Method for producing decorative sheet, decorative sheet, and decorative member

Abstract

To provide a method for producing a decorative sheet which has a more realistic texture, expresses a more favorable realistic hue, and is excellent in post-processing resistance to post-processing such as V-groove bending.SOLUTION: On one surface of a colored thermoplastic resin layer 2, a picture layer 5 with a picture, a transparent thermoplastic resin layer 6 containing a nano-sized nucleating agent, and a surface protective layer 7 are layered in this order; a pattern layer 8a is formed using a colorless or light-colored ink and a material with a greater light absorbability of light of a predetermined wavelength than the colored thermoplastic resin layer 2 by arranging, on the other surface of the colored thermoplastic resin layer, a pattern portion for gloss mat expression 3, which is a light-absorbing region, to match with the picture; then irradiating light in which power of light of a predetermined wavelength is greater than power of light of other wavelength is emitted; and then an embossed portion 7a is formed by pressing an embossing plate for forming an embossed shape against the surface protective layer 7.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Decorative sheets have been developed and expanded in the process of the development of residential construction as an industry. Originally, materials suited to the characteristics of the region, such as wood and stone, were used for housing, but as the housing industry developed, industrialization progressed, and natural materials were replaced by artificial materials. In recent years, the heavy use of high-quality wood and stone materials has been feared to lead to deforestation and environmental problems, which has become one of the factors expanding the demand for decorative sheets. For example, decorative members in which decorative sheets are bonded to wood substrates such as plywood, MDF (medium density fiberboard), and particle board, resin substrates, inorganic non-combustible substrates, and metal substrates are widely used (see, for example, Patent Document 1). Furthermore, the design of decorative sheets is often designed to imitate the surfaces of wood, stone, and 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] By the way, decorative sheets tend to have a flat surface texture compared to real wood or stone. Real wood and stone have unevenness in different places due to differences in the surface material and structure, and there are differences in texture. Areas with different textures often also have different colors, but decorative sheets do not express this, and in terms of design, the more expensive real thing is far superior.

[0005] Furthermore, applications of decorative panels using decorative sheets are expanding, and there is a demand for improved post-processing resistance against bending processes such as V-groove bending.

[0006] The present invention has been made in consideration of the above-mentioned points, and aims to provide a manufacturing method for a decorative sheet, a decorative sheet, and a decorative member that have a texture and color that are closer to the real thing, and that have excellent resistance to post-processing such as V-groove bending. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, one aspect of the present invention provides a method for manufacturing a decorative sheet having an embossed shape that is in harmony with a pattern, the method comprising the steps of: laminating, in this order, a pattern layer having a pattern, a transparent resin layer containing a nano-sized nucleating agent, and a surface protective layer on one side of a colored resin layer; forming a pattern layer on the other side of the colored resin layer using a colorless or light-colored ink and a material that is more light-absorbent for light of a predetermined wavelength than the colored resin layer, arranging light-absorbent regions in harmony with the pattern; after the step of forming the pattern layer, irradiating with light having a predetermined wavelength that is stronger in power than the light of other wavelengths; and, after the step of irradiating with light, pressing an embossing plate for forming the embossed shape into the surface protective layer.

[0008] In another aspect of the present invention, there is provided a decorative sheet comprising a design layer, a transparent resin layer and a surface protective layer laminated in that order on one side of a colored resin layer, and a pattern layer laminated on the other side of the colored resin layer and having areas which are more light absorbing than the colored resin layer for light of a predetermined wavelength and which are arranged in harmony with the design of the design layer, wherein the transparent resin layer contains a nano-sized nucleating agent, the light absorbing areas are formed from a material containing a colorless or light-colored ink and a light absorbing material, and an embossed portion is formed in the surface protective layer at a position which overlaps with the light absorbing areas in a planar view.

[0009] Furthermore, another aspect of the present invention provides a decorative member comprising a substrate and a decorative sheet of the above aspect provided on at least one side of the substrate, wherein the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate. Effect of the Invention

[0010] According to one aspect of the present invention, a manufacturing method for a decorative sheet, a decorative sheet, and a decorative member can be obtained that have a texture closer to the real thing, a good color that is also closer to the real thing, and have excellent post-processing resistance to post-processing such as V-groove bending. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic example of a decorative sheet according to one embodiment of the present invention. [Diagram 2] 1A to 1C are process diagrams illustrating an example of a manufacturing procedure for a decorative sheet according to an embodiment of the present invention. [Diagram 3] FIG. 4 is a cross-sectional view illustrating an example of a decorative member according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present technology will be described with reference to the drawings. In the present embodiment, a decorative sheet and a decorative member for floors or fittings will be described as an example, but the present technology may be a decorative sheet for use in other parts.

[0013] Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. are different from the actual ones. Furthermore, the embodiments shown below are examples of configurations for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims described in the claims.

[0014] A manufacturing method for a decorative sheet according to one embodiment of the present invention is a manufacturing method for a decorative sheet having an embossed shape that is in harmony with a pattern, and includes the steps of laminating a pattern layer having a pattern, a transparent resin layer containing a nano-sized nucleating agent, and a surface protective layer, in that order, on one side of a colored resin layer; forming a pattern layer on the other side of the colored resin layer using a colorless or light-colored ink and a material that is more light-absorbent for light of a predetermined wavelength than the colored resin layer, arranging light-absorbent regions in harmony with the pattern; after the step of forming the pattern layer, irradiating with light having a predetermined wavelength that is stronger in power than the light of other wavelengths; and after the step of irradiating with light, pressing an embossing plate for forming the embossed shape into the surface protective layer.

[0015] In addition, a decorative sheet according to another embodiment of the present invention comprises a pattern layer, a transparent resin layer, and a surface protective layer laminated in that order on one side of a colored resin layer, and a pattern layer laminated on the other side of the colored resin layer and having areas which are more light absorbing than the colored resin layer for light of a predetermined wavelength and which are arranged in harmony with the pattern of the pattern layer, wherein the transparent resin layer contains a nano-sized nucleating agent, the light absorbing areas are formed from a material containing a colorless or light-colored ink and a light absorbing material, and an embossed portion is formed in the surface protective layer at a position which overlaps with the light absorbing areas in a planar view.

[0016] Furthermore, a decorative member according to another embodiment of the present invention is a decorative member comprising a base material and a decorative sheet of the above-described aspect provided on at least one side of the material, wherein the base material is any one of a wood base material, a resin base material, a non-flammable base material, and a metal base material.

[0017] A decorative sheet 1 manufactured by a manufacturing method for a decorative sheet according to one embodiment of the present invention is formed by laminating a colored thermoplastic resin layer (colored resin layer) 2, a pattern layer 5, a transparent thermoplastic resin layer (transparent resin layer) 6, and a surface protective layer 7 in this order, as shown in Fig. 1, and an embossed portion (embossed shape) 7a is formed in the surface protective layer 7. In addition, a pattern layer 8a consisting of a pattern portion 3 for expressing gloss matte and a primer layer 8 are formed on the surface of the colored thermoplastic resin layer 2 opposite to the pattern layer 5. As will be described in detail later, the pattern portion 3 for expressing gloss matte is an area containing a predetermined material having light absorption properties for light of a predetermined wavelength.

[0018] [Colored thermoplastic resin layer] Examples of the colored thermoplastic resin layer 2 as a substrate include 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, etc. Among them, polyolefin 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 the ease of sheeting, printability, and suitability for bending.

[0019] The colored thermoplastic resin layer 2 can have an appropriate hue selected as the base color of the picture layer 5. The colored thermoplastic resin layer 2 can be colored, for example, by mixing or kneading a colorant such as a pigment when sheeting the thermoplastic resin. Alternatively, a colored layer can be provided as a solid ink layer by using a coating or printing technique before providing the pattern portion 3 for expressing gloss matte.

[0020] [Pattern layer] The pattern layer 5 is a printing layer on which a pattern is printed in order to impart design to the decorative sheet 1. A known printing method can be used to form the pattern layer 5. The printing method is not particularly limited, but gravure printing is preferred in consideration of productivity and pattern quality. For example, when the colored thermoplastic resin layer 2 can be prepared in a rolled state, printing for forming the pattern layer 5 can be performed using a roll-to-roll printing device. In addition to these, other printing methods include offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, and transfer printing from a transfer sheet. When using such a printing method, the pattern of the pattern layer 5 can be formed by multi-color printing using normal process colors of yellow, red, blue, and black, as well as by multi-color printing using special colors performed by preparing plates of each color that constitute the pattern.

[0021] In addition, the pattern of the pattern layer 5 may be any pattern taking into consideration the design of the flooring material or fittings. For example, the pattern may be a marble grain pattern imagining a stone floor such as marble. For example, in the case of a wood-based pattern, various wood grains and cork may be used as the pattern. In addition to the pattern of natural materials, artificial pattern patterns such as artificial pattern patterns and geometric patterns based on these motifs may also be used. In addition to these, examples of the pattern patterns include wood grain patterns composed of spring wood regions and autumn wood regions of the cross section of tree rings, vessel parts, etc., leather (skin grain) patterns, stone grain patterns on the surface of stone materials such as marble, granite, and sandstone, sand grain patterns, tile patterns, brick masonry patterns, cloth patterns, geometric figures, letters, symbols, abstract patterns, floral patterns, landscapes, characters, etc.

[0022] Printing ink is a mixture of a solvent and solids 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.

[0023] Examples of the binder resin include chlorine-based resin, urethane resin, acrylic urethane resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin (nitrocellulose), cellulose acetate resin, etc. Examples of the chlorine-based resin include polyvinyl chloride resins such as polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, polypropylene chloride, chlorinated polypropylene, etc. Here, (meth)acrylic means acrylic or methacrylic. The binder resin may be one type alone or two or more types in combination.

[0024] Examples of colorants include inorganic pigments such as carbon black, iron black, titanium white (titanium oxide), antimony white, yellow lead, titanium yellow, red iron oxide, 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.

[0025] Here, the solvent contained in the printing ink will eventually evaporate, so the design layer 5 is formed mainly from solid components such as colorants and binder resins.

[0026] The printing ink may also contain other components such as stabilizers, plasticizers, catalysts, and curing agents. The printing ink may be selected according to the printing method. In particular, it is preferable to select the printing ink taking into consideration the adhesion to the colored thermoplastic resin layer 2, printability, and weather resistance as a flooring material or fitting. The thickness of the pattern layer 5 can be appropriately adjusted taking into consideration the decorativeness required of the pattern layer 5, the three-dimensional formability of the decorative sheet 1, and the like. The thickness of the pattern layer 5 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.

[0027] In order to improve the adhesion between the pattern layer 5 and the transparent thermoplastic resin layer 6, an adhesive layer (not shown) may be provided on the surface of the pattern layer 5 that contacts the transparent thermoplastic resin layer 6. By strengthening this adhesion, the decorative sheet 1 can be given bending processability to follow curved surfaces and right-angled surfaces. The resin used in the adhesive layer (not shown) is not particularly limited. For example, a two-component curing urethane resin can be used. The adhesive resin may also be bonded to the pattern layer 5 by a urethane adhesive. For example, a coating device or a gravure printing device can be used to apply the resin used in the adhesive layer (not shown).

[0028] Furthermore, for the purpose of suitably imparting design effects such as a sense of depth and brightness to the decorative sheet 1, a glittering layer (not shown) may be provided between the picture layer 5 and the transparent thermoplastic resin layer 6. The glittering layer (not shown) preferably contains a glittering pigment and a binder resin. Examples of the glittering pigment include pearl pigments and metal pigments. In particular, pearl pigments are preferred because they can suppress a decrease in the light transmittance of the glittering layer and do not impair the visibility of the picture layer 5.

[0029] A pearl pigment is a pigment that can impart pearl luster. For example, the surface of a base particle is coated with a metal oxide. As the base particle, a scaly particle such as mica is preferable. As the metal oxide, an oxide of a metal such as titanium, iron, zirconium, silicon, aluminum, and cerium can be mentioned. The metal oxide may be one type alone or two or more types. Specific examples include oxide-coated mica such as titanium mica, iron oxide-coated mica, iron oxide-coated mica titanium, Prussian blue-coated mica titanium, Prussian blue-iron oxide-coated mica titanium, chromium oxide-coated mica titanium, carmine-coated mica titanium, organic pigment-coated mica titanium, titanium oxide-coated mica, and titanium oxide-coated synthetic mica; oxide-coated glass powder 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, and bismuth oxide chloride; fish scale powder, shell pieces, and pearl pieces.

[0030] Examples of metal pigments include pigments made of metals such as aluminum, brass, stainless steel, tin, zinc, copper, nickel, gold powder, and silver, and alloys of these metals. The metal pigments may be used alone or in combination of two or more kinds.

[0031] From the viewpoint of providing an excellent design effect, for example, when the glittering layer is formed by gravure printing, the average particle size of the glittering pigment is preferably 40 μm or less, and more preferably 30 μm or less. From the same viewpoint, the ratio of [average particle size of glittering pigment / thickness of glittering layer] is preferably 0.01 or more and 15 or less, and more preferably 0.5 or more and 10 or less. In this specification, the "average particle size" is a value that can be determined as the mass average value D50 in particle size distribution measurement by laser light diffraction method.

[0032] Examples of the binder resin include thermoplastic resins and cured products of curable resin compositions, and from the viewpoint of durability, the cured products of the curable resin compositions are preferred. Examples of the cured products of the curable resin compositions include cured products of thermosetting resin compositions and cured products of ionizing radiation curable resin compositions. From the viewpoint of interlayer adhesion, the cured products of the thermosetting resin compositions are preferred.

[0033] Examples of the thermosetting resin composition used in the glossy 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. These thermosetting resin compositions include a monomer and / or a prepolymer constituting each resin, and a curing agent added as necessary. The ionizing radiation curing resin composition used in the glossy layer may be the same as the ionizing radiation curing resin composition of the surface protective layer 7 described below.

[0034] The content of the glittering pigment in the glittering 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, relative to 100 parts by mass of the binder resin. By making the content of the glittering pigment 10 parts by mass or more, it is possible to impart a sufficient glossy feeling, and by making it 90 parts by mass or less, it is possible to suppress the impairment of the visibility of the pattern layer described later. From the same viewpoint, the thickness of the glittering layer is preferably 1 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less.

[0035] The glittering layer can be formed into any pattern depending on the design to be imparted. Examples include wood grain, leather, stone, sand, tile, brickwork, fabric, geometric figures, letters, symbols, abstract patterns, floral patterns, landscapes, characters, and the like. In addition, it is preferable that the arbitrary pattern has shading in order to further enhance the design effect. Shading may be formed by the size or thickness of the halftone dots, but it is preferable to form it by the density of the halftone dots (i.e., the size of the halftone dots is uniform and shading is formed by the density of the halftone dots).

[0036] The glittering layer can be formed, for example, by applying a coating liquid containing a glittering pigment and a binder resin by a general-purpose printing method such as gravure printing. When the shading of the glittering layer is formed by the density of halftone dots, the halftone dots of the printing plate can be formed by an FM (frequency modulation) screen.

[0037] [Transparent thermoplastic resin layer] The transparent thermoplastic resin layer 6 is a resin layer that provides thickness and depth for design purposes, as well as protecting the pattern layer 5 and imparting good surface properties so as to improve the weather resistance and abrasion resistance of the decorative sheet 1.

[0038] The transparent thermoplastic resin layer 6 is a resin layer containing, for example, 90 to 100% by weight of a crystalline polypropylene resin as a main component and a nucleating agent as a nano-sized additive. More preferably, the nano-sized additive is contained in a vesicle state (nucleating agent-containing vesicle). In this case, the nucleating agent-containing vesicle preferably has an average particle size of 1 / 2 or less of the wavelength of visible light. Specifically, since the wavelength region of visible light is 400 nm to 750 nm, the average particle size is preferably 375 nm or less. In addition, the nucleating agent-containing vesicle preferably has a configuration having a single-layer outer membrane. In such a transparent thermoplastic resin layer 6, it is important that the haze value is 15% or less, more preferably 10% or less, the tensile modulus is 800 MPa or more, 2000 MPa or less, and the tensile breaking elongation is 200% or more by adjusting the cooling conditions during film formation.

[0039] The crystalline polypropylene resin can be appropriately selected and designed from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof, which have different pentad fractions. More preferably, it is important that the crystalline polypropylene resin is a high crystalline polypropylene resin, i.e., a homopolymer, of propylene with an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. Note that resins other than the crystalline polypropylene constituting the transparent thermoplastic resin layer 6 can be appropriately selected depending on the purpose of blending, as long as they do not significantly adversely affect the physical properties of the crystalline polypropylene. However, in order to maintain the V-groove bending suitability, it is preferable that the resin has good compatibility with the crystalline polypropylene resin constituting the transparent thermoplastic resin layer 6.

[0040] The thickness of such a transparent thermoplastic resin layer is preferably 20 μm or more and 250 μm or less.

[0041] A nano-sized nucleating agent is a nucleating agent that has been made into nano-sized particles by a method of nano-sizing the nucleating agent (nano-processing). The particle diameter of a nano-sized nucleating agent is extremely small, so the number of nucleating agents present per unit volume and the surface area increase inversely proportional to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes close, so when crystal growth occurs from the surface of one nucleating agent particle added to a polypropylene resin, the end from which the crystal is growing immediately comes into contact with the end of the crystal that has grown from the surface of another nucleating agent particle adjacent to the nucleating agent particle, and the ends of the crystals inhibit each other's growth, stopping the growth of each crystal, so that the average particle size of the spherulites in the crystalline part of the crystalline polypropylene resin can be made extremely small.

[0042] Therefore, by adding a nano-sized nucleating agent to the transparent thermoplastic resin layer, a larger amount of finer crystal nuclei are generated in the resin compared to conventional nucleating agents, and as a result, the distance between the crystal nuclei in the crystal part is shortened, the growth of individual crystals is suppressed, and the average particle size of the spherulites is successfully reduced. This crystalline polypropylene resin has an excellent transparency with a haze value of 15% or less.

[0043] Furthermore, by containing the nano-sized nucleating agent in a vesicle state, i.e., as a nucleating agent-encapsulated vesicle, the nucleating agent is prevented from agglomerating, realizing high dispersibility in the resin material. In the resin composition, the outer membrane of the nucleating agent-encapsulated vesicle partially collapses to expose the nucleating agent, and spherulites are formed with the nano-sized nucleating agent particles as crystal nuclei during the crystallization process of the resin material.

[0044] In this case, since the nucleating agent-encapsulating vesicles obtained by the supercritical reverse phase evaporation method are particularly small in size, the average particle size of the spherulites in the crystalline portion of the crystalline polypropylene resin can be made extremely small, and the crystallinity of the crystalline portion can be dramatically improved.

[0045] In the decorative sheet 1 of the present invention, a nano-sized nucleating agent, more preferably a vesicle containing a nucleating agent, is contained in the transparent thermoplastic resin layer 6, thereby making the average particle size of the spherulites in the crystalline portion of the crystalline polypropylene resin extremely small, thereby realizing excellent scratch resistance. In particular, by containing a vesicle containing a nucleating agent, the nucleating agent is uniformly dispersed in the crystalline polypropylene resin, and the crystallinity of the crystalline polypropylene is controlled to adjust the hardness and toughness of the transparent thermoplastic resin layer to be optimal, thereby realizing excellent scratch resistance and post-processing resistance with a tensile modulus of 800 MPa or more and 2000 MPa or less, and a tensile elongation at break of 200% or more.

[0046] Examples of nano-processing include a solid-phase method in which additives are mainly mechanically pulverized to obtain nano-sized particles, a liquid-phase method in which additives or a solution in which the additives are dissolved are synthesized or crystallized, and a gas-phase method in which additives or gas or vapor from the additives are synthesized or crystallized. Briefly listing specific means for carrying out each method, the solid-phase method includes a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, and a jet mill. The liquid-phase method includes a crystallization method, a coprecipitation method, a sol-gel method, a liquid-phase reduction method, and a hydrothermal synthesis method. The gas-phase method includes an electric furnace method, a chemical flame method, a laser method, and a thermal plasma method.

[0047] To explain the specific method of nano-processing, as a specific example of the solid phase method, for example, a mixture of 100g of isopropyl alcohol and 50g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate is milled in a bead mill for 60 minutes using 30μm stabilized zirconia beads to obtain nano-sized nucleating agent particles with an average particle size of about 100nm to 150nm. As a specific example of the crystallization method, for example, 50g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate is dissolved in a mixed solvent consisting of 96g of xylene, 72g of isopropyl alcohol and 24g of water, and this solution is brought into contact with a poor solvent such as ethanol in a microreactor to precipitate nano-sized nucleating agent particles with an average particle size of 1nm to 150nm.

[0048] In addition, the additive-containing vesicle is a vesicular capsule having a membrane structure closed in a spherical shell shape, and in particular, one containing a liquid phase inside is called an additive-containing vesicle. In the present invention, the additive is contained in this liquid phase. This additive-containing vesicle has extremely high dispersibility without particles being aggregated due to the action of repulsion between the outer membranes of each other. This action makes it possible to uniformly disperse the additive in the resin composition constituting each resin layer. Among the nano-processing methods, examples of the method (vesicle processing) for obtaining nano-sized additives as additive-containing vesicles include the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, and the supercritical reverse phase evaporation method. To briefly explain such vesicle processing, the Bangham method involves putting chloroform or a chloroform / methanol mixed solvent into a container such as a flask, and further adding and dissolving phospholipids. Then, the solvent is removed using an evaporator to form a thin film of lipids, and a dispersion of additives is added, followed by hydration and dispersion in a vortex mixer to obtain vesicles. The extrusion method is a method in which a thin film of phospholipid solution is prepared and passed through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain vesicles. The hydration method is a preparation method similar to the Bangham method, but it is a method in which vesicles are obtained by gently stirring and dispersing the solution without using a mixer. The reverse phase evaporation method is a method in which phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to make a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and water is added to obtain vesicles. The freeze-thaw method is a method in which cooling and heating are used as an external perturbation, and vesicles are obtained by repeating this cooling and heating.

[0049] In particular, a method for obtaining an additive-encapsulating vesicle having an outer membrane consisting of a single-layer membrane is the supercritical reverse phase evaporation method. The supercritical reverse phase evaporation method is a method for producing a capsule 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), and carbon dioxide under temperature 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.

[0050] In the specific vesicle formation process using the supercritical reverse phase evaporation method, an emulsion of supercritical carbon dioxide and an aqueous phase is generated by injecting an aqueous phase into a mixed fluid of supercritical carbon dioxide, a phospholipid as a dispersant, and an additive as an encapsulating substance, and stirring the mixture. After that, when the pressure is reduced, the 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 membrane. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the dispersant forms multiple layers on the surface of the additive particles, it is possible to easily generate capsules with a single layer membrane, so that smaller capsules can be prepared. In addition, if multiple membrane capsules are desired, they can be easily produced by injecting supercritical carbon dioxide into a mixed fluid of phospholipids, additives, and an aqueous phase. Examples of phospholipids used in preparing the additive-encapsulating vesicle include glycerophospholipids such as phosphatidylcholine, phosphatidiethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol. The additive-encapsulating vesicle can achieve excellent compatibility with resin materials by being provided with an outer membrane made of phospholipids.

[0051] The additive-containing vesicle may have an outer membrane made of a dispersant. Examples of dispersants include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicone, wax, modified resins, and the like. Examples of polymer surfactants include aliphatic polycarboxylic acids, polycarboxylic acid alkylamines, polyacrylic acids, polymethacrylic acids, polyoxyethylene alkyl ethers, and sorbitan fatty acid esters. Examples of fatty acid metal salts include those in which stearic acid, lauric acid, 12-hydroxystearic acid, montanic acid, behenic acid, ricinoleic acid, myristic acid, and the like are combined with lithium, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, and the like. Examples of silane coupling agents include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Examples of titanate coupling agents include tetrakis[2,2-bis(allyloxymethyl)butoxy]titanium(IV), di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, isopropyl titanium triisostearate, di-n-butoxy bis(triethanolaminato)titanium, tetrakis(2-ethylhexyloxy)titanium, and di-i-propoxy bis(acetylacetonato)titanium. Examples of silicones include dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, cyclic dimethyl silicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, and higher fatty acid-modified silicone oil, which are polymerized or polyolefins are thermally decomposed, and then further oxidized or modified with maleic acid, sulfonic acid, carboxylic acid, rosin acid, etc. Examples of resins include polyolefins modified with maleic acid, sulfonic acid, carboxylic acid, rosin acid, etc.

[0052] The terms used in the above description will be briefly explained below. A nucleating agent is added to promote the generation of crystal nuclei during the crystallization of a resin or to make the nucleating agent itself a crystal nucleus. There are melt-type nucleating agents that melt into the resin of the base material when added and precipitate again to generate crystal nuclei, and non-melt-type nucleating agents that do not melt when added to the base material and become crystal nuclei with the same particle size. Examples of nucleating agents for polypropylene resin include metal phosphate salts, metal benzoate salts, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in the present invention, in order to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoate salts, metal pimelate salts, and metal rosin salts that are non-melt types and can be expected to have good transparency, but if the nano-processing can make the material transparent, colored quinacridone, cyanine blue, talc, etc. can also be used. In addition, melt-type benzylidene sorbitol may be appropriately mixed with the non-melt-type nucleating agent.

[0053] The haze value is a percentage value obtained by subtracting the integral value (linear transmittance) of only linear components of the light beams emitted from one surface of an object from the integral value (total light transmittance) of all the light beams emitted from the other surface when the light beams enter from one surface of the object and exit from the other surface, and the smaller the value, the higher the transparency. This haze value is determined by the internal haze, which is determined by the internal state of the object, such as the degree of crystallinity and spherulite size in the crystal part, and the external haze, which is determined by the surface state of the object, such as the presence or absence of unevenness on the entrance surface and exit surface. In the present invention, when simply referring to the haze value, it means a value determined by the internal haze and the external haze.

[0054] The tensile breaking elongation is a value that represents the elongation when a sample is pulled at a specified speed and breaks, and is calculated by subtracting the length of the sample before the test (L0) from the length of the sample at break (L), dividing this value by the length of the sample before the test (L0), expressed as a percentage. The smaller the value, the poorer the elongation, which will cause cracks and whitening during post-processing such as V-groove bending, and therefore poorer post-processing resistance. The larger the value, the better the elongation, which will allow easier post-processing, and therefore better post-processing resistance.

[0055] The isotactic pentad fraction (mmmm fraction) is the fraction of carbon with mass number 13 (C) (nuclear species). 13 The isotactic pentad fraction of a polypropylene resin is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating the resin material constituting the transparent thermoplastic resin layer 6 at a predetermined resonance frequency using a C-NMR measurement method (nuclear magnetic resonance measurement method), and defines the atomic arrangement, electronic structure, and molecular microstructure in the resin material. The isotactic pentad fraction of a polypropylene resin is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating the resin material at a predetermined resonance frequency using a C-NMR measurement method (nuclear magnetic resonance measurement method), and defines the atomic arrangement, electronic structure, and molecular microstructure in the resin material. 13 The isotactic pentad fraction is the ratio of five propylene units arranged side by side, determined by C-NMR, and is used as a measure of crystallinity or stereoregularity. Such an isotactic pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface, and basically, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, and therefore the better the scratch resistance.

[0056] A lamination method can be used as a method for forming the transparent thermoplastic resin layer 6. In addition, for example, when the transparent thermoplastic resin layer 6 and an adhesive layer (not shown) are formed simultaneously, a method can be used in which they are formed by co-extrusion.

[0057] In this way, the transparent thermoplastic resin layer 6 is formed containing nucleating agent vesicles in which nano-sized nucleating agents are encapsulated in vesicles with a single-layer outer membrane, thereby improving the scratch resistance and abrasion resistance of the decorative sheet 1.

[0058] [Surface protective layer] The surface protective layer 7 is a layer for imparting surface properties such as abrasion resistance to the decorative sheet 1. The surface protective layer 7 is also a layer for adjusting the surface gloss of the decorative sheet 1. The surface protective layer 7 may be a single layer or a multilayer. For example, the surface protective layer 7 may be formed by providing two layers, a first surface protective layer (not shown) and a second surface protective layer (not shown), in this order on the transparent thermoplastic resin layer 6. When providing the surface protective layer 7 consisting of the first surface protective layer (not shown) and the second surface protective layer (not shown), each layer may be applied and the coating film may be cured using a known coating device, heat drying device, and ionizing radiation irradiation device according to the type of curable resin.

[0059] The surface protective layer 7 is mainly composed of a curable resin. In other words, it is preferable that the resin component of the surface protective layer 7 is substantially composed of a curable resin. "Substantially" refers to, for example, 80 parts by mass or more when the entire resin is taken as 100 parts by mass. The surface protective layer 7 may contain weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, etc., as necessary.

[0060] As the material of the surface protection layer 7, for example, an ionizing radiation curable resin or a two-liquid curable urethane resin can be used. The ionizing radiation curable resin is not particularly limited. For example, a transparent resin mainly composed of a prepolymer (including oligomer) and / or a monomer containing a radical polymerizable double bond in the molecule that can undergo polymerization and crosslinking reaction by irradiation with ionizing radiation such as infrared rays, ultraviolet rays, and electron beams can be used. These prepolymers or monomers can be used alone or in combination. Specifically, the prepolymers or monomers include compounds having radical polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, cationic polymerizable functional groups such as epoxy groups, and the like in the molecule. Also preferred are polyene / thiol-based prepolymers obtained by combining polyene and polythiol. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0061] Examples of prepolymers 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, etc. The molecular weight of these is preferably about 250 to 100,000.

[0062] Examples of the monomer having a radically polymerizable unsaturated group include monofunctional monomers such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and phenoxyethyl(meth)acrylate. Examples of the polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0063] Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy compounds, and vinyl ether resins such as fatty acid-based vinyl ethers and aromatic vinyl ethers.

[0064] Examples of polyene-based prepolymers include those in which allyl alcohol is added to both ends of polyurethane made of diol and diisocyanate, and examples of thiol-based prepolymers include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

[0065] As the ionizing radiation, for example, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) can be used. As the curing reaction, for example, a crosslinking curing reaction can be used. As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, for example, 190 nm or more and 380 nm or less can be used. As the electron beam source, for example, an electron beam accelerator such as a Cockcroft-Walton type, a Van de Graft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, or a high frequency type can be used. In particular, it is preferable to use one that can irradiate 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).

[0066] The two-component curing urethane resin is not particularly limited. For example, a resin containing a polyol component having an OH group as a base agent and an isocyanate component as a curing agent can be used. 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 metaxylene diisocyanate.

[0067] [Embossed section] An embossed portion 7a consisting of an uneven pattern is formed on the surface of the surface protection layer 7 to impart a given design. Examples of the uneven pattern include the duct grooves of a wood grain board, the uneven surface of a stone board (such as the cleavage surface of granite), the texture of a cloth surface, matte finish, sand grain, hairline, and linear grooves. The embossed portion 7a is provided so that the uneven pattern is in harmony with the pattern of the pattern layer 5. This allows the decorative sheet 1 to be given a good texture close to that of real wood or stone.

[0068] The uneven pattern can be formed, for example, by embossing. The embossing method is not particularly limited. For example, a known sheet-fed embossing machine or rotary embossing machine can be used.

[0069] [Gloss matte pattern] The pattern portion 3 for expressing the gloss matte is formed of a material that has a light absorbing property for light of a predetermined wavelength, for example, a material that has an infrared absorbing property. As will be described in detail later, the pattern portion 3 for expressing the gloss matte is provided in order to easily form the embossed portion 7a at a desired position (a position that is in harmony with the pattern of the pattern layer 5), that is, to easily impart a texture close to that of actual wood or stone to the decorative sheet 1.

[0070] In this embodiment, the pattern portion 3 for expressing the gloss matte is formed using, for example, a colorless, transparent or relatively nearly transparent light-colored (light-colored) ink containing a material having an infrared absorbing effect. Therefore, the visibility of the pattern portion 3 for expressing the gloss matte as viewed from the surface protective layer 7 side is significantly reduced, and the influence on the color of the picture layer 5 (picture pattern) and the colored thermoplastic resin layer 2 (base color) as viewed from the surface protective layer 7 side can be greatly reduced. As the colorless, transparent or light-colored ink used for the pattern portion 3 for expressing the gloss matte, for example, a urethane-based printing ink can be used.

[0071] Here, when a dark ink such as a black ink containing carbon black is used for the pattern portion for expressing the gloss matte, the color of the dark ink may be slightly visible through the colored thermoplastic resin layer 2 and the pattern layer 5 when viewed from the surface protective layer 7 side. For example, when the base color of the colored thermoplastic resin layer 2 or the pattern of the pattern layer 5 is close to a light color (e.g., white), the dark ink may be visible through the colored thermoplastic resin layer 2 and the pattern layer 5, and may be viewed as a color different from the original color when viewed from the surface protective layer 7 side. For this reason, it is difficult to express the intended color, especially for the base color and pattern of a light color, and it may not be possible to fully express a good color close to the real thing such as actual wood or stone.

[0072] In contrast, in the decorative sheet 1 according to this embodiment, the pattern portion 3 for expressing the gloss matte, which is an area containing a material having an infrared absorbing effect, is formed using a colorless transparent or light-colored ink. In other words, the pattern portion 3 for expressing the gloss matte does not contain a dark-colored ink. This allows the original color to be seen even in a light-colored base color or pattern that is close to white, and the intended color can be expressed appropriately. Therefore, the decorative sheet 1 according to this embodiment can express a good color close to the real thing such as actual wood or stone.

[0073] As the material having infrared absorbing properties in the matte gloss pattern portion 3, at least one of inorganic materials such as tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), lanthanum hexaboride (LaB6), cesium-doped tungsten oxide, etc. may be used. Furthermore, organic materials such as near-infrared absorbing materials, infrared absorbing materials, and phthalocyanine-based materials, as well as existing materials having infrared absorbing properties, may be used.

[0074] The pattern portion 3 for expressing the gloss mat is disposed at a position that is in harmony with the pattern of the pattern layer 5. For example, in the case of the pattern layer 5 having a wood grain pattern, the pattern portion 3 for expressing the gloss mat is formed at a position that overlaps with the wood grain board duct groove of the pattern layer 5 in a plan view. In this case, "in harmony" means that the pattern portion 3 for expressing the gloss mat and the pattern of the pattern layer 5 are formed at a position that overlaps with each other in a plan view.

[0075] The thickness of the pattern portion 3 for expressing the gloss matte need only be such that it is possible to soften the transparent thermoplastic resin layer 6 and the surface protective layer 7 to a degree that allows a sufficient uneven shape to be formed in the surface protective layer 7 during the embossing process described below.

[0076] As described above, the gloss matte-producing pattern portion 3 is made of a material that is light-absorbent to light of a predetermined wavelength. Examples of light of a predetermined wavelength include infrared light, ultraviolet light, visible light, electron beams, X-rays, and ion beams.

[0077] [Pattern layer] The pattern layer 8a is formed on the surface of the colored thermoplastic resin layer 2 opposite to the design layer 5. The pattern layer 8a is composed only of a matte gloss producing pattern portion 3 formed of a material having light absorbing properties for infrared rays, for example.

[0078] [Primer layer] The primer layer 8 is a base layer for improving adhesion and corrosion resistance with a substrate (not shown) to which the decorative sheet 1 is attached. The primer layer 8 is provided on the surface of the colored thermoplastic resin layer 2 opposite the design layer 5 so as to cover the surface of the pattern portion 3 for expressing gloss matte that constitutes the pattern layer 8a. The primer layer 8 is configured to include the pattern portion 3 for expressing gloss matte.

[0079] The primer layer 8 is formed using, for example, a polyester resin, an organic additive, a pigment, etc. An anti-rust pigment may be blended into the primer layer 8 for the purpose of improving corrosion resistance. The thickness of the primer layer 8 is, for example, within the range of 1 μm to 10 μm.

[0080] [Method of manufacturing decorative sheet] Next, an example of a method for producing the decorative sheet according to this embodiment will be described with reference to FIG. First, a colored thermoplastic resin layer 2 is formed. For example, it is formed using PBT (polybutylene terephthalate resin) to a thickness of, for example, 50 μm (FIG. 2(a)).

[0081] Next, on one surface of the colored thermoplastic resin layer 2, a design layer 5 is printed using, for example, a urethane-based printing ink.

[0082] Next, a pattern layer 8a is formed by forming a pattern portion 3 for expressing a gloss matte, which is an area containing a material having a light absorbing property for light of a predetermined wavelength, on the surface of the colored thermoplastic resin layer 2 opposite to the pattern layer 5. That is, a process is carried out in which the pattern portion 3 for expressing a gloss matte, which is an area containing a material having an infrared absorbing property, is arranged so as to match the pattern of the pattern layer 5 to form the pattern layer 8a. For example, the pattern portion 3 for expressing a gloss matte is formed at a predetermined position that matches the pattern of the pattern layer 5 using a colorless transparent or light-colored ink containing a material having an infrared absorbing property (FIG. 2(b)).

[0083] Next, a primer layer 8 made of, for example, a polyester-based resin is laminated on top of the colored thermoplastic resin layer 2 including the pattern portion 3 for expressing the gloss matte so as to fill the gaps between the pattern portions 3 for expressing the gloss matte and to cover the upper surface (Figure 2(c)). Next, a PP (polypropylene) resin having a thickness of, for example, 38 μm is laminated as a transparent thermoplastic resin layer 6 on the surface of the design layer 5 opposite to the colored thermoplastic resin layer 2. Nucleating agent-encapsulating vesicles having an outer membrane made of phospholipids encapsulating a phosphate metal salt-based nucleating agent as a nano-sized nucleating agent are added to this PP resin.

[0084] Then, the surface protective layer 7 is laminated on the transparent thermoplastic resin layer 6. As a result, the design layer 5, the transparent thermoplastic resin layer 6, and the surface protective layer 7 are laminated in this order on one surface of the colored thermoplastic resin layer 2.

[0085] Next, the entire laminate in which these layers are stacked as shown in Fig. 2(d) is irradiated with infrared rays (irradiation light) (Fig. 2(e)), and immediately after the infrared irradiation, an embossing plate such as an embossing roll is pressed onto the surface of the surface protective layer 7 (Fig. 2(f)). This forms the embossed portion 7a, and the decorative sheet 1 is formed. In other words, a step of irradiating with irradiation light (e.g., infrared light) in which the power of light of a predetermined wavelength is stronger than the power of light of other wavelengths, and a step of pressing an embossing plate for forming an embossed shape onto the surface protective layer 7 are performed after the step of irradiating with the irradiation light.

[0086] Here, the pattern portion 3 for expressing the gloss matte is formed of a colorless transparent or light-colored ink having infrared absorbing properties. Therefore, when infrared rays are irradiated to a laminate in which the primer layer 8, the colored thermoplastic resin layer 2, the design layer 5, the transparent thermoplastic resin layer 6, and the surface protective layer 7 are laminated in this order, the transparent thermoplastic resin layer 6 and the surface protective layer 7 are more likely to soften in the portion of the surface protective layer 7 that overlaps with the pattern portion 3 for expressing the gloss matte in a planar view than in the portion that does not overlap with the pattern portion 3 for expressing the gloss matte. In other words, the transparent thermoplastic resin layer 6 and the surface protective layer 7 after infrared irradiation have a portion that is easy to soften and a portion that is difficult to soften. Therefore, when an embossing plate is pressed on the transparent thermoplastic resin layer 6 and the surface protective layer 7 in this state, unevenness is easily formed in the softened portion, and unevenness is not easily formed in the portion that is difficult to soften. Therefore, unevenness is easily formed in the softened portion of the transparent thermoplastic resin layer 6 and the surface protective layer 7, i.e., the portion that overlaps with the pattern portion 3 for expressing the gloss matte in a planar view. As a result, embossed portions 7a consisting of uneven shapes in harmony with the pattern portion 3 for expressing gloss matte are easily formed only at positions that overlap with the pattern portion 3 for expressing gloss matte of the transparent thermoplastic resin layer 6 and the surface protective layer 7 in a plan view. Furthermore, by using a colorless transparent or light-colored ink for the pattern portion 3 for expressing gloss matte, the effect on the pattern pattern of the picture layer 5 and the color of the base color of the colored thermoplastic resin layer 2 is very small.

[0087] This allows the embossed portion 7a to be formed in a position that is in sync with the picture layer 5, i.e., the embossed portion 7a can be easily created in sync with the picture layer 5 without performing highly accurate positioning operations. Therefore, it is possible to provide a decorative sheet 1 that has a texture close to the real thing, expresses good colors that are close to the real thing, and has excellent design properties.

[0088] The timing for pressing the embossing plate onto the transparent thermoplastic resin layer 6 and the surface protective layer 7 after infrared irradiation is not limited to immediately after infrared irradiation, but may be any timing that allows pressing onto the surfaces of the transparent thermoplastic resin layer 6 and the surface protective layer 7 to selectively form an uneven shape in the parts softened by infrared irradiation.

[0089] In addition, other steps may be included between the step of creating the surface protective layer 7 and the step of performing infrared irradiation, and the point is that the infrared irradiation is performed in a state where the transparent thermoplastic resin layer 6 and the surface protective layer 7 have been formed.

[0090] Thus, according to the manufacturing method of the decorative sheet 1 according to this embodiment, by irradiating the laminate in which the layers are stacked with infrared rays and then pressing the embossing plate, it is possible to strongly emboss the portion that overlaps with the gloss matte development pattern portion 3 in a plan view. In other words, the embossed portion 7a can be easily formed in the desired position without having to perform high-precision positioning of the area where the embossing plate is pressed. As a result, a decorative sheet with excellent design properties can be easily obtained.

[0091] In addition, since the pattern portion 3 for expressing gloss matte is provided under the colored thermoplastic resin layer 2, the visibility of the pattern portion 3 for expressing gloss matte is reduced when the decorative sheet 1 is viewed from the surface protective layer 7 side. As a result, although a colorless transparent or light-colored ink having infrared absorbing properties is used as the pattern portion 3 for expressing gloss matte, the visibility of the pattern portion 3 for expressing gloss matte can be further suppressed when the decorative sheet 1 is viewed from the surface protective layer 7 side. Therefore, even if a dark color pattern is not used as the pattern layer 5, the visibility of the pattern portion 3 for expressing gloss matte can be significantly suppressed, and as a result, a light-colored pattern can be adopted as the pattern layer 5, and the constraint on pattern expression caused by the provision of the pattern portion 3 for expressing gloss matte can be significantly suppressed.

[0092] In addition, a colored thermoplastic resin layer 2 and a picture layer 5, and further a transparent thermoplastic resin layer 6 and a surface protective layer 7 are laminated on top of a pattern layer 8a consisting of a pattern portion 3 for expressing gloss matte using a colorless, transparent or light-colored ink containing a material with infrared absorbing properties, and an embossed portion 7a is formed at a position on the surface protective layer 7 that overlaps with the pattern portion 3 for expressing gloss matte when viewed in a plane, thereby further reducing the visibility of the pattern portion 3 for expressing gloss matte. This makes it possible to greatly reduce the impact of the pattern portion 3 for expressing gloss matte, which is useful in the manufacturing process of the decorative sheet 1, on the appearance of the decorative sheet 1, and a highly attractive decorative sheet 1 can be obtained in which the pattern of the picture layer 5 and the embossed portion 7a are in harmony with each other.

[0093] Furthermore, since the pattern portion 3 for expressing the gloss matte is arranged in harmony with the pattern of the pattern layer 5, it is possible to form an uneven portion in harmony with the pattern of the pattern layer 5, that is, it is possible to easily express a gloss matte effect in harmony with the pattern.

[0094] In addition, by providing the unevenness, the gloss matte expression is achieved, and it is possible to prevent the pattern of the gloss matte from coming off, etc. Therefore, for example, the synchronous gloss matte expression can be achieved even in flooring materials, etc.

[0095] [Effects of this embodiment] (1) A method for manufacturing a decorative sheet according to this embodiment includes the steps of laminating, in this order, a pattern layer 5 having a pattern, a transparent thermoplastic resin layer 6 containing a nano-sized nucleating agent, and a surface protective layer 7 on one side of a colored thermoplastic resin layer 2; forming a pattern layer 8a on the other side of the colored thermoplastic resin layer 2 using a colorless or light-colored ink and a material that is more light-absorbent for light of a predetermined wavelength than the colored thermoplastic resin layer 2, by arranging an area that is more light-absorbent for light of a predetermined wavelength than the colored thermoplastic resin layer 2 in harmony with the pattern; after the step of forming the pattern layer 8a, irradiating with light having a predetermined wavelength that is stronger in power than the light of other wavelengths; and, after the step of irradiating with light, pressing an embossing plate for forming an embossed shape onto the surface protective layer 7.

[0096] This allows the embossed portion 7a to be provided in a position on the decorative sheet 1 that matches the pattern layer 5, and furthermore the colors of the colored thermoplastic resin layer 2 and the pattern layer 5 (base color and pattern color) are hardly affected by the color of the gloss matte-producing pattern portion 3. As a result, a decorative sheet 1 with excellent design properties can be obtained that has a texture closer to the real thing and expresses good colors closer to the real thing.

[0097] Furthermore, since the transparent thermoplastic resin layer 6 is formed containing a nucleating agent, a transparent thermoplastic resin layer 6 having high tensile elongation at break and high crystallinity can be obtained. As a result, it is possible to obtain a decorative sheet 1 having excellent post-processing resistance by suppressing the occurrence of cracks, whitening, etc. during post-processing such as V-groove bending, and it is also possible to obtain a decorative sheet 1 having excellent scratch resistance by improving the crystallinity of the decorative sheet 1.

[0098] (2) At least one type of inorganic material selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, lanthanum hexaboride, and cesium-doped tungsten oxide is used as the material having infrared light absorption properties contained in the pattern portion 3 for expressing gloss matte. Therefore, in the portion overlapping with the pattern portion 3 for expressing gloss matte, the transparent thermoplastic resin layer 6 and the surface protection layer 7 can be easily softened by infrared irradiation, and the portion overlapping with the pattern portion 3 for expressing gloss matte can be easily embossed.

[0099] (3) Furthermore, the decorative sheet according to this embodiment comprises a pattern layer 5, a transparent thermoplastic resin layer 6 and a surface protective layer 7 laminated in that order on one side of the colored thermoplastic resin layer 2, and a pattern layer 8a laminated on the other side of the colored thermoplastic resin layer 2, in which a gloss matte-producing pattern section 3, which is an area that is more light-absorbent for light of a predetermined wavelength than the colored thermoplastic resin layer 2, is arranged in harmony with the pattern of the pattern layer 5, the transparent thermoplastic resin layer 6 containing a nano-sized nucleating agent, the light-absorbent area being formed from a material containing a colorless or light-colored ink and a light-absorbent material, and an embossed section 7a is formed in a position of the surface protective layer 7 that overlaps with the light-absorbent area in a planar view.

[0100] This allows the embossed portion 7a to be provided in a position on the decorative sheet 1 that matches the pattern layer 5, and furthermore, the colors of the colored thermoplastic resin layer 2 and the pattern layer 5 (base color and pattern color) are hardly affected by the color of the gloss matte-producing pattern portion 3 formed using colorless or light-colored ink. As a result, a decorative sheet with excellent design properties can be obtained that has a texture closer to the real thing and expresses good colors closer to the real thing.

[0101] [Modifications] (1) In the above embodiment, a material having infrared absorbing properties is used as the pattern part 3 for expressing gloss matte, and infrared irradiation is performed to partially soften the transparent thermoplastic resin layer 6 and the surface protective layer 7, but the present invention is not limited to this. The material of the pattern part 3 for expressing gloss matte may be a material made of a component having light absorbing properties for light of a predetermined wavelength other than infrared rays, and containing a colorless or light-colored ink, and the transparent thermoplastic resin layer 6 and the surface protective layer 7 may be partially softened by using a light source that irradiates light of the predetermined wavelength. (2) In the above embodiment, the design layer 5 is laminated on one surface of the colored thermoplastic resin layer 2, then the pattern layer 8a and the primer layer 8 are formed on the other surface of the colored thermoplastic resin layer 2, and then the transparent thermoplastic resin layer 6 and the surface protective layer 7 are formed on the surface of the design layer 5 opposite the colored thermoplastic resin layer 2, but this is not limited to the above. For example, the steps of forming the design layer 5, the transparent thermoplastic resin layer 6, and the surface protective layer 7 on one surface of the colored thermoplastic resin layer 2 may be carried out in succession. (3) Also, as shown in Fig. 3, the decorative sheet 1 according to the above embodiment may be attached to a base material 9, which 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 side of the base material 9, or may be provided on both sides.

[0102] [Base material] The substrate 9 may be a wood substrate or a metal substrate. The substrate 9 may be, for example, a wood veneer, a wood plywood, a laminated lumber, a particle board, a medium density fiberboard, or a hard fiberboard. The substrate 9 may be, for example, a steel plate or an aluminum plate. The substrate 9 may be made of a resin such as plastic, or a composite material thereof. That is, the substrate 9 may be a resin substrate. The substrate 9 may be, for example, a non-combustible substrate made of a non-combustible material such as a non-combustible steel plate or a non-combustible material as specified by Ministry of Construction Notification No. 1400.

[0103] Thus, the decorative member 10 includes the base material 9 and the decorative sheet 1 provided on at least one surface side of the base material 9. The base material 9 can be any of a wood base material, a resin base material, a non-combustible base material, and a metal base material. EXAMPLES

[0104] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0105] Example 1 On one side of a colored thermoplastic resin layer 2 consisting of a 55 μm thick PE (polyethylene) layer, a pattern layer 5 consisting of a urethane-based printing ink, a transparent thermoplastic resin layer 6 consisting of a 80 μm thick petroleum PP (polypropylene) layer, and a surface protection layer 7 mainly composed of a resin composition containing an acrylic UV-curable resin were laminated in this order. An adhesive layer (not shown) consisting of an adhesive resin containing a urethane-based adhesive was provided between the pattern layer 5 and the transparent thermoplastic resin layer 6, thereby bonding the pattern layer 5 and the transparent thermoplastic resin layer 6.

[0106] Furthermore, a transparent ink made of a urethane-based printing ink containing an infrared absorbing material was pattern-printed on the other surface of the colored thermoplastic resin layer 2 (the surface opposite to the pattern layer 5) to form a pattern part 3 for expressing a matte gloss effect, forming a pattern layer 8a made of the pattern part 3 for expressing a matte gloss effect, and a primer layer 8 was formed on the colored thermoplastic resin layer 2 containing the pattern layer 8a, thereby obtaining a laminate. This is equivalent to forming the pattern part 3 for expressing a matte gloss effect containing an infrared absorbing material and the pattern part for expressing a non-matte gloss effect made of the primer layer 8 and not containing an infrared absorbing material on the surface of the colored thermoplastic resin layer 2 opposite to the pattern layer 5.

[0107] The transparent thermoplastic resin layer 6 was prepared in the following manner.

[0108] A highly crystalline homopolypropylene resin with an isotactic pentad fraction of 97.8%, MFR (melt flow rate) of 15g / 10min (230℃), and molecular weight distribution MWD (Mw / Mn) of 2.3 was mixed with 500PPM of a hindered phenol-based antioxidant (Irganox 1010: manufactured by BASF Japan Ltd.), 2000PPM of a benzotriazole-based UV absorber (Tinuvin 328: manufactured by BASF Japan Ltd.), and a hindered amine-based light stabilizer (Kimasoh A resin containing 2000 PPM of BASF 944 (manufactured by BASF Japan Co., Ltd.) and 1000 PPM of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate nano-processed by a solid phase method was extruded using a melt extruder to form a transparent resin sheet made of highly crystalline polypropylene with a thickness of 100 μm to be used as the transparent thermoplastic resin layer 6, and then both sides of the formed transparent resin sheet were subjected to corona treatment to set the surface wetting tension to 40 dyn / cm or more. By controlling the cooling conditions during extrusion film formation, the haze value of the crystalline polypropylene resin of the formed transparent resin sheet was 8.5%.

[0109] This transparent resin sheet was laminated onto the design layer 5 to form a transparent thermoplastic resin layer 6 .

[0110] After the primer layer 8 was formed, the laminate was heated by an infrared heater, and then an embossing roll was pressed against the surface protective layer 7 to form embossed portions 7a, thereby obtaining the decorative sheet shown in FIG.

[0111] Comparative Example 1 A decorative sheet was produced in the same manner as in Example 1, except that in the decorative sheet of Example 1, the transparent thermoplastic resin layer was produced without adding a nucleating agent. Comparative Example 2 In the decorative sheet of Comparative Example 1, a gloss matte print was applied to the surface protective layer in harmony with the pattern of the pattern layer, and the decorative sheet was produced in the same manner as in Comparative Example 1, except that the process of heating with an infrared heater was not performed.

[0112] (Reference example 1) A decorative sheet was produced in the same manner as in Comparative Example 2, except that in the decorative sheet of Comparative Example 2, the surface protective layer was made of a thermosetting resin and gloss matte printing was not performed.

[0113] 〔evaluation〕 The decorative sheets of Example 1, Comparative Examples 1 and 2, and Reference Example 1 were evaluated for design, pencil hardness, Hoffman scratch test, sliding properties, and V-groove bending suitability. The evaluation criteria were as follows.

[0114] (Design (gloss matte matching)) Each decorative sheet was visually inspected to see whether the embossed or gloss matte printed portion matched the pattern. If the two matched, it was marked "○", and if they did not match, it was marked "×".

[0115] (Pencil hardness) A pencil hardness test was conducted on a decorative member made by bonding a decorative sheet to MDF (medium density fiberboard) using pencils of different hardness, and the damage (gouging) that occurred on the surface (surface protection layer) was checked to evaluate the surface hardness. If damage occurred on the surface after the pencil hardness test using a pencil with a hardness of 4B or more, it was marked as "◎", if damage occurred on the surface after the pencil hardness test using a pencil with a hardness of 5B or more, it was marked as "○", and if damage occurred on the surface after the pencil hardness test using a pencil with a hardness of 6B or less, it was marked as "×".

[0116] The pencil hardness test was a pencil scratch test in accordance with the old JIS K5400.

[0117] (Hoffman scratch test) A scratch test was performed on the surface of the decorative sheet using a Hoffman scratch hardness tester (GARDCO). A scratch blade (a cylindrical blade with a diameter of 7 mm) was set so that it was in contact with the surface at a 45 degree angle, and the tester was moved over the decorative sheet to check for scratches.

[0118] The load (weight) was gradually increased in increments of 200g within the range of 200g to 2000g, and the sample was scratched, and the load (g) at which the sample surface was scratched was used for evaluation. If the sample was scratched with a load of 800g, "600g" was recorded as the withstand load in the table. A withstand load of "200g" was deemed to have failed.

[0119] (Sliding properties) The sliding properties of the felt were confirmed using a crock meter. Load: 500g / cm 2 The rubbing was performed under the above conditions, and the number of times was gradually increased in increments of 500 between 500 and 2000 times to check the sliding properties. If there was no difference in the gloss matte design after 2000 times, it was marked as "◯" (pass). If there was no difference in the gloss matte design after 100 to 1500 times, it was marked as "△", and if there was a difference in the gloss matte design after 500 times, it was marked as "×" (fail).

[0120] (V-groove bending suitability) The suitability for V-cut processing (presence or absence of whitening when folded) was confirmed using a decorative component made by bonding a decorative sheet to MDF (medium density fiberboard). As a result, samples that did not show any whitening were rated as "◯" (pass), samples that showed some whitening were rated as "△" (pass), and samples that showed some whitening were rated as "×" (fail). The evaluation results are shown in Table 1.

[0121] [Table 1]

[0122] As shown in Table 1, it was confirmed that the decorative sheet of Example 1 could obtain the same design as that obtained by performing gloss matte printing. In addition, it was confirmed that by adding a nucleating agent to the transparent thermoplastic resin layer 6, the pencil hardness, Hoffman scratch test, and bending processability were improved compared to the case where a nucleating agent was not added.

[0123] The present invention can have the following configurations, for example. (1) A method for producing a decorative sheet having an embossed shape that matches a pattern, comprising the steps of: laminating a pattern layer having the pattern, a transparent resin layer containing a nano-sized nucleating agent, and a surface protective layer in this order on one surface of a colored resin layer; forming a pattern layer on the other surface of the colored resin layer by using a colorless or light-colored ink and a material having a higher light absorption property for light of a predetermined wavelength than the colored resin layer, and arranging the light-absorbing region in a manner to be in harmony with the pattern; a step of irradiating the pattern layer with light having a power of the predetermined wavelength stronger than the power of light having other wavelengths, after the step of forming the pattern layer; a step of pressing an embossing plate for forming an embossed shape onto the surface protective layer after the step of irradiating with the irradiation light; A method for producing a decorative sheet, comprising:

[0124] (2) The method for producing a decorative sheet according to (1) above, wherein the light-absorbing material is a material that is light-absorbing to infrared rays.

[0125] (3) The method for producing a decorative sheet according to (1) or (2) above, wherein the light-absorbing material is at least one inorganic material selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, lanthanum hexaboride, and cesium-doped tungsten oxide.

[0126] (4) A method for producing a decorative sheet according to any one of (1) to (3) above, characterized in that the transparent resin layer is formed using a crystalline polypropylene resin to which the nano-sized nucleating agent has been added.

[0127] (5) a pattern layer, a transparent resin layer, and a surface protective layer laminated in this order on one surface of the colored resin layer; a pattern layer laminated on the other surface of the colored resin layer, the pattern layer having an area having a higher light absorption property for light of a predetermined wavelength than the colored resin layer and arranged in phase with the pattern of the pattern layer; The transparent resin layer contains a nano-sized nucleating agent, the light absorbing region is formed of a material containing a colorless or light-colored ink and a light absorbing material; A decorative sheet, comprising: an embossed portion formed on said surface protective layer at a position overlapping said light-absorbing region in a plan view.

[0128] (6) The decorative sheet according to (5), wherein the transparent resin layer contains a crystalline polypropylene resin and the nano-sized nucleating agent.

[0129] (7) A substrate; The decorative sheet according to (5) or (6) above is provided on at least one surface side of the substrate, The decorative member is characterized in that the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate. [Explanation of symbols]

[0130] 1 Decorative sheet 2 Colored thermoplastic resin layer 3 Gloss matte pattern 5. Picture layer 6 Transparent thermoplastic resin layer 7 Surface protective layer 7a Embossed section 8 Primer layer 8a Pattern layer 10. Decorative materials

Claims

1. A method for producing a decorative sheet having an embossed shape that matches a pattern, comprising the steps of: laminating a pattern layer having the pattern, a transparent resin layer containing a nano-sized nucleating agent, and a surface protective layer in this order on one surface of a colored resin layer; forming a pattern layer on the other surface of the colored resin layer by using a colorless or light-colored ink and a material having a higher light absorption property for light of a predetermined wavelength than the colored resin layer, and arranging the light-absorbing region in a manner to be in harmony with the pattern; a step of irradiating the pattern layer with light having a power of the predetermined wavelength stronger than the power of light having other wavelengths, after the step of forming the pattern layer; a step of pressing an embossing plate for forming an embossed shape onto the surface protective layer after the step of irradiating with the irradiation light; A method for producing a decorative sheet, comprising:

2. 2. The method for producing a decorative sheet according to claim 1, wherein the light-absorbing material is a material that is light-absorbing to infrared rays.

3. 3. The method for producing a decorative sheet according to claim 1, wherein the light absorbing material is at least one inorganic material selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, lanthanum hexaboride, and cesium-doped tungsten oxide.

4. The method for producing a decorative sheet according to claim 3, characterized in that the transparent resin layer is formed using a crystalline polypropylene resin to which the nano-sized nucleating agent has been added.

5. a pattern layer, a transparent resin layer, and a surface protective layer laminated in this order on one surface of the colored resin layer; a pattern layer laminated on the other surface of the colored resin layer, the pattern layer having an area having a higher light absorption property for light of a predetermined wavelength than the colored resin layer and arranged in phase with the pattern of the pattern layer; The transparent resin layer contains a nano-sized nucleating agent, the light absorbing region is formed of a material containing a colorless or light-colored ink and a light absorbing material; A decorative sheet, comprising: an embossed portion formed on said surface protective layer at a position overlapping said light-absorbing region in a plan view.

6. The decorative sheet according to claim 5 , wherein the transparent resin layer contains a crystalline polypropylene resin and the nano-sized nucleating agent.

7. A substrate; The decorative sheet according to claim 5 or 6 provided on at least one surface side of the substrate, The decorative member is characterized in that the substrate is any one of a wood substrate, a resin substrate, a non-flammable substrate, and a metal substrate.

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