Decorative sheet, method for manufacturing decorative sheet, and decorative member

Abstract

To provide a decorative sheet that has texture close to texture of a surface of a wood or a stone material used for a housing material, has excellent designability, a method for manufacturing a decorative sheet, and a decorative member.SOLUTION: A decorative sheet 1 comprises: a pattern layer 3, a transparent thermoplastic resin layer 4 and a surface protective layer 5 which are laminated in order on one face of a colored thermoplastic resin layer 2; a pattern part 6 for gloss-matte expression which is laminated on the other face of the colored thermoplastic resin layer 2, arranged in synchronization with a pattern of the pattern layer 3, and is made of a predetermined material having higher light absorbance to light having a prescribed wavelength than the colored thermoplastic resin layer 2; and an embossed part 5a which is formed on a portion of the surface protective layer 5, which overlaps the pattern part 6 for gloss-matte expression in a plan view, where the area of the pattern part 6 for gloss-matte expression for the area of the other face of the colored thermoplastic resin layer 2 is 90% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Conventionally, decorative members in which a decorative sheet is bonded to a wooden substrate such as plywood, MDF (medium density fiberboard), or particle board, a resin substrate, an inorganic non-combustible substrate, or a metal substrate have been widely used (see, for example, Patent Document 1). Furthermore, the design of the decorative sheet is often imitated to resemble the surface of wood, stone, or the like. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5045180 Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, decorative sheets tend to have a flat surface texture compared to real wood or stone. Actual wood and stone have different textures due to differences in the surface material and structure, resulting in unevenness in different locations. Areas with different textures often also have different colors, but this is not expressed in decorative sheets, and in terms of design, more expensive real ones are superior. The present invention has been made in consideration of these points, and aims to provide a decorative sheet that has a texture similar to the surface texture of wood, stone, etc. used in building materials and has excellent design properties, a manufacturing method for the decorative sheet, and a decorative member. [Means for solving the problem]

[0005] According to one aspect of the present invention, a pattern layer, a transparent resin layer, and a surface protection layer are sequentially laminated on one surface of a colored resin layer, and are laminated on the other surface of the colored resin layer and arranged in synchronization with the pattern of the pattern layer. A gloss-matte pattern portion made of a predetermined material having higher light absorptivity than the colored resin layer with respect to light of a predetermined wavelength, and an embossed portion formed in a portion of the surface protection layer that overlaps with the gloss-matte pattern portion in plan view are provided. A decorative sheet is provided in which the area of the gloss-matte pattern portion with respect to the area of the other surface of the colored resin layer is 90% or less.

[0006] Also, according to another aspect of the present invention, a step of laminating a pattern layer, a transparent resin layer, and a surface protection layer in this order on one surface of a colored resin layer, and on the other surface of the colored resin layer, a gloss-matte pattern portion that is synchronized with the pattern of the pattern layer using a predetermined material having higher light absorptivity than the colored resin layer with respect to light of a predetermined wavelength. A step of forming, and after the step of forming the gloss-matte pattern portion, irradiating the surface protection layer with irradiation light in which the power of the light of the predetermined wavelength is stronger than the power of the light of other wavelengths, and after the step of irradiating the irradiation light, embossing the surface protection layer with an embossing plate for forming an embossed shape. A method for manufacturing a decorative sheet is provided in which the gloss-matte pattern portion is formed such that the area of the gloss-matte pattern portion with respect to the area of the other surface of the colored resin layer is 90% or less.

[0007] Furthermore, according to another aspect of the present invention, a decorative member is provided that includes a base material and the decorative sheet according to the above aspect provided on at least one surface of the base material, and the base material is any one of a wood base material, a resin base material, a non-combustible base material, and a metal base material.

Effects of the Invention

[0008] According to one embodiment of the present invention, it is possible to obtain a decorative sheet having a texture similar to the texture of the surface of wood, stone, etc. used in building materials and having excellent design properties.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Mode for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present technology will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, etc. are different from the actual ones. As long as it is within the scope of the present disclosure, it is not necessarily required to be laminated in the order shown in the drawings. Also, layers not described in this drawing may be added. Further, the embodiments shown below exemplify the configurations for embodying the technical idea of the present disclosure, and the technical idea of the present disclosure is not specified to the following in terms of the material, shape, and structure of the constituent parts, etc. The technical idea of the present disclosure can be variously modified within the technical scope defined by the claims described in the claims.

[0011] Also, the directions of "left and right" and "up and down" in the following description are merely definitions for convenience of explanation and do not limit the technical idea of the present disclosure. Therefore, for example, if the paper surface is rotated 90 degrees, "left and right" and "up and down" are read in exchange, and if the paper surface is rotated 180 degrees, it goes without saying that "left" becomes "right" and "right" becomes "left".

[0012] 〔Configuration of Cosmetic Sheet〕 As shown in, for example, FIG. 1, a cosmetic sheet 1 according to an embodiment of the present invention is formed by laminating a colored thermoplastic resin layer (colored resin layer) 2, a pattern layer 3, a transparent thermoplastic resin layer (transparent resin layer) 4, and a surface protective layer 5 in this order. An embossed portion (embossed shape) 5a is formed on the surface protective layer 5. Further, a pattern portion 6 for expressing gloss and matte is formed on the surface of the colored thermoplastic resin layer 2 opposite to the pattern layer 3, and a primer layer 7 is formed so as to cover the pattern portion 6 for expressing gloss and matte and the colored thermoplastic resin layer 2.

[0013] 〔Colored thermoplastic resin layer〕 The colored thermoplastic resin layer 2 as a base material includes, for example, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, and the like. Among them, polyolefin-based resins can be preferably used in terms of environmental compatibility, processability, and price. The grade and composition of the resin can be selected in consideration of other factors such as ease of sheeting, printability, and suitability for bending.

[0014] The hue of the colored thermoplastic resin layer 2 can be appropriately selected as the base color of the pattern layer 3. The colored thermoplastic resin layer 2 can be colored, for example, by mixing or kneading a colorant such as a pigment during the sheeting of the thermoplastic resin. Alternatively, before providing the pattern portion 6 for expressing gloss and matte, the colored thermoplastic resin layer can be provided as a solid ink layer using a coating or printing method. The thickness of the colored thermoplastic resin layer 2 can be set to a value within the range of 45 μm or more and 130 μm or less.

[0015] 〔Pattern layer〕 The pattern layer 3 is a printed layer with a pattern printed thereon to impart design characteristics to the decorative sheet 1. As a method for forming the pattern layer 3, known printing techniques can be employed. The printing technique is not particularly limited, but in consideration of productivity and pattern quality, the gravure printing method is preferred. Also, for example, when the colored thermoplastic resin layer 2 can be prepared in a wound state, printing for forming the pattern layer 3 can be performed by using a roll-to-roll printing apparatus. In addition to these, examples of printing techniques include the offset printing method, screen printing method, flexographic printing method, electrostatic printing method, inkjet printing method, transfer printing method from a transfer sheet, and the like. When using such printing techniques, the pattern of the pattern layer 3 can be formed by multicolor printing using ordinary process colors such as yellow, red, blue, and black, and can also be formed by multicolor printing with a characteristic using individual color plates constituting the pattern, and the like.

[0016] Also, for the pattern of the pattern layer 3, any pattern may be adopted in consideration of the design characteristics as a floor material or a fixture. For example, imaging a stone floor such as marble, the grain of marble or the like can be used as the pattern. Also, for example, in the case of a woody pattern, various wood grains and cork can be used as the pattern. Also, for example, in addition to the pattern of natural materials, artificial pattern motifs such as artificial pattern motifs and geometric patterns using these as motifs can also be used. In addition to these, examples of patterns include, for example, a wood grain pattern composed of the spring wood region and autumn wood region of the cross-section of an annual ring, a conduit part, etc., a leather (leather texture) pattern, a grain pattern on the surface of a stone such as marble, granite, sandstone, a sandblasted pattern, a tile pasted pattern, a brick laid pattern, a cloth pattern, geometric figures, letters, symbols, abstract patterns, flower patterns, landscapes, characters, and the like.

[0017] The printing ink is a mixture of a solvent and solid components such as a colorant and a binder resin. Examples of the solvent include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. The solvent may be used alone or in combination of two or more kinds.

[0018] Examples of the binder resin include chlorine-based resins, urethane resins, acrylic urethane resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. Examples of the chlorine-based resins include polyvinyl chloride-based resins such as polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-vinyl acetate-(meth)acrylic copolymer, and polypropylene chloride and chlorinated polypropylene. Here, (meth)acrylic means acrylic or methacrylic. The binder resin may be used alone or in combination of two or more kinds.

[0019] Examples of the colorant include inorganic pigments such as carbon black, iron black, titanium white (titanium oxide), antimony white, lead yellow, titanium yellow, cadmium red, ultramarine blue, and cobalt blue; and organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue. The colorant may be used alone or in combination of two or more kinds. Here, the solvent contained in the printing ink will eventually volatilize. Therefore, the pattern layer 3 is mainly formed of solid components such as a colorant and a binder resin.

[0020] In addition, the printing ink may contain, as other components, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. As the printing ink, an ink corresponding to the printing method may be adopted. In particular, it is preferably selected in consideration of the adhesion to the colored thermoplastic resin layer 2, the printability, and the weather resistance as a floor material or a fixture. The thickness of the pattern layer 3 can be appropriately adjusted in consideration of the required decorativeness of the pattern layer 3, the three-dimensional moldability of the decorative sheet 1, etc. The thickness of the pattern layer 3 is usually 1 μm or more and 1 mm or less, preferably 2 μm or more and 0.1 mm or less, and more preferably 2 μm or more and 50 μm or less.

[0021] For the purpose of improving the adhesiveness between the pattern layer 3 and the transparent thermoplastic resin layer 4, an adhesive layer (not shown) may be provided on the surface of the pattern layer 3 on the side in contact with the transparent thermoplastic resin layer 4. By strengthening these adhesions, the decorative sheet 1 can be imparted with bendability that follows a curved surface or a right-angled surface. The resin used for the adhesive layer (not shown) is not particularly limited. For example, a two-component curable urethane-based resin can be adopted. Also, an adhesive resin may be adhered to the pattern layer 3 with a urethane-based adhesive. For the application of the resin used for the adhesive layer (not shown), for example, a coating device or a gravure printing device can be adopted.

[0022] In addition, for the purpose of preferably imparting a design effect such as a sense of depth or a sense of luminance of the decorative sheet 1, a luminous layer (not shown) may be provided between the pattern layer 3 and the transparent thermoplastic resin layer 4. The luminous layer (not shown) preferably contains a luminous pigment and a binder resin. Examples of the luminous pigment include a pearl pigment and a metal pigment. In particular, the pearl pigment is preferable because it can suppress a decrease in the light transmittance of the luminous layer and does not impair the visibility of the pattern layer 3.

[0023] Pearlescent pigments are pigments that can impart a true pearlescent luster. For example, those obtained by coating the surface of matrix particles with a metal oxide can be mentioned. As the matrix particles, scaly particles such as mica are preferable. As the metal oxide, oxides of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium can be mentioned. The metal oxide may be a single species or two or more species. Specific examples include mica titanium, iron oxide-coated mica, iron oxide-coated mica titanium, ultramarine-coated mica titanium, ultramarine-iron oxide-coated mica titanium, chromium oxide-coated mica titanium, carmine-coated mica titanium, organic pigment-coated mica titanium, titanium oxide-coated mica, titanium oxide-coated synthetic mica, etc. oxide-coated mica; oxide-coated glass powders such as titanium oxide-coated glass powder and iron oxide-coated glass powder; oxide-coated metal particles such as titanium oxide-coated aluminum powder; scaly foil pieces such as basic lead carbonate, lead hydrogen arsenate, bismuth oxychloride; fish scale powder, shell pieces, pearl pieces, etc.

[0024] In addition, as the metallic pigment, pigments composed of metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold powder, and silver, alloys of these metals, etc. can be mentioned. The metallic pigment may be used alone or in combination of two or more.

[0025] From the viewpoint of imparting an excellent design effect, the average particle diameter of the lustrous pigment is preferably 40 μm or less, more preferably 30 μm or less, for example, when forming a lustrous layer using gravure printing. From the same viewpoint, the ratio of [average particle diameter of the lustrous pigment / thickness of the lustrous layer] is preferably 0.01 or more and 15 or less, more preferably 0.5 or more and 10 or less. In this specification, the "average particle diameter" is a value that can be obtained as the mass average value D50 in the particle size distribution measurement by the laser light diffraction method.

[0026] In addition, examples of the binder resin include a thermoplastic resin, a cured product of a curable resin composition, etc., and from the viewpoint of durability, a cured product of a curable resin composition is preferred. Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionizing radiation curable resin composition. From the viewpoint of interlayer adhesion, a cured product of a thermosetting resin composition is preferred.

[0027] Examples of the thermosetting resin composition used for the light-emitting layer include a polyester resin composition, an epoxy resin composition, a polyurethane resin composition, an aminoalkyd resin composition, a melamine resin composition, a guanamine resin composition, a urea resin composition, and a thermosetting acrylic resin composition, etc. These thermosetting resin compositions include monomers and / or prepolymers constituting each resin, and a curing agent added as necessary, etc. As the ionizing radiation curable resin composition used for the light-emitting layer, the same one as the ionizing radiation curable resin composition of the surface protection layer 5 described later can be used.

[0028] The content of the light-emitting pigment in the light-emitting layer is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 50 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the binder resin. By setting the content of the light-emitting pigment to 10 parts by mass or more, a sufficient gloss can be imparted, and by setting it to 90 parts by mass or less, it is possible to suppress the visibility of the pattern layer 3 from being impaired. From the same viewpoint, the thickness of the light-emitting layer is preferably 1 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less.

[0029] The light-emitting layer can form an arbitrary pattern according to the design to be imparted. For example, wood grain patterns, leather patterns, stone patterns, sand patterns, tile pasted patterns, brick stacked patterns, cloth patterns, geometric figures, characters, symbols, abstract patterns, flower patterns, landscapes, characters, etc. can be mentioned. In addition, any pattern preferably has shading in order to enhance the design effect more. The shading may be formed from the size and thickness of the halftone dots, but it is preferred to form it from the coarseness and fineness of the halftone dots (that is, the size of the halftone dots is uniform and the density of the halftone dots forms the shading).

[0030] The luminous layer can be formed, for example, by applying a coating liquid containing a luminous pigment and a binder resin using a general printing method such as gravure printing. When forming the light and shade of the luminous layer from the coarseness and fineness of the halftone dots, the halftone dots of the printing plate may be formed by an FM (frequency modulation) screen.

[0031] 〔Transparent thermoplastic resin layer〕 The transparent thermoplastic resin layer 4 is a resin layer for protecting the pattern layer 3 and imparting good surface physical properties so as to give a thickness and depth artistically and improve the weather resistance and abrasion resistance of the decorative sheet 1. As the material of the transparent thermoplastic resin layer 4, for example, a polypropylene resin can be used. In particular, polyolefin-based resins are preferred in terms of environmental compatibility, processability, and price. In addition to environmental compatibility, processability, and price, the grade and composition of the resin can be selected in consideration of ease of seating, printability, and suitability for bending. It is important to select considering that whitening or cracking does not occur in the bent portion in terms of suitability for bending.

[0032] This transparent thermoplastic resin layer 4 may contain nano-sized additives. The nano-sized additive is an additive that has been made into nano-sized particles by a method (nano-sizing treatment) of making the additive into nano-size. Examples of the nano-sizing treatment include a solid-phase method in which mainly mechanical grinding is performed on the additive to obtain nano-sized particles, a liquid-phase method in which nano-sized particle synthesis or crystallization is performed in a solution in which the additive or the additive is dissolved, and a gas-phase method in which nano-sized particle synthesis or crystallization is performed from a gas or vapor composed of the additive or the additive. Specific means for implementing each method are briefly listed. As the solid-phase method, ball mills, bead mills, rod mills, colloid mills, conical mills, disk mills, hammer mills, jet mills, etc. can be mentioned. As the liquid-phase method, crystallization methods, coprecipitation methods, sol-gel methods, liquid-phase reduction methods, hydrothermal synthesis methods, etc. can be mentioned. And as the gas-phase method, electric furnace methods, chemical flame methods, laser methods, thermal plasma methods, etc. can be mentioned.

[0033] To describe a more specific method of nanosizing treatment, as a specific example of the solid-phase method, for example, a mixture of 100 g of isopropyl alcohol and 50 g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate can be milled for 60 minutes using 30-μm stabilized zirconia beads in a bead mill to obtain nanosized nucleating agent particles with an average particle diameter of about 100 nm to 150 nm. Further, as a specific example of the crystallization method, for example, 50 g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate is dissolved in a mixed solvent composed of 96 g of xylene, 72 g of isopropyl alcohol, and 24 g of water, and this solution is brought into contact with a poor solvent such as ethanol in a microreactor to precipitate nanosized nucleating agent particles with an average particle diameter of 1 nm to 150 nm.

[0034] Also, a vesicle refers to a vesicular capsule having a spherical shell-shaped closed membrane structure. In particular, those containing a liquid phase inside are called vesicles. In the present invention, an additive is contained in this liquid phase. These vesicles have extremely high dispersibility because the outer membranes of the vesicles repel each other and prevent the particles from aggregating. This effect enables the additive to be uniformly dispersed in the resin composition constituting each resin layer. Examples of methods (vesiculation treatment) for obtaining nano-sized additives as vesicles during the nanosizing treatment include the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse evaporation method, the freeze-thaw method, the supercritical reverse evaporation method, and the like. A brief explanation of such vesiculation treatment is as follows: In the Bangham method, chloroform or a chloroform / methanol mixed solvent is placed in a container such as a flask, and phospholipid is further added and dissolved. Then, the solvent is removed using an evaporator to form a thin film composed of lipid. After adding a dispersion of the additive, vesicles are obtained by hydrating and dispersing with a vortex mixer. The extrusion method is a method of preparing a thin film phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain vesicles. The hydration method is almost the same preparation method as the Bangham method, but vesicles are obtained by gently stirring and dispersing without using a mixer. The reverse evaporation method is a method of dissolving phospholipid in diethyl ether or chloroform, adding a solution containing an additive to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method is a method that uses cooling and heating as external perturbations, and vesicles are obtained by repeating this cooling and heating.

[0035] In particular, as a method for obtaining vesicles having an outer membrane composed of a single-layer film, the supercritical reverse phase evaporation method can be mentioned. The supercritical reverse phase evaporation method is a method for producing capsules encapsulating a target substance using carbon dioxide under supercritical state or temperature conditions or pressure conditions above the critical point. Supercritical carbon dioxide means carbon dioxide in a supercritical state above the critical temperature (30.98 °C) and critical pressure (7.3773 ± 0.0030 MPa), and carbon dioxide under temperature conditions or pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions.

[0036] In the specific vesiculation treatment by the supercritical reverse phase evaporation method, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, a phospholipid as a dispersant, and an additive as an inclusion substance, and stirred to generate an emulsion of supercritical carbon dioxide and the aqueous phase. Then, when the pressure is reduced, carbon dioxide expands and evaporates, causing a phase inversion, and nanocapsules are generated in which the phospholipid covers the surface of the additive particles with a single-layer film. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the dispersant forms a multi-layer film on the surface of the additive particles, capsules with a single-layer film can be easily generated, so that smaller-diameter capsules can be prepared. In addition, when capsules with a multi-layer film are desired, they can be easily prepared by injecting supercritical carbon dioxide into a mixed fluid of phospholipid, additive, and aqueous phase. Examples of the phospholipid used when preparing the vesicles include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and sphingomyelins such as sphingomyelin, ceramide phosphoethanolamine, and ceramide phosphorylglycerol. The vesicles can achieve excellent compatibility with the resin material by having an outer membrane composed of a phospholipid.

[0037] Further, the vehicle may include an outer membrane made of a dispersant. Examples of the dispersant include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicones, waxes, modified resins, and the like. Examples of the polymer surfactant include aliphatic polyvalent polycarboxylic acids, polycarboxylic acid alkylamines, polyacrylic acid, polymethacrylic acid, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, and the like. Examples of the fatty acid metal salt include those formed by combining stearic acid, lauric acid, 12-hydroxystearic acid, montanic acid, behenic acid, ricinoleic acid, myristic acid, etc. with lithium, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, etc. Examples of the silane coupling agent include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Examples of the titanate coupling agent include tetrakis[2,2-bis(allyloxymethyl)butoxy]titanium(IV), di-i-propoxytitanium dioctostearate, (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, isopropyltitanium triisostearate, di-n-butoxy·bis(triethanolaminato)titanium, tetrakis(2-ethylhexyloxy)titanium, di-i-propoxy·bis(acetylacetonato)titanium, and the like. Examples of the silicone include those obtained by polymerizing olefins such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, cyclic dimethyl silicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid-modified silicone oil, etc., or by pyrolyzing polyolefins, and further modified by oxidation or by maleic acid, sulfonic acid, carboxylic acid, rosin acid, etc. Examples of the resin include those obtained by modifying polyolefins with maleic acid, sulfonic acid, carboxylic acid, rosin acid, etc.

[0038] When the transparent thermoplastic resin layer 4 is made of a resin layer containing nano-sized additives, it is important that the main component is 90 to 100% by weight of crystalline polypropylene resin and it contains a nucleating agent as the nano-sized additive. More preferably, the nano-sized additive is contained in the state of vesicles (nucleating agent vesicles). In this case, it is preferable that the average particle size of the nucleating agent vesicles is 1 / 2 or less of the wavelength of visible light. Specifically, since the wavelength region of visible light is 400 to 750 nm, it is preferable that the average particle size is 375 nm or less. In such a transparent thermoplastic resin layer 4, by adjusting the cooling conditions during film formation, it is important that the haze value is 15% or less, more preferably 10% or less, the tensile modulus is 800 MPa or more and 2000 MPa or less, and the tensile elongation at break is 200% or more.

[0039] Also, the crystalline polypropylene resin can be appropriately selected and designed from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene having different pentad fractions and mixtures thereof. More preferably, it is important that the crystalline polypropylene resin is a highly crystalline homopolypropylene resin which is a homopolymer of propylene having an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. In addition, as long as the resin other than the crystalline polypropylene constituting the transparent thermoplastic resin layer 4 does not significantly adversely affect the physical properties of the crystalline polypropylene, it can be appropriately selected according to the purpose of its blending. However, in order to maintain the V-groove bending processability, it is preferable that the resin has good compatibility with the crystalline polypropylene resin constituting the transparent thermoplastic resin layer 4.

[0040] It is preferable that such a transparent thermoplastic resin layer 4 has a thickness within the range of 35 μm or more and 130 μm or less. Because the particle size of the nano-sized nucleating agent is extremely small, i.e., in the nano-size range, the number and surface area of the nucleating agents present per unit volume increase in inverse proportion to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes closer. When crystal growth occurs from the surface of one nucleating agent particle added to the polypropylene resin, the end of the growing crystal immediately contacts the end of the crystal growing from the surface of another nucleating agent particle adjacent to the said nucleating agent particle, and the growth of each crystal is inhibited as the ends of the mutual crystals impede the growth, so that the average particle diameter of the spherulites in the crystalline part of the crystalline polypropylene resin can be made extremely small.

[0041] Therefore, by incorporating a nano-sized nucleating agent into the transparent thermoplastic resin layer 4, compared with conventional nucleating agents, finer and larger amounts of crystal nuclei are generated in the resin, and as a result, the distance between the crystal nuclei in the crystalline part is shortened, the growth of individual crystals is suppressed, and the average particle diameter of the spherulites is successfully made extremely small. And in such a crystalline polypropylene resin, excellent high transparency with a haze value of 15% or less is realized.

[0042] Furthermore, by incorporating the nano-sized nucleating agent in the form of vesicles, i.e., as nucleating agent vesicles, aggregation of the nucleating agents is prevented and high dispersibility in the resin material is realized. In the resin composition, the outer membrane of the nucleating agent vesicle is partially disintegrated and the nucleating agent is in an exposed state, and in the crystallization process of the resin material, spherulites having the nano-sized nucleating agent particles as crystal nuclei are formed.

[0043] At this time, in particular, since the nucleating agent vesicles obtained by the supercritical reverse phase evaporation method are extremely small in size, the average particle diameter of the spherulites in the crystalline part of the crystalline polypropylene resin can be made extremely small, and at the same time, the crystallinity of the crystalline part can be dramatically improved.

[0044] In the cosmetic sheet of the present invention, by containing a nano-sized nucleating agent, more preferably a nucleating agent vesicle, in the transparent thermoplastic resin layer 4, the average particle diameter of spherulites in the crystalline part of the crystalline polypropylene resin is made extremely small, realizing excellent abrasion resistance. In particular, by containing the nucleating agent vesicle, the nucleating agent is uniformly dispersed in the crystalline polypropylene resin, the crystallinity of the crystalline polypropylene is controlled, and the hardness and toughness of the transparent resin layer are adjusted to be optimal, achieving excellent abrasion resistance and post-processing resistance with a tensile elastic modulus of 800 MPa or more and 2000 MPa or less, and a tensile elongation at break of 200% or more.

[0045] As a method for forming the transparent thermoplastic resin layer 4, a lamination technique can be adopted. Further, for example, when the transparent thermoplastic resin layer 4 and an adhesive layer (not shown) are formed simultaneously, a method of simultaneously extruding both by co-extrusion can be adopted.

[0046] Hereinafter, the terms used in the above description will be briefly explained. A nucleating agent is added to promote the generation of crystal nuclei during the crystallization of a resin or to use the nucleating agent itself as a crystal nucleus. There are a melting type that melts in the resin of the base material during addition and re-precipitates to generate crystal nuclei, and a non-melting type in which the nucleating agent added to the base material becomes a crystal nucleus with the same particle size without melting. Examples of nucleating agents for polypropylene resin include metal phosphate esters, metal benzoates, metal pimelates, metal rosinate, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in the present invention, it is preferable to use metal phosphate esters, metal benzoates, metal pimelates, and metal rosinate, which are non-melting types and can be expected to have good transparency, in order to maximize the effect of the nanosizing treatment. However, when transparency can be achieved by the nanosizing treatment, colored quinacridone, cyanine blue, talc, etc. can also be used. Further, a melting type of benzylidene sorbitol may be appropriately mixed with the non-melting type of nucleating agent and used.

[0047] The haze value is a value obtained by dividing, by the total light transmittance, the value (diffuse transmittance) obtained by subtracting the integrated value of only the linear component of the light rays emitted from the other side (linear transmittance) from the integrated value of all the light rays emitted from the other side (total light transmittance) when the light incident from one side of an object exits from the other side. A smaller value indicates higher transparency. This haze value is determined by the internal haze determined by the internal state of the object such as the degree of crystallinity and spherulite size in the crystalline part, and the external haze determined by the surface state of the object such as the presence or absence of unevenness on the incident surface and the exit surface. In the present invention, when simply referred to as the haze value, it means the value determined by the internal haze and the external haze.

[0048] The tensile elongation at break is a value representing the elongation when a sample is pulled at a predetermined speed and broken. It is a value obtained by dividing, by the length (L0) of the sample before the test, the value obtained by subtracting the length (L0) of the sample before the test from the length (L) of the sample at the time of break, and expressed as a percentage. A smaller value indicates poorer elongation, and cracks and whitening are likely to occur during post-processing such as V-groove bending, resulting in poor post-processability. A larger value indicates better elongation, easy post-processing, and excellent post-processability.

[0049] The isotactic pentad fraction (mmmm fraction) is calculated from the numerical value (electromagnetic wave absorption rate) obtained by resonating the resin material constituting the transparent thermoplastic resin layer 4 at a predetermined resonance frequency by means of 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclide) with a mass number of 13. It defines the atomic arrangement, electronic structure, and fine structure of the molecule in the resin material. The isotactic pentad fraction of a polypropylene resin refers to the ratio of five propylene units arranged side by side as determined by 13C-NMR, and is used as a measure of the degree of crystallinity or stereoregularity. Such an isotactic pentad fraction is one of the important factors mainly determining the scratch resistance of the surface. Basically, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, and thus the scratch resistance is improved.

[0050] [Surface protection layer] The surface protective layer 5 is a layer for imparting surface physical properties such as abrasion resistance to the decorative sheet 1. Further, the surface protective layer 5 is also a layer for adjusting the gloss of the surface of the decorative sheet 1. The surface protective layer 5 may be a single layer or multiple layers. For example, as the surface protective layer 5, two layers of a first surface protective layer (not shown) and a second surface protective layer (not shown) can be provided in this order on the transparent thermoplastic resin layer 4. When providing the surface protective layer 5 composed of the first surface protective layer (not shown) and the second surface protective layer (not shown), each layer can be applied and the coating film can be cured using a known coating device, a heat drying device, and an ionizing radiation irradiation device according to the type of the curable resin.

[0051] The surface protective layer 5 is mainly composed of a curable resin. That is, it is preferable that the resin component of the surface protective layer 5 is substantially composed of a curable resin. Substantially means, for example, 80 parts by mass or more when the total resin is 100 parts by mass. The surface protective layer 5 may contain, as necessary, weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, and the like.

[0052] As the material of the surface protective layer 5, for example, an ionizing radiation curable resin or a two-component curable urethane resin can be adopted. The ionizing radiation curable resin is not particularly limited. For example, a transparent resin mainly composed of a prepolymer (including an oligomer) and / or a monomer containing a radical polymerizable double bond capable of undergoing a polymerization crosslinking reaction by irradiation with ionizing radiation such as infrared rays, ultraviolet rays, and electron beams can be adopted. These prepolymers or monomers can be used alone or in combination of a plurality. Specifically, examples of the prepolymer or monomer include compounds having a radical polymerizable unsaturated group such as a (meth)acryloyl group and a (meth)acryloyloxy group, and a cationic polymerizable functional group such as an epoxy group in the molecule. Also, a polyene / thiol-based prepolymer formed by a combination of a polyene and a polythiol is also preferable. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0053] Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, silicone (meth)acrylate, and the like. The molecular weight of these is preferably about 250 to 100,000. Examples of the monomer having a radically polymerizable unsaturated group include, as monofunctional monomers, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like. Examples of the polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

[0054] Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of the polyene prepolymer include those obtained by adding allyl alcohol to both ends of a polyurethane made from a diol and a diisocyanate. Examples of the thiol prepolymer include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

[0055] As the ionizing radiation, for example, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in an ionizing radiation-curable resin (composition) can be adopted. Examples of the curing reaction include a crosslinking curing reaction. As the ultraviolet light source, for example, light sources such as a super-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp can be adopted. As the wavelength of the ultraviolet light, for example, 190 nm or more and 380 nm or less is preferable. As the electron beam source, for example, electron beam accelerators such as a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, a dynatron type, and a high frequency type can be adopted. In particular, those capable of irradiating electrons having an energy of 100 keV or more and 1000 keV or less (more preferably electrons having an energy of 100 keV or more and 300 keV or less) are preferable.

[0056] Also, the two-component curable urethane resin is not particularly limited. For example, those containing a polyol component having an OH group as the main agent and an isocyanate component as the curing agent component can be adopted. Examples of the polyol component having an OH group include acrylic polyol, polyester polyol, polyether polyol, and epoxy polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylylene diisocyanate.

[0057] 〔Embossed portion〕 On the surface of the surface protection layer 5, an embossed portion 5a formed of a concavo-convex pattern is formed in order to impart a given design property. Examples of the concavo-convex pattern include a wood grain board conduit groove, a concavo-convex pattern on a slate surface (such as a granite cleavage surface), a cloth surface texture, a satin finish, a matte finish, a hairline, and a multi-line groove. This embossed portion 5a is provided so that the concavo-convex pattern thereof is synchronized with the pattern of the pattern layer 3.

[0058] As a method for forming the concavo-convex pattern, for example, embossing can be adopted. The method of embossing is not particularly limited. For example, a known sheet-fed embossing machine or a rotary embossing machine can be adopted. Thereby, a good texture similar to that of actual wood or stone can be imparted to the decorative sheet 1.

[0059] 〔Pattern part for expressing gloss matte〕 The pattern part 6 for expressing gloss matte is formed of a material having light absorptivity with respect to light of a predetermined wavelength, and is formed of, for example, a material having an infrared absorption effect. The pattern part 6 for expressing gloss matte is formed of a material containing ink containing carbon black, and is formed of, for example, urethane-based printing ink. The pattern part 6 for expressing gloss matte is disposed at a position synchronized with the pattern of the pattern layer 3 on the side opposite to the pattern layer 3 of the colored thermoplastic resin layer 2. For example, in the case of the pattern layer 3 having a wood grain pattern, the pattern part 6 for expressing gloss matte is formed at a position overlapping the wood grain conduit groove of the pattern layer 3 in a plan view. Here, the synchronization means that it is formed at a position where the pattern part 6 for expressing gloss matte and the pattern of the pattern layer 3 overlap in a plan view.

[0060] The thickness of the pattern part 6 for expressing gloss matte may be such that the transparent thermoplastic resin layer 4 and the surface protective layer 5 can be softened to a degree that an uneven shape can be sufficiently formed on the surface protective layer 5 during the embossing process described later. Further, in order to obtain a sufficient gloss matte effect, it is preferable that the difference in glossiness between the portion where the pattern part 6 for expressing gloss matte is formed and the portion where it is not formed is 5 or more, that is, the image density level is 60% or more.

[0061] In addition, the pattern part 6 for expressing gloss matte is formed such that the area of the pattern part 6 for expressing gloss matte is 90% or less with respect to the area of the surface on the side opposite to the pattern layer 3 of the colored thermoplastic resin layer 2, that is, the surface on the side where the pattern part 6 for expressing gloss matte is formed.

[0062] Here, when the area of the gloss matte pattern portion 6 is larger than the area of the surface of the colored thermoplastic resin layer 2 that forms the gloss matte pattern portion 6, it is difficult for the primer layer 7 to uniformly cover the gloss matte pattern portion 6, and it is difficult for the surface of the primer layer 7 on the side opposite to the gloss matte pattern portion 6 to be uniform. In this state, when a base material (not shown) is attached to the surface of the decorative sheet 1 on the primer layer 7 side, peeling is likely to occur between the decorative sheet 1 and the base material because the surface of the primer layer 7 is not uniform. Further, since the colored thermoplastic resin layer 2 is more compatible and has a higher adhesive strength compared to the gloss matte pattern portion 6, when the area of the gloss matte pattern portion 6 is large, the area where the primer layer 7 and the colored thermoplastic resin layer 2 are in direct contact is small, so the adhesive strength between the primer layer 7 and the colored thermoplastic resin layer 2 becomes weak, and peeling is likely to occur between the primer layer 7 and the colored thermoplastic resin layer 2.

[0063] By setting the area of the gloss matte pattern portion 6 to 90% or less with respect to the area of the surface of the colored thermoplastic resin layer 2 on the side where the gloss matte pattern portion 6 is formed, a certain area where the colored thermoplastic resin layer 2 and the primer layer 7 are in direct contact is ensured, so the adhesive strength between the colored thermoplastic resin layer 2 and the primer layer 7 can be ensured. Also, the uniformity of the surface of the decorative sheet 1 on the primer layer 7 side can be ensured to a certain extent. As a result, peeling between the colored thermoplastic resin layer 2 and the primer layer 7, and between the primer layer 7 and the base material is suppressed.

[0064] 〔Light of a predetermined wavelength〕 The gloss matte pattern portion 6 is formed of a material having light absorbency with respect to light of a predetermined wavelength. Examples of the light of a predetermined wavelength include infrared rays, ultraviolet rays, visible light, electron beams, X-rays, ion beams, and the like.

[0065] 〔Primer layer〕 The primer layer 7 is a base layer and is a layer for improving the adhesion and corrosion resistance to a base material (not shown) to which the decorative sheet 1 is attached. The primer layer 7 is formed on the surface of the colored thermoplastic resin layer 2 on the side opposite to the pattern layer 3 so as to cover the gloss matte pattern portion 6.

[0066] The primer layer 7 is formed using, for example, a polyester resin, an organic additive, a pigment, etc. A rust preventive pigment may be blended into the primer layer 7 for the purpose of improving corrosion resistance. The thickness of the primer layer 7 is, for example, in the range of 1 μm or more and 10 μm or less.

[0067] [Manufacturing method of the decorative sheet] Next, an example of the manufacturing method of the decorative sheet according to the present embodiment will be described with reference to FIG. 2.

[0068] First, the colored thermoplastic resin layer 2 is formed. For example, using a PBT (polybutylene terephthalate) resin, the colored thermoplastic resin layer 2 is formed with a thickness of, for example, 50 μm (FIG. 2(a)). The colored thermoplastic resin layer 2 is not limited to the PBT resin, and a PE resin, a PP resin, etc. may also be used. Also, the thickness of the colored thermoplastic resin layer 2 may be a value within the range of 45 μm or more and 130 μm or less.

[0069] Next, a pattern layer 3 is printed on one surface of the colored thermoplastic resin layer 2 using, for example, a urethane-based printing ink. Next, a gloss / matte expression pattern portion 6 is formed on the surface of the colored thermoplastic resin layer 2 opposite to the pattern layer 3. For example, using a urethane-based printing ink containing carbon black-containing ink, the gloss / matte expression pattern portion 6 is formed at a predetermined position synchronized with the pattern of the pattern layer 3 (FIG. 2(b)).

[0070] Next, on the colored thermoplastic resin layer 2 including the gloss / matte expression pattern portion 6, a primer layer 7 made of, for example, a polyester resin is formed so as to fill the gaps between the gloss / matte expression pattern portions 6 and cover the upper surface thereof (FIG. 2(c)). Next, a PP (polypropylene) resin with a thickness of, for example, 90 μm is laminated as the transparent thermoplastic resin layer 4 on the surface of the pattern layer 3 opposite to the colored thermoplastic resin layer 2. A nucleating agent subjected to a nano-sizing treatment is added to this transparent thermoplastic resin layer 4. Then, a surface protective layer 5 mainly composed of, for example, an acrylic resin composition is laminated on the transparent thermoplastic resin layer 4. As a result, the pattern layer 3, the transparent thermoplastic resin layer 4, and the surface protective layer 5 are laminated in this order on one surface of the colored thermoplastic resin layer 2 (Fig. 2(d)).

[0071] Note that the thickness of the transparent thermoplastic resin layer 4 may be a value within the range of 35 μm or more and 130 μm or less. Also, an adhesive resin containing a urethane-based adhesive may be provided as an adhesive layer between the pattern layer 3 and the transparent thermoplastic resin layer 4.

[0072] Subsequently, the entire laminate shown in Fig. 2(d) with these layers laminated is irradiated with infrared rays (irradiation light) from the surface protective layer 5 side (Fig. 2(e)), and immediately after the infrared ray irradiation, an embossing plate such as an embossing roll is pressed against the surface of the surface protective layer 5 (Fig. 2(f)). As a result, an embossed portion 5a is formed, and the decorative sheet 1 is formed.

[0073] Here, the pattern portion 6 for gloss / matte expression is formed of an ink having infrared absorption characteristics. Therefore, when the laminate is irradiated with infrared rays, in a plan view, the portion of the surface protective layer 5 that overlaps with the pattern portion 6 for gloss / matte expression is more likely to soften the transparent thermoplastic resin layer 4 and the surface protective layer 5 compared to the portion that does not overlap with the pattern portion 6 for gloss / matte expression. That is, in the transparent thermoplastic resin layer 4 and the surface protective layer 5 after the infrared ray irradiation, there are portions that are likely to soften and portions that are less likely to soften. Therefore, when an embossing plate is pressed against the surface protective layer 5 in this state, unevenness is likely to be formed in the softened portion, and unevenness is less likely to be formed in the portion that is less likely to soften. That is, unevenness is likely to be formed in the softened portion of the transparent thermoplastic resin layer 4 and the surface protective layer 5, that is, the portion that overlaps with the pattern portion 6 for gloss / matte expression in a plan view. As a result, an embossed portion 5a having an uneven shape synchronized with the pattern portion 6 for gloss / matte expression is likely to be formed only at the position overlapping with the pattern portion 6 for gloss / matte expression of the transparent thermoplastic resin layer 4 and the surface protective layer 5 in a plan view.

[0074] As a result, the embossed portion 5a can be formed at a position synchronized with the pattern layer 3, that is, the embossed portion 5a synchronized with the pattern layer 3 can be easily created without performing a highly accurate positioning operation. Note that the timing of pressing the embossing plate against the transparent thermoplastic resin layer 4 and the surface protective layer 5 after the infrared ray irradiation is not limited to immediately after the infrared ray irradiation, and any timing can be used as long as an uneven shape can be selectively formed in the portion softened by the infrared ray irradiation by pressing the plate against the surfaces of the transparent thermoplastic resin layer 4 and the surface protective layer 5.

[0075] Also, other processes may be included between the process of creating the surface protective layer 5 and the process of performing the infrared ray irradiation. The key is that the infrared ray irradiation may be performed in a state where the transparent thermoplastic resin layer 4 and the surface protective layer 5 are formed.

[0076] 〔Effects of this Embodiment〕 (1) According to the cosmetic sheet 1 according to this embodiment, after irradiating the infrared rays on the laminate in which each layer is laminated, the embossing plate is pressed, so that in a plan view, strong embossing can be performed on the portion overlapping with the gloss-matte pattern portion 6. That is, even if the positioning of the area where the embossing plate is pressed is not performed with high precision, the embossing portion can be easily formed at a desired position. As a result, a cosmetic sheet having excellent design can be easily obtained.

[0077] (2) The area of the gloss-matte pattern portion 6 is 90% or less with respect to the area of the surface of the colored thermoplastic resin layer 2 on the side where the gloss-matte pattern portion is laminated. Therefore, by providing the gloss-matte pattern portion 6, it is possible to suppress peeling between the colored thermoplastic resin layer 2 and the primer layer 7, and also between the base material to which the cosmetic sheet 1 is attached and the primer layer.

[0078] (3) Since the gloss-matte pattern portion 6 is provided in the lower layer of the colored thermoplastic resin layer 2, when the cosmetic sheet 1 is viewed from the surface protective layer 5 side, the visibility of the gloss-matte pattern portion 6 is lowered. As a result, although a high-concentration ink having infrared absorption characteristics is used as the gloss-matte pattern portion 6, it is possible to suppress the gloss-matte pattern portion 6 from being visually recognized when the cosmetic sheet 1 is viewed from the surface protective layer 5 side. For this reason, even if a dark pattern is not used as the pattern layer 3, it is possible to suppress the gloss-matte pattern portion 6 containing ink from being visually recognized. As a result, it is also possible to adopt a light-colored pattern as the pattern layer 3, and it is possible to suppress the restriction of the pattern expression by the pattern layer 3 caused by providing the gloss-matte pattern portion 6.

[0079] Further, a colored thermoplastic resin layer 2, a pattern layer 3, a transparent thermoplastic resin layer 4, and a surface protection layer 5 are laminated on the upper layer of the gloss-matte expression pattern portion 6 using a highly concentrated ink having infrared absorption characteristics. An embossed portion 5a is formed at a position overlapping the gloss-matte expression pattern portion 6 in a plan view of the surface protection layer 5. Therefore, the visibility of the gloss-matte expression pattern portion 6 using the ink can be reduced, the influence of the useful gloss-matte expression pattern portion 6 in the manufacturing process of the decorative sheet 1 on the appearance of the decorative sheet 1 can be suppressed, and a decorative sheet 1 with high design quality in which the pattern of the pattern layer 3 and the embossed portion 5a are in sync can be obtained.

[0080] (4) Further, since the gloss-matte expression pattern portion 6 is provided in synchronization with the pattern of the pattern layer 3, concavo-convex portions in synchronization with the pattern of the pattern layer 3 can be formed, that is, a gloss-matte effect in synchronization with the pattern can be easily expressed.

[0081] (5) Also, since a gloss-matte expression is performed by providing concavo-convexities, it is possible to suppress the occurrence of gloss-matte pattern breakage and the like. Therefore, for example, a synchronized gloss-matte expression can also be performed on flooring materials and the like.

[0082] (6) Further, a nucleating agent subjected to nanosizing treatment is added to the transparent thermoplastic resin layer 4. Therefore, the transparency of the transparent thermoplastic resin layer 4 can be improved, and the scratch resistance and post-processing properties such as V-groove bending processing can be improved, and the occurrence of cracks or cracks on the surface in the subsequent process can be avoided.

[0083] As described above, since the occurrence of gloss-matte pattern breakage and the like can be suppressed and the post-processing properties can be further improved, a synchronized gloss-matte expression can be enabled in flooring materials.

[0084] 〔Modification example〕 (1) In the above-described embodiment, the case where a material containing ink is used as the gloss / matte expression pattern portion 6 and infrared irradiation is performed to partially soften the transparent thermoplastic resin layer 4 and the surface protection layer 5 has been described, but the present invention is not limited thereto. By using a material containing any ink composed of a component having light absorbency with respect to light of a predetermined wavelength as the material of the gloss / matte expression pattern portion 6 and using a light source that irradiates the light of the predetermined wavelength, the transparent thermoplastic resin layer 4 and the surface protection layer 5 may be partially softened.

[0085] (2) In the above-described embodiment, the pattern layer 3 is laminated on one surface of the colored thermoplastic resin layer 2, and then the gloss / matte expression pattern portion 6 and the primer layer 7 are formed on the other surface of the colored thermoplastic resin layer 2. Thereafter, the transparent thermoplastic resin layer 4 and the surface protection layer 5 are formed on the surface of the pattern layer 3 opposite to the colored thermoplastic resin layer 2, but the present invention is not limited thereto. For example, the steps of forming the pattern layer 3, the transparent thermoplastic resin layer 4, and the surface protection layer 5 on one surface of the colored thermoplastic resin layer 2 may be continuously executed.

[0086] (3) Further, as shown in FIG. 3, the decorative sheet 1 according to the above-described embodiment may be bonded to a base material 9 that is a base material for a decorative member to form a decorative member 10. In the decorative member 10, the decorative sheet 1 may be provided on at least one surface side of the base material 9, and may be provided on both surfaces.

[0087] [Base Material] As the base material 9, any one of a wood base material, a resin base material, a non-combustible base material, and a metal base material can be used. As the wood base material, for example, a wood veneer, a plywood, a laminated wood, a particle board, a medium density fiber board, and a hard fiber board can be adopted. As the resin base material, for example, resins such as plastics or their composite materials can be adopted. As the non-combustible base material, for example, a steel plate with a non-combustible specification or a base material composed of non-combustible materials defined in the Ministry of Construction Notification No. 1400 can be adopted. Further, as the metal base material, a steel plate, an aluminum plate, etc. can be adopted. Further, the base material 9 may be a resin such as plastic or their composite materials. That is, the base material 9 may be a resin base material. Further, the base material 9 may be a non-combustible base material composed of, for example, a steel plate with a non-combustible specification or non-combustible materials defined in the Ministry of Construction Notification No. 1400.

[0088] Thus, the decorative member 10 includes the base material 9 and a decorative sheet 1 provided on at least one surface side of the base material 9. Further, as the base material 9, any one of a wood base material, a resin base material, a non-combustible base material, or a metal base material can be used. As described above, since the decorative sheet 1 can ensure the adhesiveness with the base material, it is possible to suppress the peeling between the decorative member 10 on the decorative sheet 1 side and the base material 9 side.

Examples

[0089] Hereinafter, the present invention will be described in detail by showing examples and comparative examples. Note that the present invention is not limited to the following examples. (Preparation of Decorative Sheet for Evaluation) A pattern layer 3 made of a urethane-based printing ink was formed on one surface of a colored thermoplastic resin layer 2 made of a 50 μm thick PBT layer.

[0090] Next, on the other surface of the colored thermoplastic resin layer 2, ink made of urethane-based ink was printed with a printing plate having a pattern area level to form a pattern portion 6 for expressing gloss and matte. A primer layer 7 was formed by laminating a polyester-based resin on the colored thermoplastic resin layer 2 including the pattern portion 6 for expressing gloss and matte. Next, a transparent thermoplastic resin layer 4 with a thickness of 90 μm was formed by laminating a PP resin on the surface of the colored thermoplastic resin layer 2 where the pattern layer 3 was formed.

[0091] After forming a surface protection layer 5 using a resin mainly composed of an acrylic resin composition on this transparent thermoplastic resin layer 4, the laminate was heated by an infrared heater, and then an embossed roll was pressed against it to form an embossed portion 5a, thereby obtaining an evaluation decorative sheet composed of the decorative sheet 1 shown in FIG. 1.

[0092] Here, as printing plates with different pattern area levels, a plurality of printing plates were prepared in which the ratio of the area of the gloss-matte pattern portion 6 to the area of the surface of the colored thermoplastic resin layer 2 where the gloss-matte pattern portion 6 was formed was different. The ratio of the area of the gloss-matte pattern portion 6 to the area of the surface of the colored thermoplastic resin layer 2 where the gloss-matte pattern portion 6 was formed was 5% for Example 1, 10% for Example 2, 20% for Example 3, 40% for Example 4, 60% for Example 5, 80% for Example 6, 90% for Example 7, 95% for Comparative Example 1, and 100% for Comparative Example 2. As a reference example 1, an evaluation decorative sheet without the gloss-matte pattern portion 6 was also prepared. Each of the evaluation decorative sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1 is the same except that the ratio of the area of the gloss-matte pattern portion 6 to the area of the surface of the colored thermoplastic resin layer 2 where the gloss-matte pattern portion 6 was formed is different.

[0093] 〔Evaluation〕 For the evaluation decorative sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1, long-term substrate adhesion evaluation, heat-resistant creep test, and sensory evaluation were carried out. The evaluation methods are as follows.

[0094] (Long-term substrate adhesion evaluation) For each of the evaluation cosmetic sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1, they were bonded to a substrate with an adhesive to obtain evaluation cosmetic boards. As the adhesive, a one-component curable type or two-component curable type of urethane-modified EVA adhesive, a reactive hot melt adhesive, etc. can be applied. Here, a two-component curable type of urethane-modified EVA adhesive was used.

[0095] Six evaluation cosmetic boards were prepared for each of the evaluation cosmetic sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1. First, six evaluation cosmetic boards using the evaluation cosmetic sheet of Example 1 were each placed in environments of normal temperature, 60 °C, 80 °C, 40 °C / 90%, and 85 °C / 85% for 500 h. Thereafter, for each of the evaluation cosmetic boards after 500 h of placement, a substrate adhesion test was carried out. The substrate adhesion test was carried out at normal temperature by pulling the evaluation cosmetic sheet in the 180° direction with respect to the substrate at a speed of 200 mm / min, and the tensile adhesive strength was measured.

[0096] In the same procedure, for each of the evaluation cosmetic sheets of Examples 2 to 7, Comparative Examples 1 and 2, and Reference Example 1, evaluation cosmetic members were prepared, and using these evaluation cosmetic members, a substrate adhesion test was carried out under the same conditions. As a result of the substrate adhesion test, a case where the tensile adhesive strength was 19.6 N or more was regarded as a pass. And as a result of evaluating using six evaluation cosmetic boards for each of the evaluation cosmetic sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1, a case where all six evaluation cosmetic boards passed the substrate adhesion test was marked as "〇", and otherwise as "×".

[0097] The evaluation results of the long-term substrate adhesion evaluation are shown in Table 1 as "substrate adhesion". (Heat Resistance Creep Test) For each of the evaluation cosmetic sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1, they were bonded to a substrate with an adhesive to obtain evaluation cosmetic boards. As the adhesive, a one-component curable type or two-component curable type of urethane-modified EVA adhesive, a reactive hot melt adhesive, etc. can be applied. Here, a two-component curable type of urethane-modified EVA adhesive was used.

[0098] For each evaluation cosmetic sheet of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1, three sheets were prepared.

[0099] First, three evaluation cosmetic boards using the evaluation cosmetic sheet of Example 1 were each placed in an environment of 60 °C, 70 °C, and 80 °C for 30 minutes. Then, for each of the evaluation cosmetic boards placed for 30 minutes, a load of 500 g / 25 mm was applied to the evaluation cosmetic sheet in the 90° direction with respect to the base material and pulled, and the distance peeled in 30 minutes was measured.

[0100] In the same procedure, for each of the evaluation cosmetic sheets of Examples 2 to 7, Comparative Examples 1 and 2, and Reference Example 1, an evaluation cosmetic member was created, and using this evaluation cosmetic member, a load of 500 g / 25 mm was applied to the evaluation cosmetic sheet in the 90° direction with respect to the base material and pulled, and the distance peeled in 30 minutes was measured. As a result of the heat resistance creep test, the case where the sheet peeling length in 30 minutes was 10 mm or less was regarded as passing.

[0101] Then, as a result of evaluating each of the evaluation cosmetic sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1 using three evaluation cosmetic boards, the case where all three evaluation cosmetic boards passed the heat resistance creep test was marked as "〇", and the others were marked as "×". The evaluation results of the heat resistance creep test are shown in Table 1 as "Heat resistance creep test".

[0102] (Sensory evaluation) For each of the evaluation cosmetic sheets of Examples 1 to 7, Comparative Examples 1 and 2, and Reference Example 1, visual inspection was performed to confirm whether the gloss-matte expression could be visually recognized. The case where the gloss-matte expression could be visually recognized was marked as "○", and the case where the gloss-matte expression could not be visually recognized was marked as "×". The evaluation results of the sensory evaluation are shown in Table 1 as GM design property.

[0103]

Table 1

[0104] As shown in Table 1, when the ratio of the area of the actual pattern portion 6 for expressing the gloss matte to the area of the surface forming the pattern portion 6 for expressing the gloss matte of the colored thermoplastic resin layer 2 is 5% or more and 90% or less, good results can be obtained in the substrate adhesion test and the heat resistance creep test, and it was confirmed that the gloss matte expression was exhibited. On the other hand, when the ratio of the area of the actual pattern portion 6 for expressing the gloss matte to the area of the surface forming the pattern portion 6 for expressing the gloss matte of the colored thermoplastic resin layer 2 is 95% and 100%, although it was confirmed that the gloss matte expression was exhibited, the tensile adhesive strength was small in the substrate adhesion test, and the sheet peeling length was large in the heat resistance creep test, and it was confirmed that the adhesiveness and the adhesion were insufficient. In addition, when the pattern portion 6 for expressing the gloss matte is not provided on the colored thermoplastic resin layer 2, good results can be obtained in the substrate adhesion test and the heat resistance creep test, but the gloss matte expression could not be exhibited.

[0105] In addition, the present invention can have, for example, the following configurations. (1) A pattern layer, a transparent resin layer, and a surface protection layer laminated in this order on one surface of the colored resin layer, A pattern portion for expressing gloss matte formed of a predetermined material laminated on the other surface of the colored resin layer, arranged in synchronization with the pattern of the pattern layer, and having higher light absorptivity than the colored resin layer with respect to light of a predetermined wavelength, An embossed portion formed in a portion of the surface protection layer that overlaps the pattern portion for expressing gloss matte in plan view, A decorative sheet, wherein the area of the pattern portion for expressing gloss matte with respect to the area of the other surface of the colored resin layer is 90% or less. (2) The decorative sheet according to (1) above, wherein the predetermined material is formed by including an ink containing carbon black, and the light of the predetermined wavelength is infrared light. (3) A step of laminating a pattern layer, a transparent resin layer, and a surface protection layer in this order on one surface of the colored resin layer, A step of forming a pattern portion for gloss and matte expression that synchronizes with the pattern of the pattern layer on the other surface of the colored resin layer using a predetermined material having higher light absorbency than the colored resin layer for light of a predetermined wavelength; After the step of forming the pattern portion for gloss and matte expression, a step of irradiating the surface protection layer with irradiation light in which the power of light of the predetermined wavelength is stronger than the power of light of other wavelengths; After the step of irradiating the irradiation light, a step of pressing an embossing plate for embossing shape formation against the surface protection layer, comprising: The step of forming the pattern portion for gloss and matte expression forms the pattern portion for gloss and matte expression such that the area of the pattern portion for gloss and matte expression with respect to the area of the other surface of the colored resin layer is 90% or less. A method for manufacturing a decorative sheet. (4) A base material; The decorative sheet according to the above (1) or (2) provided on at least one surface of the base material, comprising: The base material is any one of a wood base material, a resin base material, a non-combustible base material, and a metal base material. A decorative member characterized by that.

Explanation of symbols

[0106] 1 Decorative sheet 2 Colored thermoplastic resin layer 3 Pattern layer 4 Transparent thermoplastic resin layer 5 Surface protection layer 6 Pattern portion for gloss and matte expression 7 Primer layer 9 Base material 10 Decorative member

Claims

1. A pattern layer, a transparent resin layer, and a surface protection layer laminated in this order on one surface of a colored resin layer; A gloss-matte pattern portion made of a predetermined material that is laminated on the other surface of the colored resin layer, arranged in synchronization with the pattern of the pattern layer, and has higher light absorbency than the colored resin layer for light of a predetermined wavelength; An embossed portion formed in a portion of the surface protection layer that overlaps the gloss-matte pattern portion in plan view; A decorative sheet, characterized in that the area of the gloss-matte pattern portion with respect to the area of the other surface of the colored resin layer is 90% or less.

2. The decorative sheet according to claim 1, wherein the predetermined material is formed by including ink containing carbon black, and the light of the predetermined wavelength is infrared light.

3. A step of laminating a pattern layer, a transparent resin layer, and a surface protection layer in this order on one surface of a colored resin layer; A step of forming a gloss-matte pattern portion that is in synchronization with the pattern of the pattern layer using a predetermined material that has higher light absorbency than the colored resin layer for light of a predetermined wavelength on the other surface of the colored resin layer; After the step of forming the gloss-matte pattern portion, a step of irradiating the surface protection layer with irradiation light in which the power of the light of the predetermined wavelength is stronger than the power of the light of other wavelengths; After the step of irradiating the irradiation light, a step of pressing an embossing plate for forming an embossed shape on the surface protection layer; and The method for manufacturing a decorative sheet, characterized in that the step of forming the gloss-matte pattern portion forms the gloss-matte pattern portion so that the area of the gloss-matte pattern portion with respect to the area of the other surface of the colored resin layer is 90% or less.

4. A base material; The decorative sheet according to claim 1 or claim 2 provided on at least one surface of the base material; and A decorative member, characterized in that the base material is any one of a wood base material, a resin base material, a non-combustible base material, and a metal base material.

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