Decorative sheet and decorative laminate using the same

Abstract

To provide: a decorative sheet capable of significantly reducing discoloration of a pattern layer even if a side of the pattern layer disposed on a raw fabric layer is bonded to a woody substrate; and a decorative laminate using the decorative sheet.SOLUTION: A decorative sheet 10 includes: a raw fabric layer 14 composed of a single layer film containing transparent thermoplastic resin and at least one of a nucleating agent and an inorganic filler; a surface protection layer 15 disposed on a side of a surface of the raw fabric layer 14; a pattern layer 13 disposed on a side of a rear surface of the raw fabric layer 14; and a coloring layer 12 disposed on a side of a rear surface of the pattern layer 13. The decorative sheet includes a barrier layer 16 that is disposed on a side of a rear surface of the coloring layer 12 and is composed of an acrylic resin material.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet for decorating the interior surfaces of a house or the like, and a decorative board utilizing the same. [Background technology]

[0002] For example, decorative sheets are used to decorate the surfaces of interior fittings (e.g., interior doors, entrance storage, etc.), construction materials (e.g., trim, moldings, baseboards, window frames, door frames, etc.), and floors in houses, etc. In recent years, olefin-based resin materials have been mainly used for such decorative sheets due to the problem of gas generated during combustion (see, for example, Patent Documents 1 to 3 below, etc.).

[0003] In order to prevent damage to the surface pattern due to wear, such decorative sheets are widely used in which a pattern is printed on a colored olefin resin film, and then a transparent olefin resin film is attached to laminate the pattern. Such conventional decorative sheets are produced through two steps, a printing step for printing the pattern, and a lamination step for attaching a film to the surface of the pattern, which is time-consuming.

[0004] Therefore, a design layer is provided by directly printing a design on the back surface of an original layer made of a transparent olefin-based resin material, thereby eliminating the need for a lamination process and simplifying the manufacturing process (see, for example, Patent Document 4 below). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2006-110929 A [Patent Document 2] JP 2015-199313 A [Patent Document 3] JP 2016-101663 A [Patent Document 4] International Publication No. 2022 / 107701 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in a decorative board in which the above-mentioned decorative sheet is bonded to a wood-based substrate such as medium density fiberboard (MDF), particle board, or plywood, the terpenes in the substrate may diffuse to the decorative sheet side and discolor the design layer. In particular, if the design layer is light-colored, there is a high possibility that it will be discolored by caryophyllene such as α-caryophyllene or β-caryophyllene. Caryophyllene is a volatile organic compound that is released from heat-treated compressed wood used for wood-based substrates, and is a type of terpene.

[0007] For these reasons, the present invention aims to provide a decorative sheet and a decorative board utilizing the same that can significantly suppress discoloration of the pattern layer even when the pattern layer provided on the base layer is bonded to a wood-based substrate. [Means for solving the problem]

[0008] In order to solve the above-mentioned problems, the decorative sheet of the present invention is a decorative sheet comprising an original fabric layer made of a single-layer film containing a transparent thermoplastic resin and at least one of a nucleating agent and an inorganic filler, a surface protective layer provided on the front side of the original fabric layer, a pattern layer provided on the back side of the original fabric layer, and a colored layer provided on the back side of the pattern layer, and is characterized in having a barrier layer made of an acrylic resin material provided on the back side of the colored layer.

[0009] The decorative sheet according to the present invention is the decorative sheet described above, wherein the barrier layer has a thickness of 1 g / m 2 More than 6g / m 2 It is preferable that the following is provided.

[0010] In addition, the decorative sheet of the present invention is preferably such that, in the above-mentioned decorative sheet, the raw fabric layer has a core portion and a skin portion located on at least one of the sides, either side, of the core portion, and the skin portion contains the thermoplastic resin and at least one of the nucleating agent and the inorganic filler.

[0011] In addition, the decorative sheet according to the present invention is preferably the above-mentioned decorative sheet, in which an embossed portion is formed on the outermost surface in harmony with the pattern of the pattern layer.

[0012] In addition, the decorative sheet of the present invention is preferably such that, in the above-mentioned decorative sheet, the surface protective layer has a first protective layer and a second protective layer provided between the first protective layer and the base fabric layer, and the first protective layer is provided so as to be in harmony with the pattern of the pattern layer.

[0013] In the decorative sheet according to the present invention, it is preferable that the first protective layer has a higher gloss than the second protective layer.

[0014] In addition, the decorative sheet according to the present invention is preferably the decorative sheet described above, further comprising a base layer provided on the back surface side of the barrier layer.

[0015] In addition, the decorative sheet according to the present invention is preferably the decorative sheet described above, further comprising a moisture-proof layer provided on the back surface side of the barrier layer.

[0016] In the decorative sheet according to the present invention, it is preferable that a base layer is provided on the back surface side of the moisture-proof layer in the above-mentioned decorative sheet.

[0017] On the other hand, in order to solve the above-mentioned problems, the decorative board of the present invention is characterized in that it comprises the above-mentioned decorative sheet, a wood-based substrate provided on the back side of the base layer of the decorative sheet, and an adhesive layer provided between the base layer of the decorative sheet and the substrate.

[0018] In the decorative board according to the present invention, it is preferable that a moisture-proof layer is provided on the back surface side of the substrate in the above-mentioned decorative board. Effect of the Invention

[0019] With the decorative sheet of the present invention and the decorative board utilizing the same, even if a wood-based substrate is adhered to the colored layer and patterned layer side of the base layer, the barrier layer made of acrylic resin can suppress the diffusion of volatile organic compounds in the wood-based substrate, thereby significantly suppressing discoloration of the colored layer and patterned layer. [Brief description of the drawings]

[0020] [Figure 1] 1 is a cross-sectional view showing a schematic structure of a first embodiment of a decorative sheet according to the present invention. [Diagram 2] 2 is a cross-sectional view showing a schematic structure of a first embodiment of a decorative board that uses the decorative sheet of FIG. 1. [Diagram 3] FIG. 2 is a cross-sectional view showing a schematic structure of a second embodiment of a decorative sheet according to the present invention. [Figure 4] FIG. 2 is a cross-sectional view showing a schematic structure of a third embodiment of a decorative sheet according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The embodiments of the decorative sheet and the decorative board using the same according to the present invention will be described with reference to the drawings. Note that the present invention is not limited to the following embodiments described with reference to the drawings, and various technical matters described in each embodiment can be appropriately combined or replaced as necessary.

[0022] [First embodiment] A first embodiment of a decorative sheet and a decorative board using the same according to the present invention will be described with reference to FIGS.

[0023] <Basic structure of decorative sheet> As shown in Fig. 1, a colored layer 12 that imparts a desired color is provided on a base layer 11 that improves adhesion to a surface to be attached, such as a flooring material or a wall surface. A pattern layer 13 that is printed with a pattern to impart design is provided on the colored layer 12. A base fabric layer 14 formed of a transparent thermoplastic resin film that serves as a support is provided on the pattern layer 13. A surface protection layer 15 that protects the outermost surface and adjusts the gloss is provided on the base fabric layer 14.

[0024] A barrier layer 16 that suppresses gas permeation is provided between the base layer 11 and the colored layer 12. The surface protective layer 15 has an overcoat layer 15B that is a first protective layer, and an undercoat layer 15A that is a second protective layer provided between the overcoat layer 15B and the original fabric layer 14. That is, the surface protective layer 15 is composed of two layers of two kinds, the undercoat layer 15A and the overcoat layer 15B in this order.

[0025] That is, in the decorative sheet 10, a surface protective layer 15 is provided on one surface side of an original fabric layer 14 made of a single-layer film, a pattern layer 13 is provided with its surface side facing one surface side to a back surface side that is the other surface side of the original fabric layer 14, and a colored layer 12 is provided with its surface side facing one surface side to a back surface side that is the other surface side of the pattern layer 13. Furthermore, the decorative sheet 10 does not have a laminate layer formed of another film on the surface side and back surface side of the original fabric layer 14.

[0026] Such decorative sheets 10 are used, for example, by being attached to the surfaces of interior fittings in a house (e.g., interior doors, entrance storage, etc.) and construction materials (e.g., trim, moldings, baseboards, window frames, door frames, etc.).

[0027] In the decorative sheet 10 described above, when the barrier layer 16 functions as a base layer, it is possible to omit the base layer 11. That is, the barrier layer 16 can also serve as the base layer 11. In addition, when the adhesion between the design layer 13 and the base fabric layer 14 is insufficient, it is also possible to interpose an adhesive layer between the design layer 13 and the base fabric layer 14.

[0028] In other words, the decorative sheet 10 has a structure having, in this order, at least a colored layer 12, a design layer 13, a base layer 14, a surface protective layer 15, and a barrier layer 16. Each layer will now be described in detail.

[0029] <Configuration of each layer of the decorative sheet> 《Base layer 11》 As shown in Fig. 1, the underlayer 11 is located on the back side of the original fabric layer 14 and is provided mainly for the purpose of improving adhesion, and also has functions such as surface stabilization after surface treatment, corrosion protection of the metal surface, imparting adhesion, and preventing deterioration of the adhesive. The underlayer 11 is provided on the back side of the original fabric layer 14, laminated on the barrier layer 16. In other words, the underlayer 11 is provided on the side opposite to the side of the barrier layer 16 on which the colored layer 12 is provided. The underlayer 11 is printed on the barrier layer 16 with a solid content of 1 g / m2 by, for example, gravure printing or the like. 2 The urethane resin is applied to the surface so as to form the void.

[0030] 《Colored layer 12》 1, the colored layer 12 is located on the back side of the base layer 14, more specifically, on the back side of the design layer 13, and on the front side of the undercoat layer 11, more specifically, on the front side of the barrier layer 16, and is provided mainly for the purpose of imparting concealment. The colored layer 12 can be provided by printing with a two-component curing urethane resin, for example, by gravure printing or the like. The two-component curing urethane resin can also be a urethane resin mixed with a white pigment such as titanium oxide.

[0031] "Pattern layer 13" 1, the pattern layer 13 is located on the back side of the base fabric layer 14 and on the front side of the colored layer 12, and is provided mainly for the purpose of imparting design. The pattern layer 13 is formed by printing a pattern with ink such as urethane resin by a printing method or the like.

[0032] As the printing method, various printing methods such as gravure printing, offset printing, letterpress printing, flexographic printing, screen printing, inkjet printing, and electrostatic printing can be used.

[0033] Examples of inks that can be used include urethane-based resins, for example, vinyl chloride-vinyl acetate-based inks (cyan, magenta, yellow), and colorants such as organic or inorganic dyes or pigments, as well as inks in which various additives such as fillers, tackifiers, plasticizers, stabilizers, dispersants, defoamers, leveling agents, surfactants, and drying agents are dispersed in a binder made of synthetic resin or the like together with a solvent or diluent.

[0034] The type of pattern of the picture layer 13 may be any type depending on the purpose of use, the preferences of the user, etc., and common examples include wood grain patterns, stone patterns, abstract patterns, etc. The types of patterns are not limited to the types exemplified above, and may be, for example, a full-surface solid print.

[0035] "Original Layer 14" The thickness of the raw fabric layer 14 is preferably in the range of 50 μm to 150 μm, and more preferably in the range of 70 μm to 120 μm. When the thickness of the raw fabric layer 14 is 50 μm or more, the decorative sheet 10 can be given a suitable strength when used as a flooring material, and scratch resistance can be improved. In particular, when the thickness of the raw fabric layer 14 is 70 μm or more, the strength can be further increased, and scratch resistance can be more reliably improved.

[0036] On the other hand, when the thickness of the raw fabric layer 14 is 150 μm or less, the decorative sheet 10 can be made both thin and strong while suppressing defects such as whitening and cracking during processing, i.e., the processing suitability can be improved, and sufficient transparency can be maintained to allow the pattern of the pattern layer 13 to be seen from the front side (the surface protection layer 15 side). In particular, when the thickness of the raw fabric layer 14 is 120 μm or less, the decorative sheet 10 can be made both thin and strong while more reliably improving the processing suitability.

[0037] A film in which a weathering agent or the like is added to a transparent thermoplastic resin is applied to the raw fabric layer 14. The thermoplastic resin constituting the raw fabric layer 14 is not particularly limited, and the same material as the thermoplastic resin used as a base layer or the like in conventional decorative sheets can be used.

[0038] Specific examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate, polyarylate, and polycarbonate; olefins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid (ester) copolymer, and ethylene-unsaturated carboxylic acid copolymer metal neutralized product (ionomer); Examples of the resin include polyolefin-based resins such as poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, polyacrylamide, and other acrylic resins, polyamide-based resins such as 6-nylon, 6,6-nylon, and 6,10-nylon, styrene-based resins such as polystyrene, AS resin, and ABS resin, vinyl-based resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, and polyvinyl butyral, fluorine-based resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and ethylene-perfluoroalkyl vinyl ether copolymer, and mixtures, copolymers, composites, and laminates of two or more of these resins.

[0039] In particular, in view of the recent increase in social interest in environmental issues, it is not preferable to use a thermoplastic resin containing chlorine (halogen), such as polyvinyl chloride resin, as the thermoplastic resin, and it is preferable to use a non-halogen thermoplastic resin. In particular, from the viewpoints of various physical properties, processability, versatility, economic efficiency, etc., it is preferable to use a polyester resin (amorphous or biaxially stretched) or a polyolefin resin as the non-halogen thermoplastic resin, and more preferably, a polyolefin resin. For example, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more as the polyolefin resin.

[0040] The raw fabric layer 14 is formed by adding a dispersant or the like as a nano-sized additive to a transparent thermoplastic resin (hereinafter also referred to as "dispersant nano specification"). It is also possible to use the raw fabric layer 14 to which a weathering agent has been added. The raw fabric layer 14 contains a resin material and a nucleating agent that improves the crystallinity of the resin material, and has an uneven surface. The nucleating agent is added to the resin material in the form of nucleating agent vesicles that are encapsulated in an outer membrane and turned into vesicles.

[0041] The raw fabric layer 14 contains a nucleating agent as a nano-sized additive. The nano-sized nucleating agent is preferably used by being added to the thermoplastic resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a single-layer outer membrane. The nucleating agent in the thermoplastic resin constituting the raw fabric layer 14 can also be encapsulated in a vesicle with a part of the nucleating agent exposed. Since the raw fabric layer 14 contains a nucleating agent, it can improve the crystallization degree and improve the scratch resistance (scratch resistance) of the decorative sheet 10.

[0042] It is preferable that the average particle size of the nano-sized nucleating agent is 1 / 2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is 400 nm or more and 750 nm or less, it is preferable that the average particle size is 375 nm or less.

[0043] Nano-sized nucleating agents have extremely small particle sizes, so 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 closer, so that when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the end of the growing crystal immediately comes into contact with the end of the crystal growing from the surface of another nucleating agent particle adjacent to the one nucleating agent particle, and the ends of the crystals hinder each other's growth, stopping the growth of each crystal.

[0044] Therefore, the average particle size of the spherulites in the crystalline portion of the crystalline resin can be reduced, for example, the size of the spherulites can be reduced to 1 μm or less. As a result, a resin film with high crystallinity and high hardness can be obtained, and stress concentration between the spherulites that occurs during bending can be efficiently dispersed, thereby realizing a resin film that suppresses cracking and whitening during bending.

[0045] When a nucleating agent is simply added, the particle size becomes larger due to secondary aggregation of the nucleating agent in the resin. On the other hand, when a nucleating agent vesicle is added, the dispersibility in the resin is improved, so the number of crystal nuclei per amount of nucleating agent added is significantly increased compared to when a nucleating agent is simply added. As a result, the average particle size of the spherulites in the crystalline part of the resin becomes smaller, and the occurrence of cracks and whitening during bending processing can be suppressed. Therefore, by adding a nucleating agent vesicle, the degree of crystallization can be further increased, and it is possible to achieve both improved elastic modulus and processability.

[0046] The raw fabric layer 14 is formed of a resin material to which a nucleating agent is added, for example, in an amount of preferably 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass, relative to 100 parts by mass of polypropylene resin as the main component. When a nucleating agent vesicle is used, the amount of the nucleating agent added to the resin material is the amount of the nucleating agent added converted into the amount of the nucleating agent in the nucleating agent vesicle. The "main component" refers to a resin material that occupies 50% or more by mass of the resin material constituting the raw fabric layer 14.

[0047] If the amount of the nucleating agent added is less than 0.05 parts by mass, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the raw fabric layer 14 may not be sufficiently improved. If the amount of the nucleating agent added is more than 0.5 parts by mass, the spherulite growth of the polypropylene may be inhibited due to an excess of crystal nuclei, and as a result, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the raw fabric layer 14 may not be sufficiently improved.

[0048] Methods for nano-sizing a nucleating agent include, for example, a solid-phase method in which the nucleating agent is primarily subjected to mechanical grinding to obtain nano-sized particles, a liquid-phase method in which nano-sized particles are synthesized or crystallized in a nucleating agent or a solution in which the nucleating agent is dissolved, and a gas-phase method in which nano-sized particles are synthesized or crystallized from a nucleating agent or a gas or vapor comprising the nucleating agent.

[0049] Examples of the solid phase method include a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, a jet mill, etc. Examples of the liquid phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid phase reduction method, a hydrothermal synthesis method, etc. Examples of the gas phase method include an electric furnace method, a chemical flame method, a laser method, a thermal plasma method, etc.

[0050] The method of nano-sizing the nucleating agent is preferably the supercritical reverse phase evaporation method. The supercritical reverse phase evaporation method is a method of producing a capsule (nano-sized vesicle) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030MPa). Carbon dioxide under temperature or pressure conditions above the critical point means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical condition.

[0051] In the specific nano-processing by the supercritical reverse phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipids as an outer membrane forming substance, and a nucleating agent as an encapsulating substance, and an emulsion of supercritical carbon dioxide and aqueous phase is generated by stirring. Next, the pressure is reduced, causing the carbon dioxide to expand and evaporate, resulting in phase inversion, and generating nanocapsules (nanovesicles) in which the phospholipids cover the surface of the nucleating agent particles with a single layer membrane. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer membrane on the surface of the nucleating agent particles becomes multiple membranes, it is possible to easily generate capsules with a single layer membrane, and therefore to prepare capsules with a smaller diameter.

[0052] The nucleating agent vesicle is prepared, for example, by the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method, etc. Among these, the nucleating agent vesicle is preferably prepared by using the supercritical reverse phase evaporation method.

[0053] The outer membrane constituting the nucleating agent vesicle is, for example, composed of a monolayer membrane. The outer membrane is composed of a substance containing a biological lipid such as a phospholipid. In this specification, the nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome.

[0054] Examples of phospholipids constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin; sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0055] Other substances that form the outer membrane of the vesicle include dispersants such as nonionic surfactants and mixtures of these with cholesterols or triacylglycerols.

[0056] As the nonionic surfactant, for example, one or more of polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. can be used.

[0057] Examples of cholesterols that can be used include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadiene-3β-ol), sodium cholate, and cholecalciferol.

[0058] The outer membrane of the liposome can also be formed from a mixture of phospholipids and a dispersant. In the decorative sheet 10 according to this embodiment, it is preferable that the nucleating agent vesicle is a radical scavenger liposome having an outer membrane made of phospholipids, and by forming the outer membrane from phospholipids, it is possible to improve the compatibility between the resin material, which is the main component of the decorative sheet 10, and the vesicle.

[0059] The nucleating agent is not particularly limited as long as it is a substance that is the starting point of crystallization when the resin crystallizes. Examples of the nucleating agent include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts that are non-melting and can be expected to have good transparency, but if the material itself can be made transparent by the nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. It is also possible to appropriately mix melting benzylidene sorbitol with a non-melting nucleating agent.

[0060] As described above, in the decorative sheet 10 according to this embodiment, the raw fabric layer 14 is formed containing a resin material (for example, a polyolefin-based thermoplastic resin such as a transparent polypropylene resin) and a nucleating agent. In addition, the raw fabric layer 14 preferably contains one or more additives selected from various additives such as 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, as necessary.

[0061] Furthermore, the decorative sheet 10 according to this embodiment is characterized in that a nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material when forming the raw fabric layer 14. By adding the nucleating agent encapsulated in vesicles to the resin composition, the dispersibility of the nucleating agent in the resin material, i.e., in the raw fabric layer 14, is dramatically improved.

[0062] However, it may be difficult or impractical to directly identify the nucleating agent encapsulated in the vesicles based on the structure and properties of the finished decorative sheet 10, depending on the circumstances. The reasons for this are as follows.

[0063] The nucleating agent added in the form of vesicles is in a dispersed state with high dispersibility, and is also highly dispersed in the raw fabric layer 14 in the form of a laminate, which is the precursor of the produced decorative sheet 10. However, in the process of producing the decorative sheet 10, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment, and such treatments may cause the outer membrane of the vesicles encapsulating the nucleating agent to break down or cause a chemical reaction.

[0064] For this reason, depending on the processing steps of the decorative sheet 10, there is variation in the state in which the outer membrane of the nucleating agent in the completed decorative sheet 10 is broken or a chemical reaction occurs, and there is a high possibility that the nucleating agent is not encapsulated (enveloped) by the outer membrane. If the nucleating agent is not encapsulated by the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself within a numerical range, and it is also expected that it may be difficult to determine whether the constituent material of the broken outer membrane is the outer membrane of the vesicle or a material added separately from the nucleating agent.

[0065] Thus, although the present invention differs from the prior art in that the nucleating agent is highly dispersed in the decorative sheet 10, it is anticipated that there may be cases in which it is impractical to determine within a numerical range a structure or characteristics of the decorative sheet 10 that are analyzed based on measurements, whether this is because the nucleating agent is added in the form of vesicles encapsulating the nucleating agent.

[0066] 《Surface protective layer 15》 1, the surface protective layer 15 is located on the front side of the raw fabric layer 14, and is provided for the purpose of imparting functions (surface properties) such as abrasion resistance, water resistance, weather resistance, scratch resistance, stain resistance, and design, and is formed by a printing method. The surface protective layer 15 preferably has a degree of transparency (e.g., colorless transparent, colored transparent, translucent, etc.) that allows various layers located on the back side to be seen through.

[0067] The thickness of the surface protection layer 15 is not particularly limited, but if it is too thick or too thin, it will be ineffective, and if it is too thick, it will have reduced flexibility and be prone to cracking, so it is preferable for the thickness to be 2 μm or more and 20 μm or less, and more preferably 4 μm or more and 10 μm or less.

[0068] In order to provide weather resistance, the surface protective layer 15 preferably contains an ultraviolet absorbing agent such as a benzotriazole, benzoate, benzophenone, triazine, cyanoacrylate, etc. In addition, the surface protective layer 15 preferably contains a hindered amine-based light radical scavenger (hindered amine-based light stabilizer) in order to capture harmful radicals and prevent deterioration of the resin itself due to light, heat, water, etc.

[0069] Moreover, it is preferable that the surface protective layer 15 is subjected to an antiviral treatment. Examples of the antiviral treatment include adding an antiviral agent to the surface of the surface protective layer 15, and applying an antiviral agent to the surface of the surface protective layer 15. As the antiviral agent, for example, a silver-based inorganic additive carrying silver ions (for example, "Bioside (registered trademark) TB-B100 (product number)" manufactured by Taisho Technos Co., Ltd.) is preferably used. Furthermore, it is preferable that the surface protective layer 15 contains various functional additives such as an antibacterial agent and an antifungal agent.

[0070] The surface protective layer 15 has a low-gloss matte undercoat layer 15A provided on the entire surface of the base fabric layer 14, and a high-gloss topcoat layer 15B provided on a portion of the surface of the undercoat layer 15A so as to match the pattern of the pattern layer 13. Since the surface protective layer 15 has the undercoat layer 15A and the topcoat layer 15B, the above-mentioned various functional agents can be added to both the undercoat layer 15A and the topcoat layer 15B, or only to the topcoat layer 15B located on the surface side of the surface protective layer 15.

[0071] (Undercoat layer 15A) The material of the undercoat layer 15A may be, for example, a thermosetting resin, an ionizing radiation curing resin, etc. The thermosetting resin may be, for example, a reaction product such as an acrylic urethane resin that uses an acrylic polyol compound as a base compound and an isocyanate compound as a curing agent.

[0072] Examples of the acrylic polyol compound include acrylic polymer compounds having hydroxyl groups in the side chains, which are obtained by blending and copolymerizing ordinary acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate with monomers containing hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate, and, if necessary, copolymerizable polymerizable monomers such as styrene, α-methylstyrene, vinyl toluene, divinylbenzene, vinyl acetate, vinyl butyrate, vinyl versatate, ethyl vinyl ether, acrylonitrile, and methacrylonitrile.

[0073] Examples of isocyanate compounds that can be used include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc. When weather resistance is taken into consideration, non-yellowing isocyanate compounds that do not have an aromatic ring, that is, aliphatic or alicyclic isocyanate compounds, are preferred.

[0074] The ionizing radiation curable resin may be, for example, a composition mainly composed of at least one of a prepolymer, oligomer, and monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group, which has the property of undergoing a crosslinking reaction when irradiated with ionizing radiation. Additives such as a polymerization initiator and a sensitizer may be added to the ionizing radiation curable resin as necessary.

[0075] Examples of the prepolymer or oligomer having a polymerizable unsaturated bond that can be used include melamine (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and polyol (meth)acrylate. As the monomer, for example, monofunctional monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate; bifunctional monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, and hexanediol diacrylate; and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate can be used.

[0076] The ionizing radiation for curing the ionizing radiation curable resin is electromagnetic waves or charged particles having energy capable of causing a curing reaction of the molecules in the ionizing radiation curable resin (composition). Generally, ultraviolet rays or electron beams are used, but visible light, X-rays, ion beams, etc. can also be used.

[0077] Examples of the ultraviolet light source that can be used include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, etc. The wavelength of the ultraviolet light is usually preferably in the range of 190 nm to 380 nm.

[0078] As the electron beam source, various electron beam accelerators can be used, such as Cockcroft-Walton type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Among them, those capable of irradiating electrons having an energy in the range of 100 keV to 1000 keV are particularly preferred, and those capable of irradiating electrons having an energy in the range of 100 keV to 300 keV are more preferred.

[0079] The undercoat layer 15A contains a filler having a particle size of 2 μm or more and 12 μm or less. That is, the undercoat layer 15A contains a filler having a particle size of 2 μm or less and 12 μm or less. As the filler, for example, an inorganic filler, an organic filler, etc. can be applied. As the particle shape of the filler, for example, a spherical shape, an indefinite shape, a plate shape, a needle shape, a fiber shape, etc. can be applied. When applying particles other than a spherical shape such as an indefinite shape, a plate shape, a needle shape, a fiber shape, etc., the circle equivalent diameter can be adopted as the particle size of the filler.

[0080] The undercoat layer 15A contains a filler, and thus unevenness is formed on the surface thereof, and this unevenness leads to the formation of unevenness on the surface of the topcoat layer 15B, that is, the surface of the surface protection layer 15. It should be noted that the topcoat layer 15B does not contain such a filler.

[0081] The undercoat layer 15A preferably has a filler content of 5% by mass to 35% by mass based on the total solid content, and the undercoat layer 15A preferably has a thickness of 1 μm to 15 μm, more preferably 2.5 μm to 6.5 μm.

[0082] (Top coat layer 15B) The material of the topcoat layer 15B is a silicone-modified acrylic urethane resin. The silicone-modified acrylic urethane resin is a resin obtained by adding an isocyanate compound to an acrylic polyol compound and a reactive silicone oil and hardening the mixture. By using the silicone-modified acrylic urethane resin, it is possible to improve the stain resistance and to create a matte design.

[0083] The reactive silicone oil may be, for example, one obtained by introducing a primary hydroxyl group into the terminal alkyl group of a polysiloxane resin. The thickness of the topcoat layer 15B is preferably 1 μm or more and 5 μm or less, and more preferably 1.5 μm or more and 3.5 μm or less.

[0084] (embossed part) In order to impart a three-dimensional design to the surface of the surface protection layer 15, an embossed portion 15a is formed on the outermost surface side, if necessary, in harmony with the pattern (e.g., a wood grain vessel pattern) of the pattern layer 13. The embossed portion 15a can have any concave-convex shape, such as a wood grain vessel shape, a stone grain shape, a cloth grain shape, an abstract pattern shape, a Japanese paper shape, a suede shape, a leather shape, a matte texture shape, a sand grain shape, a hairline shape, a group of parallel straight lines, or a combination of these.

[0085] Barrier Layer 16 1, the barrier layer 16 is located on the back surface side of the base layer 14, more specifically, on the back surface side of the colored layer 12 and on the front surface side of the undercoat layer 11, and is provided mainly for the purpose of suppressing gas permeation. The barrier layer 16 can be provided by applying or printing a two-component curing acrylic resin using, for example, a bar coater or a gravure printing method.

[0086] The barrier layer 16 is 1 g / m 2 It is preferable that the content is 3 g / m or more. 2 More preferably, the barrier layer 16 has a thickness of 6 g / m 2 In other words, the barrier layer 16 has a solid content of 1 g / m or less. 2 More than 6g / m 2It is preferable to apply or print a two-component curing acrylic resin so that the solid content is 3 g / m or less. 2 It is more preferable to apply or print a two-component curing acrylic resin so that the thickness is 1 g / m or more. 2 If it is less than 6 g / m, it may be difficult to sufficiently suppress gas permeation. 2 If it exceeds this amount, there is a risk of it becoming excessive and causing waste.

[0087] <Method of manufacturing decorative sheet 10> The decorative sheet 10 according to this embodiment can be manufactured in-line by the following first to third steps. Here, "in-line" means that multiple printing steps can be processed on one line, i.e., in one pass, without a lamination step for laminating films together. In other words, the manufacturing process from printing to providing the surface protective layer 15 can be performed in one pass.

[0088] "First step" The first step is to produce the raw fabric layer 14, which is a single-layer film obtained by extruding a resin material obtained by adding a dispersing agent as a nano-sized additive to a polyolefin thermoplastic resin such as a transparent polypropylene resin.

[0089] Specifically, a nucleating agent vesicle is mixed with a polyolefin thermoplastic resin such as a transparent polypropylene resin, and inorganic pigments, etc. are added as necessary to form a resin material, which is then heated and melted, extruded from an extruder, and cooled with a cooling roll to obtain a raw layer 14 of a single-layer film.

[0090] The second step The second step is a step A in which a pattern layer 13 and a colored layer 12 are provided in this order on the back side of the raw fabric layer 14 produced in the first step, and a step B in which a barrier layer 16 and an undercoat layer 11 are provided in this order after step A. Steps A and B can be performed continuously or intermittently with other steps interposed therebetween.

[0091] The third step The third step is a step of providing a surface protective layer 15 on the surface side of the raw fabric layer 14 produced in the first step before or after the second step, or during the second step, i.e., between step A and step B. The above-mentioned steps can be performed in three different orders: the first step, the second step, and the third step; the first step, the third step, and the second step; and the first step, the second step A, the third step, and the second step A.

[0092] Through these steps, a decorative sheet 10 can be obtained in which the undercoat layer 11, barrier layer 16, colored layer 12, design layer 13, base layer 14, and surface protective layer 15 are laminated in this order.

[0093] In other words, the decorative sheet 10 according to this embodiment can be made into a single-layer film by printing the pattern layer 13 on the back surface of the original fabric layer 14 formed from a transparent thermoplastic resin film, eliminating the need to laminate the pattern layer 13. This not only reduces the number of steps required to provide the pattern layer 13, colored layer 12, barrier layer 16, undercoat layer 11, and surface protective layer 15 on the original fabric layer 14, but also enables in-line production in one step.

[0094] <Basic structure of decorative panels> 2, the decorative board 100 according to this embodiment includes a decorative sheet 10, an adhesive layer 102 having one surface side provided on the back side, which is the other surface side, of a base layer 11 of the decorative sheet 10, and a wood-based substrate 101 having one surface side provided on the back side, which is the other surface side, of the adhesive layer 102. In other words, in the decorative board 100, the substrate 101 is provided on the back side of the base layer 11 of the decorative sheet 10, and the adhesive layer 102 is provided between the base layer 11 and the substrate 101, so that the decorative sheet 10 is attached to the substrate 101 via the adhesive layer 102.

[0095] "PCB 101" Examples of substrate 101 include wood plywood, tropical wood plywood, particle board, medium density fiberboard (MDF), ordinary plywood as specified by the Japanese Agricultural Standards, etc. By providing substrate 101, decorative board 100 capable of suppressing the occurrence of scratches can be provided.

[0096] 《Adhesive layer 102》 The adhesive layer 102 is provided on at least one surface of the substrate 101 in order to bond the decorative sheet 10 and the substrate 101. Since the substrate 101 is wood-based, examples of the adhesive layer 102 include an emulsion type vinyl acetate resin, a two-component curing urethane resin, and the like.

[0097] In the decorative board 100 according to this embodiment, even if caryophyllene in the wood-based substrate 101 attempts to diffuse toward the decorative sheet 10, the barrier layer 16 made of an acrylic resin can suppress the diffusion of caryophyllene into the colored layer 12 and the design layer 13. Therefore, even if the colored layer 12 and the design layer 13 are light-colored, discoloration of the colored layer 12 and the design layer 13 can be significantly suppressed.

[0098] Therefore, according to the decorative sheet 10 and decorative board 100 of this embodiment, even if a wood-based substrate 101 is adhered to the colored layer 12 and pattern layer 13 side provided on the original fabric layer 14, discoloration of the colored layer 12 and pattern layer 13 can be significantly suppressed.

[0099] [Second embodiment] A second embodiment of the decorative sheet and decorative board using the same according to the present invention will be described with reference to Fig. 3. However, for parts similar to those in the above-mentioned embodiment, the same reference numerals as those used in the description of the above-mentioned embodiment will be used, and descriptions that overlap with those in the above-mentioned embodiment will be omitted.

[0100] <Basic structure of decorative sheet> 3, the decorative sheet 20 includes a base layer 11, a barrier layer 16, a colored layer 12, a design layer 13, a base fabric layer 24, and a surface protective layer 15. In other words, the decorative sheet 20 according to this embodiment is obtained by applying a base fabric layer 24 instead of the base fabric layer 14 of the decorative sheet 10 according to the first embodiment.

[0101] "Original Layer 24" The raw fabric layer 24 has a transparent core portion 24C made of a thermoplastic resin, and a pair of transparent skin portions 24A, 24B located on both sides of the core portion 24C. That is, the raw fabric layer 24 is formed of two kinds of three parts by providing the back side skin portion 24A, the core portion 24C, and the front side skin portion 24B in this order, and by simultaneously extruding the layers so that the thickness ratio of the "back side skin portion 24A:core portion 24C:front side skin portion 24B" is "0.5:9:0.5".

[0102] Here, in Fig. 3, the original fabric layer 24 is illustrated as if the skin portion 24A on the back side, the core portion 24C, and the skin portion 24B on the front side are each separate, but in reality, the skin portions 24A, 24B, and the core portion 24C are a continuous integral body, and a single-layer film (single-layer sheet) is formed with no interface between the skin portions 24A, 24B and the core portion 24C. Note that the original fabric layer 24 only needs to have at least one of the skin portion 24A on the back side and the skin portion 24B on the front side. In other words, it is only necessary to have a skin portion on at least one surface side.

[0103] (Core part 24C) The core portion 24C is made of a film of a transparent thermoplastic resin to which a weathering agent or the like has been added. The thermoplastic resin constituting the core portion 24C is not particularly limited, and the same material as the thermoplastic resin used in the base layer 14 of the decorative sheet 10 according to the above-mentioned embodiment can be used.

[0104] It is preferable that the core portion 24C contains, as necessary, one or more additives selected from various additives such as 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.

[0105] (Skin parts 24A, 24B) The skin portion 24B is located on the front side of the core portion 24C, i.e., on the surface protective layer 15 side of the core portion 24C. The skin portion 24A is located on the back side of the core portion 24C, i.e., on the side of the core portion 24C opposite to the side where the skin portion 24B is provided (the surface protective layer 15 side) (the pattern layer 13 side).

[0106] The thickness of the skin portions 24A, 24B is preferably 1 μm or more and 50 μm or less, and more preferably 2 μm or more and 10 μm or less. When the thickness of the skin portions 24A, 24B is 1 μm or more, the scratch resistance of the decorative sheet 20 is sufficiently high. When the thickness of the skin portions 24A, 24B is 50 μm or less, the bendability of the decorative sheet 20 is not too high more than necessary, so that even when the attachment surface to which the decorative sheet 20 is attached is not flat, the decorative sheet 20 can be applied in a state in which it is in close contact with the attachment surface.

[0107] The skin parts 24A and 24B are formed by using the same type of thermoplastic resin as the core part 24C, for example, a polyolefin resin such as a transparent polypropylene resin, and adding a dispersant as a nano-sized additive (dispersant nano specification). As with the core part 24C, the skin parts 24A and 24B can also be made of a material containing a weathering agent. There are no particular limitations on the thermoplastic resin that constitutes the skin parts 24A and 24B, and the same resin material as the core part 24C can be used.

[0108] The skin portions 24A and 24B contain a resin material and a nucleating agent that improves the crystallinity of the resin material, and have an uneven surface. The nucleating agent is added to the resin material in the form of a nucleating agent vesicle that is encapsulated in an outer membrane and turned into a vesicle.

[0109] The skin parts 24A and 24B contain a nucleating agent as a nano-sized additive. The nano-sized nucleating agent is preferably added to the thermoplastic resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a single-layer outer membrane. The nucleating agent in the thermoplastic resin constituting the skin parts 24A and 24B may also be encapsulated in a vesicle with a part of the nucleating agent exposed.

[0110] Since the skin portions 24A, 24B contain a nucleating agent, it is possible to improve the crystallinity and improve the scratch resistance (scratch resistance) of the decorative sheet 20. In other words, the decorative sheet 20 according to this embodiment is formed by having the skin portions 24A, 24B contain a resin material (for example, a polyolefin-based thermoplastic resin such as a transparent polypropylene resin) and a nucleating agent.

[0111] <Method of manufacturing the decorative sheet 20> The decorative sheet 20 according to this embodiment can be produced in-line by the following first to third steps, similar to the decorative sheet 10 according to the previously described embodiment.

[0112] "First step" The first step is to produce the raw material layer 24, which is a single-layer film formed by extruding a core portion 24C made of a polyolefin-based thermoplastic resin such as a transparent polypropylene resin, and skin portions 24A, 24B located on the front and back sides of the core portion 24C, respectively, in which a dispersant as a nano-sized additive has been added to the thermoplastic resin.

[0113] Specifically, inorganic pigments and the like are added as necessary to a polyolefin-based thermoplastic resin material such as transparent polypropylene resin and the like, and the material is melt-kneaded to obtain a core resin material, and then nucleating agent vesicles are mixed into the polyolefin-based thermoplastic resin material such as transparent polypropylene resin to obtain a skin resin material.

[0114] Next, the core resin material and the skin resin material are heated and melted, and for example, these resin materials are simultaneously extruded from an extruder so that the core resin material is sandwiched between the skin resin materials, and cooled with a cooling roll to form a film in which the skin resin material / core resin material / skin resin material are layered in this order. This allows the raw fabric layer 24 to be obtained, in which the skin portion 24A / core portion 24C / skin portion 24B are layered in this order.

[0115] The second step The second step, like the embodiment described above, is a step A in which a pattern layer 13 and a colored layer 12 are provided in this order on the back side of the raw fabric layer 24 produced in the first step, and a step B in which a barrier layer 16 and an undercoat layer 11 are provided in this order after step A. Steps A and B can be performed continuously or intermittently with other steps interposed therebetween.

[0116] The third step The third step is, as in the above-mentioned embodiment, a step of providing a surface protective layer 15 on the surface side of the raw fabric layer 24 produced in the first step before or after the second step, or between the second step, i.e., between step A and step B. The above-mentioned steps can be performed in three different orders: the first step, the second step, and the third step; the first step, the third step, and the second step; and the first step, the second step A, the third step, and the second step A.

[0117] Through these steps, a decorative sheet 20 can be obtained in which the undercoat layer 11, barrier layer 16, colored layer 12, design layer 13, base layer 24, and surface protective layer 15 are laminated in this order.

[0118] Therefore, the decorative sheet 20 according to this embodiment can not only obtain the same effects as those of the above-mentioned embodiment, but also obtain the following effects.

[0119] The raw fabric layer 24 has a core portion 24C and skin portions 24A, 24B located on both sides of the core portion 24C, and the skin portions 24A, 24B contain a thermoplastic resin and a nucleating agent. Therefore, the decorative sheet 20 can have both high hardness and processability more reliably than the above-mentioned embodiment.

[0120] Moreover, a decorative board can be produced by adhering a substrate 101 to the undercoat layer 11 of the decorative sheet 20 via an adhesive layer 102 in the same manner as in the above-described embodiment.

[0121] [Third embodiment] A third embodiment of the decorative sheet and decorative board using the same according to the present invention will be described with reference to Fig. 4. However, for parts similar to those in the above-mentioned embodiment, the same reference numerals as those used in the description of the above-mentioned embodiment will be used, and descriptions that overlap with those in the above-mentioned embodiment will be omitted.

[0122] <Basic structure of decorative sheet> 4, the decorative sheet 30 includes a base layer 11, a barrier layer 16, a colored layer 12, a design layer 13, a base fabric layer 34, and a surface protective layer 15. In other words, the decorative sheet 30 according to this embodiment is obtained by applying a base fabric layer 34 instead of the base fabric layer 24 of the decorative sheet 20 according to the second embodiment.

[0123] "Original Layer 34" The raw fabric layer 34 is layered in the order of the skin portion 34A on the back side, the core portion 24C, and the core portion 34B on the front side. In other words, the raw fabric layer 34 of the decorative sheet 30 according to this embodiment is configured to use the skin portions 34A and 34B instead of the skin portions 24A and 24B of the raw fabric layer 24 of the decorative sheet 20 according to the second embodiment described above. It is sufficient that the raw fabric layer 34 is provided with at least one of the skin portion 34A on the back side and the skin portion 34B on the front side. In other words, it is sufficient that a skin portion is provided on at least one surface side.

[0124] (Skin parts 34A, 34B) The skin parts 34A, 34B are layers containing a resin material and an inorganic filler. In the decorative sheet 20 according to the second embodiment described above, a highly scratch-resistant resin sheet having high crystallinity is formed by using a resin material containing a nucleating agent and having a nano-dispersant specification, to form the skin parts 24A, 24B. In contrast, in the decorative sheet 30 according to the present embodiment, instead of a nucleating agent, a nano-sized inorganic filler (inorganic nanoparticles) having high hardness is added to a resin material (for example, a transparent polyolefin-based thermoplastic resin) to form the skin parts 34A, 34B (hereinafter also referred to as "inorganic nanoparticle specification"). This allows the skin parts 34A, 34B to be formed with high hardness, and the decorative sheet 30 having high scratch resistance to be obtained.

[0125] Examples of the inorganic filler include nano-sized particles made of inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, barium sulfate, etc. The skin portions 34A and 34B are formed of a resin material to which an inorganic filler is added in an amount of, for example, 0.05 parts by mass to 0.5 parts by mass relative to 100 parts by mass of the resin material.

[0126] The skin resin material can be obtained by, for example, mixing nano-sized inorganic fillers with a polyolefin-based thermoplastic resin material such as transparent polypropylene resin. Then, similar to the second embodiment described above, the core resin material and the skin resin material are heated and melted, and for example, these resin materials are simultaneously extruded from an extruder so that the core resin material is sandwiched between the skin resin materials, and cooled by a cooling roll. This allows the raw fabric layer 34 to be obtained, in which the skin portion 34A / core portion 24C / skin portion 34B are layered in this order.

[0127] The skin parts 34A and 34B are formed of inorganic nanoparticles containing inorganic filler. The present invention is not limited to this, and in addition to the inorganic nanoparticles, it is also possible to add a dispersant nano specification containing a nucleating agent. In other words, the skin part can contain both a dispersant and an inorganic filler.

[0128] Therefore, with the decorative sheet 30 according to this embodiment, it is possible to obtain the same effects as with the decorative sheet 20 according to the second embodiment described above.

[0129] Moreover, a decorative board can be produced by adhering a substrate 101 to the undercoat layer 11 of the decorative sheet 30 via an adhesive layer 102 in the same manner as in the above-described embodiment.

[0130] [Other embodiments] In the above-described embodiment, the decorative sheets 10, 20, and 30 are provided with the embossed portion 15a on the outermost surface side of the surface protective layer 15, but the present invention is not limited thereto. As another embodiment, for example, it is possible to provide a decorative sheet provided with a surface protective layer that omits the embossed portion, and a decorative board using the same.

[0131] In the above-mentioned embodiment, the decorative sheets 10, 20, 30 are provided so that the surface of the base layer 11 is attached to the back surface of the barrier layer 16, but the present invention is not limited to this. As another embodiment, for example, when moisture resistance is highly required, it is possible to provide a decorative sheet in which a moisture-proof layer is provided on the back surface of the barrier layer 16 so that the surface of one side of the moisture-proof layer is attached, and the base layer 11 is provided so that the surface of the base layer 11 is attached to the back surface of the other side of the moisture-proof layer.

[0132] Here, the moisture-proof layer is made of a resin that does not allow water vapor to pass through, and is preferably, for example, an olefin-based thermoplastic resin such as low-density polyethylene having a melting point of 100° C. or more and less than 200° C. The moisture-proof layer preferably has a thickness of 20 μm or more and less than 70 μm.

[0133] In the above-mentioned embodiment, the decorative board 100 is described in which the substrate 101 is bonded to the base layer 11 via the adhesive layer 102, but the present invention is not limited to this. As another embodiment, for example, it is possible to make a decorative tack sheet by attaching one side of an adhesive layer to the base layer 11 and attaching a release paper to the other side of the adhesive layer, and during construction, the release paper is peeled off from the adhesive layer and the adhesive layer is attached to the wood-based substrate 101 to make a decorative board.

[0134] In the above-mentioned embodiment, the decorative sheets 10, 20, 30 are provided with the base layer 11, but the present invention is not limited thereto. In another embodiment, for example, when the barrier layer 16 or the moisture-proof layer functions as a base, the base layer 11 can be omitted.

[0135] In the above-described embodiment, the decorative board has a decorative sheet attached only to one side of the substrate 101, but the present invention is not limited to this. As other embodiments, for example, a decorative board having a decorative sheet attached to one side of the substrate 101 and a moisture-proof layer attached to the other side of the substrate 101, or a decorative board having decorative sheets attached to both sides of the substrate 101, is also possible. EXAMPLES

[0136] Examples of the decorative sheet according to the present invention and the decorative board using the same will be described below, but the present invention is not limited to the specific examples described below.

[0137] [Preparation of test specimens and comparison specimens] Test specimen 1 "First step" A transparent polypropylene resin was formulated with the addition of weather resistance agents and dispersants as nano-sized additives (nano-dispersant specifications). The resin material for the base layer was extruded to produce a film-shaped base layer (thickness 70 μm).

[0138] "Second Process A" After corona treatment was performed on the back side of the prepared base layer, a wood grain pattern was printed with urethane resin by gravure printing to form a pattern layer, and then a colored layer (thickness 20 μm) was formed with two-component curing urethane resin by gravure printing.

[0139] The third step Then, an acrylic urethane resin containing silica (inorganic filler) (35% by mass based on the total solid content) was applied to the surface side of the base layer and cured by heating to provide an undercoat layer (4.5 μm thick). Next, a silicone-modified acrylic urethane resin was applied to the surface side of the undercoat layer and cured by heating to provide a topcoat layer (2.5 μm thick).

[0140] "Second B Process" Furthermore, a bar coater was used to coat the back side of the prepared base layer with a solid content of 1 g / m 2 A two-component curing acrylic resin was applied to provide a barrier layer so that the thickness of the barrier layer became 100 μm. In this way, the decorative sheet of specimen 1 was produced.

[0141] <<Making process of decorative panels>> Next, a two-part curing water-based emulsion adhesive ("Rikabond (registered trademark)" (weight ratio BA-10L:BA-11B = 100:2.5) manufactured by Japan Coating Resin Co., Ltd.) was applied in a wet state (80 g / m) on the surface of an MDF (hardwood) substrate (thickness 3 mm). 2 ) to provide an adhesive layer. The adhesive layer of the substrate and the decorative sheet were then bonded together to prepare a decorative board specimen 1.

[0142] Test specimen 2 In the second B step, the solid content is 3 g / m 2 A decorative board specimen 2 was produced under the same conditions as specimen 1, except that a barrier layer was provided by applying a two-component curing acrylic resin so as to give a coating of 100% water.

[0143] Test specimen 3 In the second B step, the solid content is 6 g / m 2A decorative board specimen 3 was produced under the same conditions as specimen 1, except that a barrier layer was provided by coating a two-component curing acrylic resin so as to give a coating thickness of 100 mm.

[0144] Test specimen 4 "First step" A transparent polypropylene resin was formulated with the addition of weather resistance agents and dispersants as nano-sized additives (nano-dispersant specifications). The resin material for the base layer was extruded to produce a film-shaped base layer (thickness 70 μm).

[0145] The second step After corona treatment was performed on the back side of the prepared base layer, a wood grain pattern was printed with urethane resin by gravure printing to form a pattern layer. Next, a colored layer (thickness 20 μm) was formed with a two-component curing urethane resin by gravure printing (above, step A). ​​Next, a colored layer (thickness 20 μm) was formed with a two-component curing urethane resin by gravure printing to form a colored layer (thickness 20 μm) with a solid content of 3 g / m 2 A two-component curing acrylic resin was applied to provide a barrier layer (this is process B).

[0146] The third step Then, an acrylic urethane resin containing silica (inorganic filler) (35% by mass based on the total solid content) was applied to the surface side of the raw layer and cured by heating to provide an undercoat layer (4.5 μm thick). Next, a silicone-modified acrylic urethane resin was applied to the surface side of the undercoat layer and cured by heating to provide a topcoat layer (2.5 μm thick). This produced the decorative sheet of specimen 4.

[0147] <<Making process of decorative panels>> Next, a two-part curing water-based emulsion adhesive ("Rikabond (registered trademark)" (weight ratio BA-10L:BA-11B = 100:2.5) manufactured by Japan Coating Resin Co., Ltd.) was applied in a wet state (80 g / m) on the surface of an MDF (hardwood) substrate (thickness 3 mm). 2 ) to provide an adhesive layer. The adhesive layer of the substrate and the decorative sheet were then attached to each other to prepare specimen 4 of the decorative board.

[0148] Comparison body 1 In the second step B, a comparative decorative board specimen 1 was produced under the same conditions as those of the test specimen 1, except that a barrier layer was provided by applying a two-component curing urethane resin.

[0149] Comparison body 2 In the second step B, a comparative decorative board specimen 2 was produced under the same conditions as those of specimen 2, except that a barrier layer was provided by applying a two-component curing urethane resin.

[0150] Comparison 3 In the second step B, a comparative decorative board specimen 3 was produced under the same conditions as those of test specimen 3, except that a barrier layer was provided by applying a two-component curing urethane resin.

[0151] <Comparative example 4> Comparative decorative board specimen 4 was produced under the same conditions as specimen 1, except that the second step B was omitted, that is, the barrier layer was omitted.

[0152] [Evaluation method] <Color change evaluation> Test specimens 1 to 4 and comparative specimens 1 to 4 were left for 24 hours in an environment of a temperature of 85° C. and a humidity of 85%, and the change in color tone before and after leaving the specimens was evaluated.

[0153] Visual confirmation The color change of the above test specimens 1 to 4 and comparative specimens 1 to 4 before and after being left standing was visually confirmed. The results are shown in the following Table 1. In Table 1, "○" indicates that no discoloration was observed, "△" indicates that slight discoloration that is not problematic in practical use was observed, and "×" indicates that discoloration that is problematic in practical use was observed.

[0154] Color difference measurement The color difference of the above test specimens 1 to 4 and comparative specimens 1 to 4 before and after being left standing was measured using a color difference meter "CR-400 (product number)" manufactured by Konica Minolta, Inc. The results are shown in Table 1 below. In Table 1, "○" indicates that the color difference ΔE was less than 2.0 (ΔE<2.0), "△" indicates that the color difference ΔE was 2.0 or more and less than 3.0 (2.0≦ΔE<3.0), and "×" indicates that the color difference ΔE was 3.0 or more (ΔE≧3.0).

[0155] [Table 1]

[0156] As can be seen from Table 1, in Comparative Examples 1 to 3 (barrier layer made of urethane resin) and Comparative Example 4 (no barrier layer), both visual confirmation and color difference measurement were scored as "X", resulting in an overall rating of "X". In contrast, in Examples 1 to 4 (barrier layer made of acrylic resin), both visual confirmation and color difference measurement were scored as "△" or better, resulting in an overall rating of "△" or better. In particular, in Examples 2 to 4 (barrier layer 3 to 6 mm), both visual confirmation and color difference measurement were scored as "○", resulting in an overall rating of "○".

[0157] Therefore, the effects of the decorative sheet according to the present invention and the decorative board using the same were confirmed. [Industrial Applicability]

[0158] The decorative sheet of the present invention and the decorative board using the same can significantly suppress discoloration of the colored layer and patterned layer even when a wood-based substrate is bonded to the colored layer and patterned layer side of the base layer, and therefore can be used extremely advantageously in various industries including the construction industry. [Explanation of symbols]

[0159] 10 Decorative Sheet 11 Base layer 12 Colored layer 13 Picture layer 14 Original layer 15 Surface protection layer 15a Embossed section 15A Undercoat layer 15B Top coat layer 16 Barrier Layer 20 Decorative Sheet 24 Original layer 24A, 24B Skin section 24C Core 30 Decorative Sheet 34 Original layer 34A, 34B Skin section 100 Veneer 101 Substrate 102 Adhesive layer

Claims

1. a raw layer made of a single-layer film containing a transparent thermoplastic resin and at least one of a nucleating agent and an inorganic filler; A surface protective layer provided on the surface side of the raw fabric layer; A pattern layer provided on the back side of the base fabric layer; A coloring layer provided on the back side of the design layer; A decorative sheet comprising: A barrier layer made of an acrylic resin material is provided on the back side of the colored layer. A decorative sheet characterized by:

2. The barrier layer has a thickness of 1 g / m ２ 6g / m or more ２ It is set up so that 2. The decorative sheet according to claim 1.

3. The raw fabric layer is A core portion; a skin portion located on at least one of one and the other surfaces of the core portion; having The skin portion is The thermoplastic resin; At least one of the nucleating agent and the inorganic filler; Contains 2. The decorative sheet according to claim 1.

4. An embossed portion is formed on the outermost surface in accordance with the pattern of the pattern layer.

2. The decorative sheet according to claim 1.

5. The surface protective layer is A first protective layer; A second protective layer provided between the first protective layer and the original fabric layer; having The first protective layer is provided to match the pattern of the pattern layer.

2. The decorative sheet according to claim 1.

6. The first protective layer has a higher gloss than the second protective layer.

6. The decorative sheet according to claim 5.

7. An undercoat layer is provided on the back side of the barrier layer.

2. The decorative sheet according to claim 1.

8. A moisture-proof layer is provided on the back side of the barrier layer.

2. The decorative sheet according to claim 1.

9. A base layer is provided on the back side of the moisture-proof layer.

9. The decorative sheet according to claim 8.

10. The decorative sheet according to claim 7 or 9, a wood-based substrate provided on the back surface side of the base layer of the decorative sheet; an adhesive layer provided between the undercoat layer of the decorative sheet and the substrate; A decorative panel comprising:

11. A moisture-proof layer is provided on the back side of the substrate. The decorative board according to claim 10.

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