface strength, impact resistance, and petroleum dependency, demonstrating excellent performance. Specifically, all of the decorative sheets of Examples 1 to 8 were rated "good" or above for surface strength (scratch resistance) and impact resistance, both physical properties related to the durability of the decorative sheets. This is thought to be because, in the decorative sheets of each Example, the tensile modulus in the MD and TD directions of the colored substrate layer containing biomass-derived polyolefin was within the range of 700 MPa or more and 1000 MPa or less, and the tensile break strength in the MD and TD directions of the colored substrate layer was within the range of 30 MPa or more and 100 MPa or less. Furthermore, the decorative sheets of Examples 1 to 8 were rated either "medium" or "low" in petroleum dependency. This is thought to be because the colored substrate layer (colored resin layer) contained biomass-derived polyolefin, and the transparent resin layer contained at least one of petroleum-derived polyolefin and biomass-derived polyolefin.

[0107] In this way, it has been confirmed that a decorative sheet in which the colored substrate layer is a resin layer formed using a resin composition containing biomass-derived polyolefin, the transparent resin layer is formed using a resin composition containing at least one of petroleum-derived polyolefin and biomass-derived polyolefin, and further has a tensile modulus and tensile break strength in the MD and TD directions within the above ranges (specific ranges), can maintain or improve physical properties suitable for use as a decorative sheet (surface strength (scratch resistance) and impact resistance) even when formed using plant-derived materials. It has also been confirmed that it is possible to reduce dependency on petroleum in materials and conserve petroleum resources. Furthermore, the decorative sheets of Examples 1 to 8 passed all of the tests for design, suitability for bending, weather resistance, and laminate strength, demonstrating excellent performance.

[0108] On the other hand, the decorative sheet of Comparative Example 1 did not contain a biomass-derived polyolefin in the colored substrate layer, and the physical properties related to the durability of the decorative sheet (surface strength (scratch resistance) and impact resistance) were reduced compared to the Examples. Furthermore, the decorative sheets of Comparative Examples 3-6 used a resin composition containing a biomass-derived polyolefin in the colored substrate layer and transparent resin layer, but the above physical properties related to the durability of the decorative sheet were reduced compared to the Examples. This is thought to be because the tensile modulus and tensile breaking strength in the MD and TD directions were outside the above-mentioned specific ranges. In addition, the decorative sheet of Comparative Example 2 is a decorative sheet equivalent to current products in which both the colored substrate layer and the transparent resin layer are made of petroleum-derived polyolefin, and although the above physical properties are good, it does not use plant-derived polyolefin, and its petroleum dependency was rated as "high."

[0109] The decorative sheet and decorative material of the present disclosure are not limited to the above-described embodiments and examples, and various modifications are possible within the scope that does not impair the features of the invention.

[0110] Furthermore, for example, the present disclosure can be configured as follows. (1) At least 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 is a resin layer formed using a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin, A decorative sheet characterized in that the tensile modulus of the colored thermoplastic resin layer in each of the MD direction, which indicates the flow direction of the sheet, and the TD direction, which is perpendicular to the MD direction, is within the range of 700 MPa or more and 1000 MPa or less, and the tensile breaking strength of the colored thermoplastic resin layer in each of the MD direction and the TD direction is within the range of 30 MPa or more and 100 MPa or less. (2) The decorative sheet according to (1) above, characterized in that the transparent thermoplastic resin layer is a resin layer formed using a resin composition containing at least one of a fossil fuel-derived polyolefin and a biomass-derived polyolefin. (3) The decorative sheet according to (1) or (2) above, characterized in that the resin composition forming the colored thermoplastic resin layer contains the biomass-derived polyolefin and the fossil fuel-derived polyolefin. (4) The colored thermoplastic resin layer contains 5% by mass or more of biomass-derived ethylene relative to the total mass of the colored thermoplastic resin layer, and the content of the biomass-derived ethylene is 0.90 g / cm 3 More than 1.50g / cm 3 The decorative sheet according to any one of (1) to (3) above, characterized in that it has a density within the following range and a thickness within the range of 10 μm or more and 150 μm or less. (5) The transparent thermoplastic resin layer contains 5% by mass or more of biomass-derived propylene relative to the total mass of the transparent thermoplastic resin layer, and the content of the biomass-derived propylene is 0.90 g / cm 3 More than 0.96g / cm 3 The decorative sheet according to any one of (1) to (4) above, characterized in that it has a density within the following range and a thickness within the range of 30 μm or more and 200 μm or less. (6) The transparent thermoplastic resin layer contains 5% by mass or more of biomass-derived ethylene relative to the total mass of the transparent thermoplastic resin layer, and the content of the biomass-derived ethylene is 0.85 g / cm 3 More than 0.99g / cm 3 The decorative sheet according to any one of (1) to (4) above, characterized in that it has a density within the following range and a thickness within the range of 30 μm or more and 200 μm or less. (7) The transparent thermoplastic resin layer contains 5% by mass or more of biomass-derived ethylene relative to the total mass of the transparent thermoplastic resin layer, and the content of the biomass-derived ethylene is 0.90 g / cm 3 More than 0.98g / cm 3The decorative sheet according to any one of (1) to (4) above, characterized in that it has a density within the following range and a thickness within the range of 30 μm or more and 200 μm or less. (8) a pattern layer is provided between the colored thermoplastic resin layer and the adhesive resin layer, the design layer is a layer containing a colorant and a urethane (meth)acrylate which is a reaction product of a polyol, an isocyanate compound, and a hydroxy (meth)acrylate; The decorative sheet according to any one of (1) to (6) above, characterized in that at least one component of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a component derived from biomass. (9) A substrate; A decorative material comprising the decorative sheet according to any one of (1) to (8) above, attached to at least one surface of the substrate. [Explanation of symbols]

[0111] 1...decorative sheet, 2...colored substrate layer, 3...pattern layer, 4...adhesive resin layer, 5...transparent resin layer, 6...surface protection layer, 7...concave and convex portion, 8...primer layer, 9...substrate, 10...decorative material

Claims

1. At least 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 is a resin layer formed using a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin, The tensile modulus of the colored thermoplastic resin layer in each of the MD direction indicating the flow direction of the sheet and the TD direction perpendicular to the MD direction is within a range of 700 MPa or more and 1000 MPa or less, and the tensile breaking strength of the colored thermoplastic resin layer in each of the MD direction and the TD direction is within a range of 30 MPa or more and 100 MPa or less. A decorative sheet characterized by:

2. the transparent thermoplastic resin layer is a resin layer formed using a resin composition containing at least one of a fossil fuel-derived polyolefin and a biomass-derived polyolefin; 2. The decorative sheet according to claim 1.

3. the resin composition forming the colored thermoplastic resin layer contains the biomass-derived polyolefin and the fossil fuel-derived polyolefin.

3. The decorative sheet according to claim 2.

4. The colored thermoplastic resin layer contains 5% by mass or more of biomass-derived ethylene relative to the mass of the entire colored thermoplastic resin layer, and has a density of 0.90 g / cm ３ 1.50g / cm or more ３ and a thickness in the range of 10 μm to 150 μm. The decorative sheet according to claim 3 .

5. The transparent thermoplastic resin layer contains 5% by mass or more of biomass-derived propylene relative to the mass of the entire transparent thermoplastic resin layer, and has a density of 0.90 g / cm ３ 0.96g / cm or more ３ and a thickness in the range of 30 μm to 200 μm.

5. The decorative sheet according to claim 4.

6. The transparent thermoplastic resin layer contains 5% by mass or more of biomass-derived ethylene relative to the mass of the entire transparent thermoplastic resin layer, and has a density of 0.85 g / cm ３ 0.99g / cm or more ３ and a thickness in the range of 30 μm to 200 μm.

5. The decorative sheet according to claim 4.

7. The transparent thermoplastic resin layer contains 5% by mass or more of biomass-derived ethylene relative to the mass of the entire transparent thermoplastic resin layer, and has a density of 0.90 g / cm ３ 0.98g / cm or more ３ and a thickness in the range of 30 μm to 200 μm.

5. The decorative sheet according to claim 4.

8. a pattern layer is provided between the colored thermoplastic resin layer and the adhesive resin layer, the design layer is a layer containing a colorant and a urethane (meth)acrylate which is a reaction product of a polyol, an isocyanate compound, and a hydroxy (meth)acrylate; At least one component selected from the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a biomass-derived component.

2. The decorative sheet according to claim 1.

9. A substrate; and the decorative sheet according to any one of claims 1 to 8 bonded to at least one surface of the substrate. A cosmetic material characterized by:

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