Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material capable of suppressing color variation and deterioration of physical properties even when formed using a recycled resin.SOLUTION: There is provided a decorative sheet 1 obtained by laminating 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. A base material 9 is laminated on a surface on the opposite side to the pattern layer 3 of the colored base material layer 2 via a primer layer 8, the colored base material layer 2 is composed of a resin composition comprising a virgin resin and a recycled resin and is formed to contain 10% or more and 80% or less of a recycled resin in the single layer of the colored base material layer 2. Therefore, the color variation and deterioration of physical properties in the decorative sheet 1 can be suppressed even when comprising a recycled resin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

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

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

[0004] Most conventional decorative sheets have been made from petroleum-derived materials, but in recent years, with improvements in recycling technology and consideration for the environment, attention has been focused on replacing them with recycled materials. However, decorative sheets containing recycled materials have concerns such as variations in color and deterioration of physical properties.

[0005] In view of the above-mentioned problems, the present invention aims to provide a decorative sheet and decorative material that can suppress color variation and deterioration of physical properties even when formed using recycled materials. [Means for solving the problem]

[0006] A decorative sheet according to one embodiment of the present invention comprises a colored thermoplastic resin layer, an adhesive layer, and a transparent thermoplastic resin layer, in that order, and the colored thermoplastic resin layer is a layer made of a resin composition containing virgin resin and recycled resin, and is characterized in that the colored thermoplastic resin layer alone contains 10% to 80% recycled resin. A decorative material according to another aspect of the present invention is characterized by comprising a substrate and a decorative sheet laminated on at least one surface of the substrate. [Effects of the Invention]

[0007] According to one aspect of the present invention, even when a decorative sheet is formed using recycled resin, it is possible to suppress the occurrence of color variations, deterioration of physical properties, and the like. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of the configuration of a decorative sheet and a decorative material according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In the drawings, identical or similar parts are denoted by the same or similar reference numerals, and redundant explanations are omitted. The drawings are schematic and may differ from the actual product. The following embodiments are illustrative of configurations embodying the technical concept of the present invention. The technical concept of the present invention is not limited to the materials, shapes, structures, etc. of the components exemplified in the following embodiments. Various modifications can be made to the technical concept of the present invention within the technical scope defined by 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 concept of the present invention. 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."

[0010] FIG. 1 is a cross-sectional view that schematically shows a decorative material according to one embodiment of the present invention. As shown in FIG. 1, the decorative material 10 comprises a decorative sheet 1 and a substrate 9. The base material 9 is formed into a plate shape using, for example, a wood board, an inorganic board, a metal plate, or the like, and has a decorative sheet 1 laminated on one surface (the upper surface in FIG. 1) thereof. That is, the decorative material 10 comprises the base material 9 and the decorative sheet 1 laminated on one surface of the base material 9.

[0011] The decorative material 10 is not limited to a configuration in which the decorative sheet 1 is provided on only one side of the base material 9, but may also be configured to provide the decorative sheet 1 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.

[0012] (Composition of decorative sheet) As shown in Figure 1, the decorative sheet 1 comprises a colored substrate layer (colored thermoplastic resin layer) 2, a design layer 3, an adhesive resin layer (adhesive 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. An adhesive layer may be further provided between the design layer 3 and the adhesive resin layer 4. The decorative sheet 1 only needs to comprise at least the colored substrate layer 2, the adhesive resin layer 4, and the transparent resin layer 5.

[0013] <Colored base material layer> The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed from a resin composition containing virgin resin and recycled resin. The recycled resin is a resin extracted from a component that has been processed into a decorative sheet or the like after being laminated with other layers, for example.

[0014] The colored substrate layer 2 preferably contains 10% to 80% recycled resin for the colored substrate layer alone. The decorative sheet 1 preferably contains 5% or more recycled resin for the entire decorative sheet 1. In other words, other layers of the colored substrate layer 2 may contain recycled resin, but the decorative sheet 1 as a whole preferably contains 5% or more recycled resin.

[0015] Polyethylene or polypropylene, which is a colored thermoplastic polyolefin resin, can be used as the thermoplastic resin forming the colored substrate layer 2. Alternatively, any of polybutylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin, and polyvinyl chloride (PVC) resin can be used as the thermoplastic resin forming the colored substrate layer 2.

[0016] The colored substrate layer 2 contains an inorganic substance. The inorganic substance may be one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, other oxides, etc. Adding an inorganic substance to the colored substrate layer 2 can improve the hiding power of the colored substrate layer 2.

[0017] If necessary, one or more additives selected from various additives such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, gloss adjusters, etc. The colored substrate layer 2 preferably contains one or both of a benzotriazole-based or triazine-based weathering agent and a hindered amine light stabilizer (HALS), which is a light stabilizer using a hindered amine compound.

[0018] There are no particular restrictions on the thickness of the colored substrate layer 2, and it may be determined depending on the location where it is to be applied. For example, when laid on a flooring material or the like, if the thickness of the colored substrate layer 2 is 40 μm or more, it can absorb the unevenness and steps of the underlying flooring material, etc., and provide a good application finish for the decorative sheet 1, and if the thickness of the colored substrate layer 2 is 200 μm or less, it is not necessary to form the colored substrate layer 2 thicker than necessary, and the manufacturing costs of the decorative sheet 1 can be reduced.

[0019] <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. Note that the pattern layer 3 can be omitted if the coloring of the colored substrate layer 2 can serve as a substitute.

[0020] 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.

[0021] Examples of binder resins that can be used include, but are not limited to, urethane resins, acrylic resins, vinyl chloride acetate resins, polyimide resins, soluble nitrocellulose, and mixtures thereof. Any pattern can be used as the design, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, letters, symbols, solid colors, or combinations thereof. To improve the hiding power of the decorative sheet 1, a concealing layer may be provided between the design layer 3 and the colored substrate layer 2. The concealing layer may be formed using, for example, an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0022] The thickness of the design layer 3 is preferably in the range of 1 μm or more and 10 μm or less. This is because when the thickness of the design layer 3 is 1 μm or more, it is possible to make the printing clear. On the other hand, 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 the production costs.

[0023] 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 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.

[0024] <Adhesive resin layer> The adhesive resin layer 4 is provided to bond the colored substrate layer 2 provided with the pattern layer 3 and the transparent resin layer 5 together. The material for the adhesive resin layer 4 is not particularly limited as long as it contributes to improving the adhesive strength between any resins, and various materials such as acrylic, polyester, polyurethane, and epoxy can be used. Generally, a two-component curing polyurethane adhesive with high coating film cohesive strength is used as the material for the adhesive resin layer 4. The coating method can also be selected appropriately depending on the viscosity of the coating liquid, etc. The thickness of the adhesive resin layer 4 is preferably about 0.5 μm to 10 μm.

[0025] <Transparent resin layer> The transparent resin layer 5 is a resin layer formed using a thermoplastic resin. The transparent resin layer 5 may be formed from a resin composition containing a virgin resin and a recycled resin, or may be formed from a resin composition containing a virgin resin but not a recycled resin. The thermoplastic resin forming the transparent resin layer 5 can be polyethylene or polypropylene, which are thermoplastic polyolefin resins, or any of polybutylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin, and polyvinyl chloride (PVC) resin.

[0026] Furthermore, the transparent resin layer 5 contains a nano-nucleating agent. More specifically, the nano-sized additive preferably has an average particle size of 375 nm or less. Furthermore, the nano-sized additive is preferably in a vesicle state, and more preferably, the vesicle has a single-layer outer membrane.

[0027] Nano-sized additives are additives that have been converted into nano-sized particles by a nano-sizing technique (nanofiber processing). Examples of nanofiber processing include solid-phase methods, which primarily involve mechanical pulverization of additives to obtain nano-sized particles; liquid-phase methods, which involve synthesizing or crystallizing nano-sized particles in an additive or a solution in which the additive is dissolved; and gas-phase methods, which involve synthesizing or crystallizing nano-sized particles from an additive or a gas or vapor comprising the additive. Briefly listing specific means for implementing each method, solid-phase methods include ball mills, bead mills, rod mills, colloid mills, conical mills, disk mills, hammer mills, and jet mills. Liquid-phase methods include crystallization, coprecipitation, sol-gel processes, liquid-phase reduction, and hydrothermal synthesis. Gas-phase methods include electric furnace processes, chemical flame processes, laser processes, and thermal plasma processes.

[0028] To explain more specific methods of nano-processing, a specific example of the solid-phase method is to mill a mixture of 100 g of isopropyl alcohol and 50 g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate in a bead mill for 60 minutes using 30 μm stabilized zirconia beads to obtain nano-sized nucleating agent particles with an average particle size of approximately 100 nm to 150 nm. A specific example of the crystallization method is to dissolve 50 g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate in a mixed solvent consisting of 96 g of xylene, 72 g of isopropyl alcohol, and 24 g of water, and then contact this solution with a poor solvent such as ethanol in a microreactor to precipitate nano-sized nucleating agent particles with an average particle size of 1 nm to 150 nm.

[0029] A vesicle is a small, vesicular capsule with a closed membrane structure like a spherical shell, and those containing a liquid phase are particularly referred to as vesicles. In the present invention, additives are contained in this liquid phase. These vesicles have extremely high dispersibility, preventing particle aggregation due to the mutual repulsion of their outer membranes. This effect enables the additives to be uniformly dispersed in the resin composition constituting each resin layer. Among nano-processing methods, methods for obtaining nano-sized additives as vesicles (vesicle formation processes) include, for example, the Bangham method, extrusion, hydration, surfactant dialysis, reverse-phase evaporation, freeze-thawing, and supercritical reverse-phase evaporation. Briefly, the Bangham method involves placing chloroform or a chloroform / methanol mixed solvent in a container such as a flask, followed by the addition and dissolution of phospholipids. The solvent is then removed using an evaporator to form a thin lipid film, and the additive dispersion is added, followed by hydration and dispersion using a vortex mixer to obtain vesicles. The extrusion method is a method for obtaining vesicles by preparing a thin film of phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method. The hydration method is a preparation method similar to the Bangham method, but without the use of a mixer, vesicles are obtained by gentle stirring and dispersion. The reverse-phase evaporation method involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method uses cooling and heating as an external perturbation, and vesicles are obtained by repeating this cooling and heating process.

[0030] In particular, supercritical reverse-phase evaporation is a method for obtaining vesicles with a monolayer outer membrane. Supercritical reverse-phase evaporation is a method for producing capsules encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Supercritical carbon dioxide refers to carbon dioxide in a supercritical state at or above its critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa). Carbon dioxide under temperature or pressure conditions above its critical point refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions.

[0031] The specific vesicle formation process using supercritical reverse-phase evaporation involves injecting an aqueous phase into a mixture of supercritical carbon dioxide, phospholipids as a dispersant, and additives as encapsulated substances, followed by stirring to form an emulsion of supercritical carbon dioxide and aqueous phase. The carbon dioxide then expands and evaporates under reduced pressure, resulting in phase inversion, producing nanocapsules in which the phospholipids form a monolayer membrane covering the surface of the additive particles. Unlike conventional encapsulation methods, in which the dispersant forms multiple membranes on the surface of the additive particles, this supercritical reverse-phase evaporation method easily produces monolayer capsules, allowing for the preparation of smaller capsules. Furthermore, multilayer capsules can be easily produced by injecting supercritical carbon dioxide into a mixture of phospholipids, additives, and aqueous phase. Examples of phospholipids used in preparing vesicles include glycerophospholipids such as phosphatidylcholine, phosphatidiethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphoryethanolamine, and ceramide phosphorylglycerol. The vesicles can achieve excellent compatibility with resin materials by having an outer membrane made of phospholipids.

[0032] The vesicles may also have an outer membrane made of a dispersant. Examples of dispersants include polymeric surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicones, waxes, and modified resins. Examples of polymeric surfactants include aliphatic polycarboxylic acids, polycarboxylic acid alkylamines, polyacrylic acids, polymethacrylic acids, polyoxyethylene alkyl ethers, and sorbitan fatty acid esters. Examples of fatty acid metal salts include those obtained by combining stearic acid, lauric acid, 12-hydroxystearic acid, montanic acid, behenic acid, ricinoleic acid, and myristic acid with lithium, sodium, potassium, magnesium, calcium, barium, zinc, and aluminum. Examples of silane coupling agents include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Titanate coupling agents include tetrakis[2,2-bis(allyloxymethyl)butoxy]titanium(IV), di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, isopropyl titanium triisostearate, di-n-butoxy bis(triethanolaminato)titanium, tetrakis(2-ethylhexyloxy)titanium, and di-i-propoxy bis(acetylacetonato)titanium. Silicones include those obtained by polymerizing olefins such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, cyclic dimethyl silicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, and higher fatty acid-modified silicone oil, or by pyrolysis of polyolefins, which are then further oxidized or modified with maleic acid, sulfonic acid, carboxylic acid, rosin acid, etc. Resins include those obtained by modifying polyolefins with maleic acid, sulfonic acid, carboxylic acid, rosin acid, etc.

[0033] When the transparent resin layer 5 is made of a resin containing a nano-sized additive, it is important that the resin contains, for example, 90 to 100% by weight of crystalline polypropylene resin as the main component and contains a nucleating agent as the nano-sized additive. More preferably, the nano-sized additive is contained in a vesicle state (nucleating agent vesicle). In this case, the average particle size of the nucleating agent vesicle is preferably equal to or less than half the wavelength of visible light. Specifically, since the wavelength range of visible light is 400 to 750 nm, the average particle size is preferably equal to or less than 375 nm. For such a transparent resin layer 5, it is important that the haze value is 15% or less, more preferably 10% or less, the tensile modulus is 800 MPa or more and 2000 MPa or less, and the tensile elongation at break is 200% or more, by adjusting the cooling conditions during film formation.

[0034] The crystalline polypropylene resin can be designed by appropriately selecting from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof, which have different pentad fractions. It is more important that the crystalline polypropylene resin is a highly crystalline homopolypropylene resin, i.e., a homopolymer of propylene, having an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. Resins other than the crystalline polypropylene that constitute the transparent resin layer can be appropriately selected depending on the purpose of blending, as long as they do not significantly adversely affect the physical properties of the crystalline polypropylene.

[0035] The transparent resin layer 5 preferably has a thickness of 20 μm or more and 250 μm or less. Because nano-sized nucleating agents have extremely small particle diameters, the number of nucleating agents present per unit volume and their surface area increase inversely proportional to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes shorter. When a nucleating agent is added to a polypropylene resin and crystal growth occurs on the surface of one particle, the end of the growing crystal immediately comes into contact with the end of a crystal growing on the surface of another nucleating agent particle adjacent to that nucleating agent particle. The ends of the crystals inhibit each other's growth, stopping the growth of each crystal. This allows the average diameter of spherulites in the crystalline portion of the crystalline polypropylene resin to be extremely small.

[0036] Therefore, by incorporating a nano-sized nucleating agent into the transparent resin layer 5, a larger number of finer crystal nuclei are generated in the resin than with conventional nucleating agents, which results in a shorter distance between crystal nuclei in the crystalline portion, suppressing the growth of individual crystals and successfully reducing the average particle size of spherulites. Furthermore, this crystalline polypropylene resin achieves excellent transparency with a haze value of 15% or less.

[0037] Furthermore, by incorporating the nano-sized nucleating agent in a vesicle state, i.e., as a nucleating agent vesicle, aggregation of the nucleating agent particles is prevented, thereby realizing high dispersibility in the resin material. In the resin composition, the outer membrane of the nucleating agent vesicle partially collapses, exposing the nucleating agent, and during the crystallization process of the resin material, spherulites are formed with the nano-sized nucleating agent particles as crystal nuclei.

[0038] In this case, since the nucleating agent vesicles obtained by the supercritical reverse phase evaporation method are extremely small in size, the average particle size of the spherulites in the crystalline portion of the crystalline polypropylene resin can be made extremely small, and the crystallinity of the crystalline portion can be dramatically improved.

[0039] In the decorative sheet 1 of the present invention, by incorporating a nano-sized nucleating agent, more preferably nucleating agent vesicles, into the transparent resin layer 5, the average particle size of the spherulites in the crystalline portion of the crystalline polypropylene resin is made extremely small, thereby realizing excellent abrasion resistance. In particular, by incorporating nucleating agent vesicles, the nucleating agent is uniformly dispersed in the crystalline polypropylene resin, and the crystallinity of the crystalline polypropylene is controlled to optimize the hardness and toughness of the transparent resin layer, thereby realizing excellent abrasion resistance and post-processing resistance with a tensile modulus of 800 MPa or more and 2000 MPa or less, and a tensile elongation at break of 200% or more.

[0040] The terms used in the above description will be briefly explained below. Nucleating agents are added to promote the formation of crystal nuclei during resin crystallization or to convert the nucleating agent itself into a crystal nucleus. These include melt-type nucleating agents, which melt into the base resin upon addition and re-precipitate to form crystal nuclei, and non-melt-type nucleating agents, which do not melt and remain as crystal nuclei after addition to the base resin. Examples of nucleating agents for polypropylene resin include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in the present invention, in order to maximize the effects of nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts, which are non-melt-type and expected to have good transparency. However, if transparency can be achieved by nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. Furthermore, melt-type benzylidene sorbitol may be appropriately mixed with a non-melt-type nucleating agent.

[0041] The haze value is a percentage value obtained by subtracting the integral value of only the linear components of the light rays emitted from one surface (linear transmittance) from the integral value of all the light rays emitted from the other surface (total luminous transmittance), and dividing the result (diffuse transmittance) by the total luminous transmittance. The smaller the value, the higher the transparency. This haze value is determined by internal haze, which is determined by the internal state of the object, such as the degree of crystallinity and spherulite size in the crystalline part, and external haze, which is determined by the surface state of the object, such as the presence or absence of irregularities on the entrance and exit surfaces. In the present invention, when simply referring to the haze value, it means a value determined by internal haze and external haze.

[0042] The tensile elongation at break is a value that represents the elongation when a sample is pulled at a specified speed and breaks. It is calculated by subtracting the length of the sample before the test (L0) from the length of the sample at break (L), dividing this value by the length of the sample before the test (L0), and expressing it as a percentage. The smaller the value, the poorer the elongation, which will cause cracking and whitening during post-processing such as V-groove bending, and therefore poorer post-processing resistance. The larger the value, the better the elongation, which will allow for easier post-processing, and therefore better post-processing resistance.

[0043] The isotactic pentad fraction (mmmm fraction) is calculated from the numerical value (electromagnetic wave absorption rate) obtained by resonating the resin material constituting the transparent resin layer at a predetermined resonance frequency using C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclear species) with a mass number of 13. This value defines the atomic arrangement, electronic structure, and molecular microstructure of the resin material. The isotactic pentad fraction of a polypropylene resin is the proportion of five propylene units arranged in a row as determined by C-NMR and is used as a measure of crystallinity or stereoregularity. This isotactic pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface. Basically, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, and therefore the better the scratch resistance.

[0044] Furthermore, the transparent resin layer 5 may contain, as needed, one or more additives selected from a variety of 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.

[0045] The method for producing the transparent resin layer 5 is not particularly limited, and the layer can be produced by a conventionally known method. In this embodiment, the layer is preferably formed by extrusion molding, and more preferably, the extrusion molding is performed by a T-die method or an inflation method.

[0046] 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.

[0047] <Surface protective layer> The surface protective layer 6 is laminated on one side of the transparent resin layer 5 (the upper side in Figure 1), and is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1.

[0048] The surface protection layer 6 can be made of a thermosetting resin or an ionizing radiation curable resin, and is formed using, for example, an acrylic resin composition. Furthermore, the surface protective layer 6 may contain various additives, such as weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss adjusters, as needed. Furthermore, the surface protective layer 6 may contain functional additives such as antibacterial agents and antifungal agents, if necessary.

[0049] <Uneven part> The uneven portion 7 is formed by recesses provided at a plurality of locations on the transparent resin layer 5 and the surface protection layer 6.

[0050] <Primer layer> The primer layer 8 is a base layer that serves to improve 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). The primer layer 8 is formed using, for example, a polyester resin, an organic additive, a pigment, and the like.

[0051] 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. The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even in forms other than this embodiment, as long as they do not deviate from the technical idea of ​​the present invention.

[0052] (Effects of this embodiment) The decorative sheet 1 of this embodiment can achieve the following effects. (1) The colored substrate layer 2 contains virgin resin and recycled resin, and the colored substrate layer 2 itself contains 10% to 80% recycled resin. By limiting the proportion of recycled resin contained in the colored substrate layer 2 to 10% or more and 80% or less, it is possible to reduce color variations in the decorative sheet 1 caused by the inclusion of recycled resin, and also to suppress deterioration in the physical properties of the colored substrate layer 2 caused by the inclusion of recycled resin. (2) Since a nano-sized nucleating agent is added to the transparent resin layer 5, the hardness of the transparent resin layer 5 can be improved, and the hardness of the entire decorative sheet 1 can be improved. (3) Not only the colored substrate layer 2 but also the transparent resin layer 5 is formed from recycled resin, which can further contribute to environmental conservation. (4) The colored substrate layer 2 contains, as an inorganic substance, one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, a titanium composite, and oxides thereof. Therefore, it is possible to form a colored substrate layer 2 having the same degree of hiding power as when the colored substrate layer 2 is formed using only virgin materials. (5) Since the colored substrate layer 2 contains one or more of a benzotriazole-based weather resistant agent, a triazine-based weather resistant agent, and HALS (Hindered Amine Light Stabilizers), the weather resistance of the decorative sheet 1 can be improved. (6) The decorative sheet 1 contains 5% or more recycled resin throughout, which contributes to environmental conservation. (7) The decorative material 10 comprises a substrate 9 and a decorative sheet 1 laminated on at least one surface of the substrate 9. As a result, even when formed using recycled resin, it is possible to provide a decorative material 10 that can suppress a decrease in surface hardness and suppress color variation. [Example]

[0053] Examples and comparative examples will be described below with reference to this embodiment. Example 1 A colored polypropylene resin was extrusion-molded to form a colored substrate layer, and one side of the colored substrate layer was subjected to a corona discharge treatment. A pattern layer printed with a urethane-based printing ink, an adhesive layer made of a urethane-based adhesive, and an adhesive resin layer made of a transparent resin were then laminated in this order. A transparent resin layer was then extrusion-molded onto the adhesive resin layer, and a surface protection layer made primarily of an acrylic resin composition was laminated onto this transparent resin layer. The other side of the colored substrate layer was then subjected to a corona discharge treatment, and a primer layer was then formed. This resulted in a decorative sheet.

[0054] Next, a substrate was attached to the primer layer side of the decorative sheet using "BA-10L (hardener: BA-11B)" manufactured by Japan Coating Resin Co., Ltd., to form the decorative material of Example 1. MDF (medium density fiberboard) was used as the substrate.

[0055] (Colored base material layer) Material: Polypropylene Thickness: 60μm ·Colored base material layer composition Colored polypropylene resin Polypropylene recycled resin: Post-industrial recycled material (PIR): (content) 60% of the colored base layer composition UV absorber: Tinuvin 326 (manufactured by BASF Japan Ltd.): 0.25 parts by weight Light stabilizer: Tinuvin XT55 (manufactured by BASF Japan Ltd.): 0.5 parts by weight

[0056] (Transparent resin layer) Material: Polypropylene Thickness: 70μm ·Transparent resin layer composition Transparent homopolypropylene resin: Prime Polypro; manufactured by Prime Polymer Co., Ltd.: 99 parts by weight Polypropylene recycled resin: Post-industrial recycled material (PIR) UV absorber: Tinuvin 326 (manufactured by BASF Japan Ltd.): 0.5 parts by weight Light stabilizer: Tinuvin XT55 (manufactured by BASF Japan Ltd.): 0.5 parts by weight Nano-nucleating agents

[0057] (Surface protective layer) Thickness: 5μm ·Surface protective layer composition Main ingredient: methyl methacrylate / cyclohexyl methacrylate = 80 / 20:90 parts by weight UV absorber: Tinuvin 329 (manufactured by BASF Japan Ltd.): 6 parts by weight Light stabilizer: Tinuvin 292 (manufactured by BASF Japan Ltd.): 4 parts by weight Hardener: Takenate D170; Mitsui Chemicals, Inc.: 10 parts by weight Solvent (ethyl acetate): 240 parts by weight

[0058] (primer layer) Thickness: Between 1 μm and 2 μm (decorative sheet) Thickness: Between 135 μm and 140 μm

[0059] <Example 2> A decorative material was prepared in the same manner as in Example 1, except that the amount of recycled polypropylene resin added to the colored substrate layer was 40% of the colored substrate layer composition. Example 3 In Example 1, a decorative material was prepared using the same procedure as in Example 1, except that the amount of recycled polypropylene resin added to the colored substrate layer was 60% of the colored substrate layer composition, and no recycled resin was used as the polypropylene resin in the transparent resin layer.

[0060] Example 4 In Example 1, a decorative material was prepared using the same procedure as in Example 1, except that the amount of recycled polypropylene resin added to the colored substrate layer was 40% of the colored substrate layer composition, and no recycled resin was used as the polypropylene resin in the transparent resin layer. <Example 5> In Example 1, a decorative material was prepared using the same procedure as in Example 1, except that the amount of recycled polypropylene resin added to the colored substrate layer was 10% of the colored substrate layer composition, and no recycled resin was used as the polypropylene resin in the transparent resin layer.

[0061] Example 6 In Example 1, a decorative material was prepared using the same procedure as in Example 1, except that the amount of recycled polypropylene resin added to the colored substrate layer was 80% of the colored substrate layer composition, and no recycled resin was used as the polypropylene resin in the transparent resin layer. Example 7 A decorative material was prepared in the same manner as in Example 1, except that no nano-nucleating agent was added to the transparent resin layer.

[0062] Example 8 A decorative material was produced in the same manner as in Example 1, except that no nano-nucleating agent was added to the transparent resin layer and no recycled resin was used as the polypropylene resin for the transparent resin layer.

[0063] <Comparative Example 1> In Example 1, the colored substrate layer was formed using only colored polypropylene resin as polypropylene without adding recycled polypropylene resin, and a decorative material was produced using the same procedure as in Example 1, except that no nano-nucleating agent was added to the transparent resin layer. <Comparative Example 2> A decorative material was produced in the same manner as in Example 1, except that the amount of recycled polypropylene resin added to the colored substrate layer was 85% of the colored substrate layer composition.

[0064] <Comparative Example 3> A decorative material was produced in the same manner as in Comparative Example 1, except that recycled resin was not used as the polypropylene resin for the transparent resin layer. <Comparative Example 4> In Comparative Example 2, a decorative material was produced in the same manner as in Comparative Example 2, except that recycled resin was not used as the polypropylene resin for the transparent resin layer.

[0065] (Performance evaluation, evaluation results) Each of the evaluation decorative materials of Examples 1 to 8 and 2 and Comparative Examples 1 to 4 was subjected to a pencil hardness test, a coin scratch test, and evaluation of suitability for extrusion film formation, and virgin dependency. The evaluation was carried out by the method described below.

[0066] <Pencil hardness test> The pencil hardness (pencil hardness) of the surface of the decorative sheet side of each evaluation decorative material was measured by a scratch hardness (pencil method) test specified in JIS K5600-5-4:1999 as a pencil hardness test. The pencil hardness was measured using an automatic pencil hardness tester (manufactured by Yoshimitsu Seiki Co., Ltd., model number C221A). After conducting the pencil hardness test using pencils of different hardness, the surface hardness was evaluated by checking for damage (gouges) that occurred on the surface (surface protective layer).

[0067] The evaluation criteria are as follows: ◎: When damage occurs to the surface after performing a pencil hardness test using a pencil with a pencil hardness of 2B or higher. ○: When damage occurs to the surface after performing a pencil hardness test using a pencil with a pencil hardness of 4B or higher. ×: Damage to the surface occurs after the pencil hardness test is performed using a pencil with a pencil hardness of "5B" or less.

[0068] <Coin scratch test> A coin scratch test was carried out on the surface of the decorative sheet side of each evaluation decorative material, and the load when no continuous scratches were produced on the surface of the decorative sheet side was measured. In the coin scratch test, a 10 yen coin with no jagged edges was placed on the surface of the decorative sheet at a 45°C angle, and the test was started with a load of 1 kg, gradually increasing the load by 1 kg each time up to 4 kg. The coin was scratched at a speed of 100 mm per minute, and the load at which scratches began to appear was visually confirmed.

[0069] The evaluation criteria are as follows: 〇: No continuous scratches were observed on the surface. The maximum load was 2 kg or more. ×: No continuous scratches were observed on the surface. The maximum load was less than 2 kg.

[0070] <Suitable for extrusion film formation> An evaluation was made to see if there was any problem in the film formation of the colored substrate layer on the production line. The evaluation criteria are as follows: ⊚: A colored substrate layer can be formed in the same manner as when only virgin polypropylene resin is used as the polypropylene resin without using recycled polypropylene resin. ◯: Although some ingenuity is required, it is possible to form a colored substrate layer in the same manner as when only virgin polypropylene resin is used as the polypropylene resin without using recycled polypropylene resin. Δ: It is difficult to form a colored substrate layer, as in the case where only virgin polypropylene resin is used as the polypropylene resin without using recycled polypropylene resin.

[0071] <Virgin Dependence> Low: Recycled polypropylene resin is used for the colored base layer. High: Recycled polypropylene resin is not used in the colored base layer. The evaluation results are shown in Table 1.

[0072] [Table 1]

[0073] As a result of evaluating various performance characteristics using the above-mentioned methods, the decorative materials of Examples 1 to 8, which used recycled polypropylene resin and virgin polypropylene resin for the colored substrate layer, and in which the colored substrate layer alone contained 10% to 80% recycled polypropylene resin and had low virginity dependency, obtained good results in pencil hardness tests, coin scratch tests, and extrusion film formation suitability, and Examples 1 to 6, in which a nano-nucleating agent was added to the transparent resin layer, showed better results in the pencil hardness test than the decorative materials of Examples 7 and 8, in which no nano-nucleating agent was added. Furthermore, the decorative materials of Examples 1 to 8 were evaluated as "○" or "◎," demonstrating performance within the acceptable range comparable to the evaluation results of the decorative materials of Comparative Examples 1 and 3, which used only virgin polypropylene resin without virgin polypropylene resin as the polypropylene resin for the colored substrate layer, and it was confirmed that even decorative materials using virgin polypropylene resin can be obtained with performance comparable to that of decorative materials not using virgin polypropylene resin.

[0074] On the other hand, the decorative materials of Comparative Examples 2 and 4, which used recycled polypropylene resin and virgin polypropylene resin for the colored substrate layer but contained 85% recycled polypropylene resin in the colored substrate layer alone, showed results similar to those of Examples 1 to 8 in the pencil hardness test and coin scratch test, but had low suitability for extrusion film formation, making it difficult to form a colored substrate layer, just as when only virgin polypropylene resin was used as the polypropylene resin.

[0075] The present invention can have the following configurations, for example. (1) A colored thermoplastic resin layer, an adhesive layer, and a transparent thermoplastic resin layer are provided in this order, The decorative sheet is characterized in that the colored thermoplastic resin layer is a layer made of a resin composition containing virgin resin and recycled resin, and the colored thermoplastic resin layer alone contains 10% to 80% of the recycled resin. (2) The decorative sheet according to (1) above, wherein the transparent thermoplastic resin layer contains a nano-sized nucleating agent. (3) The decorative sheet according to (1) or (2) above, characterized in that each of the colored thermoplastic resin layer and the transparent thermoplastic resin layer is composed of one of polypropylene resin, polyethylene resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and vinyl chloride resin. (4) the colored thermoplastic resin layer contains an inorganic substance, The decorative sheet according to any one of (1) to (3) above, characterized in that the inorganic substance is one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and oxides thereof. (5) The decorative sheet according to any one of (1) to (4) above, characterized in that the colored thermoplastic resin layer contains one or more of a benzotriazole-based weathering agent, a triazine-based weathering agent, and a HALS (Hindered Amine Light Stabilizer). (6) A decorative sheet according to any one of (1) to (5) above, characterized in that it contains 5% or more of recycled resin in total. (7) A substrate; A decorative material comprising the decorative sheet according to any one of (1) to (6) above laminated on at least one surface of the substrate. [Explanation of symbols]

[0076] 1 decorative sheet 2 Colored base material layer (colored thermoplastic resin layer) 3. Picture layer 4 Adhesive resin layer (adhesive layer) 5 Transparent resin layer (transparent thermoplastic resin layer) 6 Surface protective layer 7 Uneven part 8 Primer layer 9 Base material 10 Cosmetic materials

Claims

1. A colored thermoplastic resin layer, an adhesive layer, and a transparent thermoplastic resin layer are provided in this order, The decorative sheet is characterized in that the colored thermoplastic resin layer is a layer made of a resin composition containing virgin resin and recycled resin, and the colored thermoplastic resin layer alone contains 10% to 80% of the recycled resin.

2. 2. The decorative sheet according to claim 1, wherein the transparent thermoplastic resin layer contains a nano-sized nucleating agent.

3. The decorative sheet according to claim 1 or 2, characterized in that each of the colored thermoplastic resin layer and the transparent thermoplastic resin layer is composed of one of polypropylene resin, polyethylene resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and vinyl chloride resin.

4. the colored thermoplastic resin layer contains an inorganic substance, 3. The decorative sheet according to claim 1, wherein the inorganic substance is one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and oxides thereof.

5. 3. The decorative sheet according to claim 1, wherein the colored thermoplastic resin layer contains one or more of a benzotriazole-based weathering agent, a triazine-based weathering agent, and a HALS (hindered amine light stabilizer).

6. 3. The decorative sheet according to claim 1 or 2, characterized in that it contains 5% or more of recycled resin in total.

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

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