Decorative sheet and method for manufacturing the same

Abstract

To provide a decorative sheet which can prevent quality deterioration, even if deep recessed and projected embossment is generated and a pattern layer has a long-cycle pattern, and a method for manufacturing the same.SOLUTION: A decorative sheet 10 has a raw fabric layer 14 which is composed of a single layer film and has an embossment 14a formed on one surface, a surface protective layer 15 provided on one surface side of the raw fabric layer 14, and a pattern layer 13 which is provided on the other surface side of the raw fabric layer 14 and is formed with a pattern, wherein the raw fabric layer 14 contains a transparent thermoplastic resin, and at least one of a nucleating agent and an inorganic filler, the pattern layer 13 has one surface directly provided on the other surface of the raw fabric layer 14, and has resolution of 200 dpi or more and 1,000 dpi or less, and the embossment 14a of the raw fabric layer 14 is formed so as to match the pattern of the pattern layer 13.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet and a method for producing the same. [Background technology]

[0002] Decorative sheets used indoors are applied to the surfaces of fixtures (interior doors, entrance storage) and construction materials (trimmings, moldings, baseboards, window frames, door frames), etc. The decorative sheets used for these purposes are used to match the patterns of the fixtures and construction materials for each house or room. Such decorative sheets can be made to have a realistic wood grain or stone grain look by forming bumps and grooves on the surface that match the pattern (see, for example, Patent Document 1 below, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2022-011844 Summary of the Invention [Problem to be solved by the invention]

[0004] In conventional decorative sheets as described above, when printing a pattern such as a wood grain pattern while applying pressure with a cylinder, as in gravure printing, if the surface is embossed with deep unevenness such as wood grain vessels, the printing pressure in the deep uneven parts is likely to be insufficient, which could result in a deterioration in quality.

[0005] Furthermore, if one attempts to lengthen the period of a pattern such as a wood grain pattern, the diameter of the cylinder on which the plate is mounted must be increased, which not only results in an increase in the size of the printing device, but also makes the plate longer, making registration difficult. In addition, the ink supplied to the plate is more likely to dry out during printing, causing clogging and potentially resulting in a decline in quality.

[0006] In view of the above, the present invention aims to provide a decorative sheet and a manufacturing method thereof that can prevent deterioration in quality even when the sheet has deep embossing or a pattern layer with a long-period pattern. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the decorative sheet of the present invention is a decorative sheet having an original fabric layer made of a single layer film and embossed on one side, a surface protective layer provided on one side of the original fabric layer, and a pattern layer provided on the other side of the original fabric layer and formed with a pattern, characterized in that the original fabric layer contains a transparent thermoplastic resin and at least one of a nucleating agent and an inorganic filler, the pattern layer is provided directly on one side of the other side of the original fabric layer, has a resolution of 200 dpi or more and 1000 dpi or less, and the embossment of the original fabric layer is formed in harmony with the pattern of the pattern layer.

[0008] In the decorative sheet according to the present invention, it is preferable that the design layer in the above-mentioned decorative sheet contains at least one of yellow, magenta and cyan.

[0009] 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.

[0010] 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.

[0011] In the decorative sheet according to the present invention, the pattern of the pattern layer is preferably a wood grain vessel pattern, and the embossment of the base fabric layer is preferably in the form of a wood grain vessel.

[0012] In the decorative sheet according to the present invention, it is preferable that the first protective layer has a lower gloss than the second protective layer.

[0013] The decorative sheet according to the present invention is preferably the decorative sheet described above, further comprising a colored layer provided on one side of the other side of the design layer.

[0014] The decorative sheet according to the present invention is preferably the decorative sheet described above, further comprising a base layer provided on one side of the other side of the colored layer.

[0015] In addition, the decorative sheet according to the present invention is preferably the above-mentioned decorative sheet, in which the colored layer serves as a base.

[0016] On the other hand, in order to solve the above-mentioned problems, the manufacturing method for decorative sheets according to the present invention is the manufacturing method for decorative sheets described above, characterized in that it includes a first step of heating and melting a raw fabric layer material, which is a mixture of the thermoplastic resin and at least one of the nucleating agent and the inorganic filler, to form a film shape while forming the embossing on one side, a second step of directly printing the pattern of the pattern layer on the other side of the raw fabric layer by inkjet printing, and a third step of providing the surface protective layer by adhering a resin material of the surface protective layer to one side of the raw fabric layer. Effect of the Invention

[0017] The decorative sheet of the present invention has a pattern layer directly formed on one side of an original fabric layer having an embossed surface, and the resolution of the pattern layer is 200 dpi or more and 1000 dpi or less, so that the pattern layer can be formed by directly printing ink on the other side of the original fabric layer using an inkjet printing method without contacting the original fabric layer.

[0018] Therefore, since there is no need to apply pressure with a cylinder as in gravure printing, even if one side of the raw fabric layer is embossed with deep unevenness such as a wood grain vessel pattern, the deep unevenness can be printed without any problems, and deterioration of quality can be prevented. Also, even if the pattern cycle of a wood grain vessel pattern or the like is long, it is not necessary to use a plate as in gravure printing, and there is no need to increase the diameter of the cylinder on which the plate is attached, so clogging of the plate and an increase in the size of the printing device can be prevented in advance, and registration can be facilitated, preventing deterioration of quality.

[0019] Therefore, with the decorative sheet of the present invention, deterioration in quality can be prevented even in a base layer having deep embossed unevenness or a pattern layer having a long-period pattern.

[0020] In addition, the manufacturing method for decorative sheets according to the present invention involves a first step of heating and melting an original fabric layer material, which is a mixture of a thermoplastic resin and at least one of a nucleating agent and an inorganic filler, to form a film shape while forming an embossment on one side, a second step of directly printing a pattern for a pattern layer on the other side of the original fabric layer by inkjet printing, and a third step of providing a surface protective layer by adhering a resin material for the surface protective layer to one side of the original fabric layer, so that decorative sheets can be manufactured without deterioration in quality, even in the case of an original fabric layer with a deep embossing of unevenness or a pattern layer with a long-period pattern. [Brief description of the drawings]

[0021] [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] FIG. 2 is a cross-sectional view showing a schematic structure of a second embodiment of a decorative sheet according to the present invention. [Diagram 3] FIG. 2 is a cross-sectional view showing a schematic structure of a third embodiment of a decorative sheet according to the present invention. [Figure 4] FIG. 11 is a cross-sectional view showing a schematic structure of a fourth embodiment of a decorative sheet according to the present invention. [Diagram 5]FIG. 11 is a cross-sectional view showing a schematic structure of a fifth embodiment of a decorative sheet according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The decorative sheet and its manufacturing method according to the present invention will be described below 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.

[0023] [First embodiment] A first embodiment of a decorative sheet and a method for producing the same according to the present invention will be described with reference to FIG.

[0024] <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 has a pattern formed thereon to impart a design is provided on the colored layer 12. A base fabric layer 14 that is made of a transparent resin sheet 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.

[0025] 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.).

[0026] In the above-mentioned decorative sheet 10, when the colored layer 12 functions as a base layer, it is possible to omit the base layer 11. That is, the colored layer 12 can also function as the base layer 11. In addition, in the above-mentioned decorative sheet 10, for example, when hiding properties are not particularly required, it is also possible to omit the colored layer 12.

[0027] In other words, the decorative sheet 10 has a surface protective layer 15 provided on one side of the original fabric layer 14 made of a single-layer film, and a design layer 13 provided on one side of the original fabric layer 14 on the other side of the original fabric layer 14. Furthermore, the decorative sheet 10 does not have a laminate layer formed of another film on the front and back sides of the original fabric layer 14.

[0028] As shown in FIG. 1, the surface protective layer 15 has a topcoat layer 15B, which is a first protective layer, and a basecoat layer 15A, which is a second protective layer provided between the topcoat layer 15B and the original fabric layer 14. That is, the surface protective layer 15 has the topcoat layer 15B on the front side, which is one side, and the basecoat layer 15A on the back side, which is the other side. In other words, the surface protective layer 15 has the topcoat layer 15B, which faces one side toward the front side, and the basecoat layer 15A, which faces one side toward the other side of the topcoat layer 15B and faces the other side toward the front side of the original fabric layer 14. That is, the decorative sheet 10 has a structure that at least has a pattern layer 13, an original fabric layer 14, and a surface protective layer 15. Furthermore, each layer will be specifically described.

[0029] <Configuration of each layer of the decorative sheet> 《Base layer 11》 As shown in Fig. 1, the undercoat layer 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 stabilizing the surface after surface treatment, preventing corrosion of the metal surface, imparting adhesion, and preventing deterioration of the adhesive. The undercoat layer 11 is provided by laminating it on the colored layer 12 on the back side of the original fabric layer 14. In other words, the undercoat layer 11 is provided on its front side (one side) on the back side (other side) of the colored layer 12 which has the pattern layer 13 provided on its front side (one side). The undercoat layer 11 is printed, for example, by a gravure printing method or the like, with a solid content of 1 g / m 2 The urethane resin is applied to the surface so as to form the void.

[0030] 《Colored layer 12》 As shown in FIG. 1, the colored layer 12 is located on the back side of the original fabric layer 14, more specifically, on the back side of the pattern layer 13, and on the front side of the undercoat layer 11. In other words, the colored layer 12 is provided on the front side (one side) of the original fabric layer 14, on the back side (other side) of the pattern layer 13. The colored layer 12 is provided mainly for the purpose of imparting hiding power, and can be provided by printing with a two-component curing urethane resin 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" The pattern layer 13 is provided mainly for the purpose of imparting design, and is located on the back side of the original fabric layer 14 and on the front side of the colored layer 12, as shown in Fig. 1. The pattern layer 13 is formed by directly printing a pattern on the back side of the original fabric layer 14 by inkjet printing. In other words, the front side of the pattern layer 13 is provided directly on the back side of the original fabric layer 14.

[0032] The design layer 13 is formed by directly printing ink for inkjet printing on the back surface of the base fabric layer 14 without contacting the base fabric layer 14 by applying an inkjet printing method, and the resolution of the design is 200 dpi or more and 1000 dpi or less. Such ink for inkjet printing contains at least one of yellow, magenta, and cyan. The type of pattern of the design layer 13 is arbitrary depending on the purpose of use and the user's preferences, and examples of common patterns include wood grain patterns, stone grain patterns, and abstract patterns.

[0033] "Original Layer 14" The thickness of the raw fabric layer 14 is preferably in the range of 70 μm to 150 μm, and more preferably in the range of 90 μm to 130 μm. When the thickness of the raw fabric layer 14 is 70 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 90 μm or more, the strength can be further increased, and scratch resistance can be more reliably improved.

[0034] 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 130 μm or less, the decorative sheet 10 can be made both thin and strong while more reliably improving the processing suitability.

[0035] In order to impart a three-dimensional design to the surface of the base fabric layer 14, an embossment 14a (e.g., a wood grain vessel shape) is provided on the surface side so as to match the pattern (e.g., a wood grain vessel pattern) of the pattern layer 13. The embossment 14a preferably has a depth of 5 μm or more and 30 μm or less.

[0036] The embossment 14a can be 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, a combination of these, etc. The embossment 14a can be easily formed on the surface (one side) of the original fabric layer 14 by applying, for example, a doubling embossing method, an extrusion lamination simultaneous embossing method, etc., when forming the original fabric layer 14.

[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, in the decorative sheet 10 according to this embodiment, 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, can be 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 decorative sheet 10 of this embodiment differs from conventional ones in that the nucleating agent is highly dispersed, it is conceivable that there may be cases in which it is impractical to determine whether this is because the nucleating agent is added in the form of vesicles encapsulating the nucleating agent, based on the numerical range analyzed based on measurements of the structure and characteristics.

[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 high gloss undercoat layer 15A provided on the entire surface of the base fabric layer 14, and a low gloss matte topcoat layer 15B provided on a part 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 preferably contains a filler having a particle size of 2 μm or more and 12 μm or less. That is, the undercoat layer 15A preferably 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, so that the surface thereof is uneven, and the 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 is preferable 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] <Method of manufacturing the 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.

[0085] "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.

[0086] Specifically, a resin material is prepared by mixing a nucleating agent vesicle with a polyolefin thermoplastic resin such as a transparent polypropylene resin and, if necessary, adding an inorganic pigment, etc., and then heating and melting the resin material, extruding it from an extruder, and cooling it with a cooling roll to obtain a raw fabric layer 14 of a single-layer film. At this time, an embossing 14a is formed on one side by applying a doubling embossing method, a simultaneous extrusion lamination embossing method, etc.

[0087] The second step The second step is a step of providing a pattern layer 13, a colored layer 12, and a base layer 11 in this order on the back side of the raw fabric layer 14 produced in the first step. Specifically, after a corona treatment is performed on the back side of the produced raw fabric layer 14, a pattern such as wood grain conduits is directly printed using inkjet printing ink by inkjet printing to provide the pattern layer 13. Next, a colored layer 12 is provided by a two-component curing urethane resin or the like by gravure printing, and then a urethane resin or the like is applied by gravure printing to provide the base layer 11.

[0088] 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. Specifically, an acrylic urethane resin or the like is applied in a sheet form to the surface side of the raw fabric layer 14 and cured by heating to provide an undercoat layer 15A, and then a silicone modified acrylic urethane resin or the like is applied to the surface side of the undercoat layer 15A in accordance with the pattern of the pattern layer 13 and cured by heating to provide a topcoat layer 15B.

[0089] Here, the third step can be performed after the second step or before the second step. That is, the above-mentioned steps can be performed in two orders: the first step, the second step, and the third step, or the first step, the third step, and the second step. By performing these steps, a decorative sheet 10 can be obtained in which the undercoat layer 11, the colored layer 12, the design layer 13, the base layer 14, and the surface protective layer 15 are laminated in this order.

[0090] Conventional decorative sheets are multi-layered, so it is difficult to achieve a harmonious expression between the application of the pattern layer and the surface protective layer on the surface of the laminate film. In contrast, the decorative sheet 10 according to the present embodiment can be manufactured in-line as described above. Therefore, in the decorative sheet 10 according to the present embodiment, the application of the pattern layer 13 to the back side of the raw fabric layer 14 and the application of the surface protective layer 15 to the front side of the raw fabric layer 14 can be performed during in-line manufacturing, so that the harmonious expression between the pattern layer 13 and the surface protective layer 15 can be easily achieved.

[0091] In the decorative sheet 10 according to this embodiment, the pattern layer 13 is provided directly on the back surface of the original fabric layer 14 which has an embossed surface, and since the resolution of the pattern layer 13 is 200 dpi or more and 1000 dpi or less, the pattern layer 13 can be formed by printing ink directly onto the back surface of the original fabric layer 14 using an inkjet printing method without contacting the original fabric layer 14.

[0092] Therefore, since there is no need to print while applying pressure with a cylinder as in gravure printing, even if the surface of the raw fabric layer 14 is processed with embossments 14a with deep projections and recesses such as wood grain vessels, the deep projections and recesses can be printed without any problems, and deterioration of quality can be prevented.

[0093] Furthermore, even if the pattern period of a wood grain vessel pattern or the like is long, it is not necessary to use a plate as in gravure printing, nor is it necessary to increase the diameter of the cylinder on which the plate is attached. This makes it possible to prevent clogging of the plate and the need for larger printing equipment, as well as to facilitate easier registration and prevent a decline in quality.

[0094] Therefore, according to the decorative sheet 10 and its manufacturing method of this embodiment, deterioration in quality can be prevented even in the case of a base layer 14 having deep embossments 14a or a pattern layer 13 having a long-period pattern.

[0095] Furthermore, since the pattern layer 13 contains at least one of yellow, magenta, and cyan, the pattern layer 13 can be formed by applying an inkjet printing method, so that even if the base layer 14 has a deep embossing 14a or the pattern layer 13 has a long-period pattern, the decorative sheet 10 can be manufactured without deterioration in quality.

[0096] [Second embodiment] A second embodiment of the decorative sheet and its manufacturing method according to the present invention will be described with reference to Fig. 2. 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 are used, and descriptions that overlap with those in the above-mentioned embodiment will be omitted.

[0097] <Basic structure of decorative sheet> 2, the decorative sheet 20 includes a base layer 11, 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.

[0098] "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".

[0099] Here, in Figure 2, the original fabric layer 24 is shown 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 entities, but in reality the skin portions 24A, 24B and the core portion 24C are a continuous, integrated body, and a single-layer sheet (single-layer film) is formed with no interface between the skin portions 24A, 24B and the core portion 24C.

[0100] (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.

[0101] 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.

[0102] (Skin parts 24A, 24B) The skin portion 24B is located on one surface side of the core portion 24C, i.e., on the surface protection layer 15 side of the core portion 24C. The skin portion 24A is located on the other surface side of the core portion 24C, i.e., on the pattern layer 13 side of the core portion 24C.

[0103] 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.

[0104] In order to impart a three-dimensional design to the surface of the skin portion 24B, an embossment 24a (e.g., a wood grain vascular shape) is provided on the surface side so as to match the pattern (e.g., a wood grain vascular pattern) of the pattern layer 13. The embossment 24a can be easily formed on the surface (one side) of the skin portion 24B by applying, for example, a doubling embossing method or an extrusion lamination simultaneous embossing method when forming the raw fabric layer 24.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] <Method of manufacturing the decorative sheet 20> The decorative sheet 20 according to this embodiment, like the decorative sheet 10 according to the previously described embodiment, can be produced in-line by the following first to third steps.

[0110] "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.

[0111] 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.

[0112] 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 makes it possible to obtain a raw fabric layer 24 in which the skin portion 24A / core portion 24C / skin portion 24B are layered in this order. At this time, as in the case of the above-mentioned embodiment, the doubling embossing method, the extrusion lamination simultaneous embossing method, or the like is applied to form an embossment 24a in the skin portion 24B.

[0113] The second step The second step is a step of providing a pattern layer 13, a colored layer 12, and a base layer 11, in that order, on the back side of the raw fabric layer 24 produced in the first step, as in the previously described embodiment.

[0114] 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 24 produced in the first step, as in the above-mentioned embodiment. Here, the third step can be performed after the second step or before the second step, as in the above-mentioned embodiment. That is, the above-mentioned steps can be performed in two orders, the first step, the second step, and the third step, and the first step, the third step, and the second step, as in the above-mentioned embodiment. By such steps, a decorative sheet 20 can be obtained in which the undercoat layer 11, the colored layer 12, the pattern layer 13, the raw fabric layer 24, and the surface protective layer 15 are laminated in this order.

[0115] Therefore, according to this embodiment, it is possible to obtain not only the same effects as in the first embodiment described above, but also the following effects.

[0116] 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 be made to have both higher hardness and processability more reliably than the above-mentioned embodiment.

[0117] [Third embodiment] A third embodiment of the decorative sheet and its manufacturing method 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 are used, and descriptions that overlap with those in the above-mentioned embodiment will be omitted.

[0118] <Basic structure of decorative sheet> 3, the decorative sheet 30 includes a base layer 11, 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 the base fabric layer 34 instead of the base fabric layer 24 of the decorative sheet 20 according to the second embodiment.

[0119] "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.

[0120] (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-sized dispersant, 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.

[0121] 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.

[0122] The skin resin material can be obtained by mixing nano-sized inorganic fillers with a polyolefin-based thermoplastic resin material such as transparent polypropylene resin. As in the second embodiment described above, the core resin material and the skin resin material are heated and melted, and these resin materials are extruded simultaneously 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.

[0123] 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.

[0124] Therefore, according to this embodiment, it is possible to obtain the same effects as those of the second embodiment described above.

[0125] [Fourth embodiment] A fourth embodiment of the decorative sheet and its manufacturing method 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.

[0126] <Basic structure of decorative panels> 4, the decorative board 100 has a decorative sheet 10 and a substrate 101 to which the decorative sheet 10 can be attached on at least one surface. In the decorative board 100, the base layer 11 of the decorative sheet 10 is attached to the substrate 101 via an adhesive layer 102. In other words, the decorative board 100 according to this embodiment is formed by attaching the decorative sheet 10 according to the first embodiment to the substrate 101.

[0127] "PCB 101" The substrate 101 is made of a hard material such as a wooden substrate such as wood plywood, a composite substrate made of a mixture of wood powder and plastic, or a resin substrate made of polyolefin such as polyethylene (PE) or polypropylene (PP) or polyvinyl chloride (PVC). Examples of the wooden substrate that can be used include tropical plywood, particle board, medium density fiberboard (hereinafter referred to as MDF), and ordinary plywood as specified by the Japanese Agricultural Standards. Substrates made of olefin resins containing wood powder can also be used. Note that the substrate 101 can also be made of metal such as aluminum, resin such as plastic, or a composite material thereof. By providing the substrate 101, a decorative board 100 that can suppress the occurrence of scratches can be provided.

[0128] 《Adhesive layer 102》 The adhesive layer 102 is provided on at least one surface of the substrate 101 in order to attach the decorative sheet 10 to the substrate 101. When the substrate 101 is made of, for example, a wood-based material, the adhesive layer 102 is generally made of a vinyl acetate emulsion-based material, a two-component curing urethane-based material, or the like.

[0129] It is also possible to provide adhesive layers 102 on both sides of substrate 101 and attach decorative sheets 10 to both sides of substrate 101 to form a decorative board. It is also possible to provide adhesive layer 102 instead of base layer 11 of decorative sheet 10, while providing base layer 11 on substrate 101, thereby attaching a decorative sheet to substrate 101. When wooden plywood or the like is used for substrate 101, if base layer 11 and adhesive layer 102 are made transparent, it is possible to utilize the wood of substrate 101 as a design.

[0130] In addition, in this embodiment, a decorative board 100 is formed by bonding a substrate 101 and a decorative sheet 10 together, but it is of course also possible to form a decorative board by bonding a substrate 101 and the decorative sheets 20, 30 of each of the embodiments described above.

[0131] Therefore, in this embodiment, it is possible to obtain the same effects as in the first embodiment described above.

[0132] [Fifth embodiment] A fifth embodiment of the decorative sheet and its manufacturing method according to the present invention will be described with reference to Fig. 5. 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.

[0133] <Basic structure of decorative tack sheet> As shown in Fig. 5, the decorative tack sheet 200 has a decorative sheet 10 and a tack sheet 201 that can attach the decorative sheet 10 to at least one surface. The decorative tack sheet 200 is formed by attaching an adhesive layer 201a of the tack sheet 201 to the base layer 11 of the decorative sheet 10. In other words, the decorative tack sheet 200 according to this embodiment is formed by attaching the tack sheet 201 to the decorative sheet 10 according to the first embodiment. In Fig. 5, 201b is a release paper.

[0134] Therefore, in this embodiment, it is possible to obtain the same effects as in the first embodiment described above. EXAMPLES

[0135] Examples of the decorative sheet and the manufacturing method thereof according to the present invention will be described below, but the present invention is not limited to only the following examples.

[0136] [Creation of test specimens and comparison specimens] Test specimen 1 "First step" A weather resistant agent was mixed into a transparent polypropylene resin, and a dispersant was added as a nano-sized additive (nano-dispersant specification) to prepare the resin material for the base layer. This resin material was extruded and embossed with a metal roll equipped with an embossing plate with wood grain vessel-like protrusions (height 30 μm) to produce a film-shaped base layer (thickness 70 μm) with wood grain vessel-like depressions (depth 30 μm).

[0137] The second step A pattern of wood grain vessels was printed on the back side of the prepared base layer by inkjet printing with inkjet printing ink (containing yellow, magenta, and cyan) at a resolution of 210 dpi to form a pattern layer. Next, a colored layer was formed by gravure printing using a two-component curing urethane resin mixed with titanium oxide white pigment. Furthermore, a colored layer was formed by gravure printing using a two-component curing urethane resin mixed with titanium oxide white pigment at a solid content of 1 g / m 2 A urethane resin was applied to provide a base layer.

[0138] The third step Next, the surface side of the base layer was subjected to a corona treatment, and then a high-gloss two-component curing acrylic resin containing silica (inorganic filler) with a particle size of 3 μm to 6 μm (35% by mass relative to the total solid content) was applied and heat-cured at 40° C. to form an undercoat layer (3 μm thick). Next, a low-gloss two-component curing acrylic resin was print-applied to the surface side of the undercoat layer in sync with the pattern of the pattern layer, and heat-cured at 40° C. to form a topcoat layer (3 μm thick). This produced decorative sheet specimen 1.

[0139] Test specimen 2 In the second step, a decorative sheet specimen 2 was produced in the same manner as specimen 1, except that a pattern layer was provided by printing a wood grain vessel pattern at a resolution of 305 dpi.

[0140] Test specimen 3 In the second step, a decorative sheet specimen 3 was produced in the same manner as specimen 1, except that a pattern layer was provided by printing a wood grain vessel pattern at a resolution of 610 dpi.

[0141] Test specimen 4 In the second step, a decorative sheet specimen 4 was produced in the same manner as specimen 1, except that a pattern layer was provided by printing a wood grain vessel pattern at a resolution of 720 dpi.

[0142] Test specimen 5 In the second step, a decorative sheet specimen 5 was produced in the same manner as specimen 1, except that a pattern layer was provided by printing a wood grain vessel pattern at a resolution of 980 dpi.

[0143] Comparison body 1 In the second step, a pattern of wood grain vessels was printed using a urethane-based resin (yellow, magenta, and cyan were not included) by gravure printing to form a pattern layer (resolution 150 dpi). Comparative decorative sheet 1 was prepared in the same manner as test specimen 1, except that

[0144] Comparison body 2 In the first step, a film-shaped base layer (70 μm thick) with pear-skinned depressions (10 μm deep) was produced by embossing with a metal roll equipped with an embossing plate having pear-skinned protrusions (10 μm high), and in the second step, a pattern layer was created by printing a picture of wood grain vessels at a resolution of 400 dpi. Comparative decorative sheet sample 2 was produced in the same manner as test sample 1, except that

[0145] [Evaluation Content] <Design> The design of test specimens 1 to 5 and comparative specimens 1 and 2 was evaluated visually. The results are shown in Table 1 below. In Table 1, excellent design is indicated with "◎", good design is indicated with "○", not bad design is indicated with "△", and bad design is indicated with "×".

[0146] <Beauty> The aesthetics of test specimens 1 to 5 and comparative specimens 1 and 2 were visually evaluated. The results are shown in Table 1 below. In Table 1, excellent aesthetics are indicated with "◎", good aesthetics are indicated with "○", not bad aesthetics are indicated with "△", and bad aesthetics are indicated with "×".

[0147] [Evaluation Results] The evaluation results of test specimens 1 to 5 and comparative specimens 1 and 2 are shown in Table 1 below.

[0148] [Table 1]

[0149] As can be seen from Table 1, in comparative sample 1, a wood grain vessel pattern picture layer was applied by gravure printing to a base fabric layer embossed with a wood grain vessel pattern to a depth of 30 μm, so the embossing and the picture could be synchronized, but the resolution was 150 dpi and the design was rated "○". Also, there were a few places where the ink was not fully transferred to the picture corresponding to the embossed recesses, so the aesthetics was rated "△". On the other hand, in comparative sample 2, the base fabric layer was embossed with a matte finish to a depth of 10 μm, so the embossing and the picture did not match, and a three-dimensional design could not be obtained, so the design was rated "△".

[0150] In contrast, in specimens 1 to 5, a wood grain vessel pattern layer was applied by inkjet printing to a base layer with a 30μm deep wood grain vessel embossing, which not only enabled the embossing and the pattern to be synchronized, but also enabled a resolution of 200 to 1000 dpi, earning a design rating of "Excellent." In addition, the ink was transferred satisfactorily to the pattern in the areas corresponding to the embossed recesses, earning a rating of "Excellent" for aesthetics.

[0151] It was therefore confirmed that the decorative sheet and its manufacturing method according to the present invention are capable of preventing deterioration in quality even in the case of a base layer having a deep embossed unevenness or a pattern layer having a long-period pattern. [Industrial Applicability]

[0152] The decorative sheet and manufacturing method of the present invention can produce a decorative sheet that can prevent deterioration in quality even in a base layer with deep embossing or a pattern layer with a long-period pattern, and can therefore be used in an extremely beneficial manner in industry. [Explanation of symbols]

[0153] 10 Decorative Sheet 11 Base layer 12 Colored layer 13 Picture layer 14 Original layer 14a Emboss 15 Surface protective layer 15A Undercoat layer 15B Top coat layer 20 Decorative Sheet 24 Original layer 24a Emboss 24A, 24B Skin section 24C Core 30 Decorative Sheet 34 Original layer 34A, 34B Skin section 100 Veneer 101 Substrate 102 Adhesive layer 200 Decorative tuck sheet 201 Tuck Sheet 201a Adhesive layer 201b Release paper

Claims

1. A base layer made of a single-layer film and having an embossed surface on one side thereof; A surface protective layer provided on one side of the raw fabric layer; a pattern layer provided on the other side of the base fabric layer and having a pattern; A decorative sheet having The raw fabric layer contains a transparent thermoplastic resin and at least one of a nucleating agent and an inorganic filler, The pattern layer is provided directly on the other surface of the base fabric layer, and has a resolution of 200 dpi or more and 1000 dpi or less. The embossment of the base fabric layer is formed to match the pattern of the pattern layer. A decorative sheet characterized by:

2. The pattern layer contains at least one of yellow, magenta, and cyan.

2. The decorative sheet according to claim 1.

3. The pattern of the pattern layer is a wood grain vessel pattern, The embossment of the raw fabric layer is in the form of a grain vessel.

2. The decorative sheet according to claim 1.

4. 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.

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 lower gloss than the second protective layer.

6. The decorative sheet according to claim 5.

7. A coloring layer is provided on one side of the other side of the design layer.

2. The decorative sheet according to claim 1.

8. A base layer is provided on one side of the colored layer.

8. The decorative sheet according to claim 7.

9. The colored layer serves as a base.

8. The decorative sheet according to claim 7.

10. A method for producing a decorative sheet according to any one of claims 1 to 3, comprising the steps of: a first step of heating and melting a raw material layer material obtained by mixing the thermoplastic resin with at least one of the nucleating agent and the inorganic filler to form a film shape while forming the embossment on one side of the raw material layer material; A second step of directly printing the pattern of the pattern layer on the other surface of the raw fabric layer by inkjet printing; a third step of providing the surface protective layer by adhering a resin material for the surface protective layer to one surface of the raw fabric layer; A method for producing a decorative sheet, comprising carrying out the steps of:

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