Decorative sheet manufacturing method and decorative sheet

Abstract

To provide a manufacturing method of a decorative sheet having texture more close to a genuine object and having excellent designability.SOLUTION: A manufacturing method of a decorative sheet includes the steps of forming a gross matte development pattern 3 at a position that has light absorption to infrared ray and synchronizes with a pattern (Fig. 2(a)), forming a hiding solid layer 4 for reducing recognizability of the gross matte development pattern 3, so as to cover a gap between the gross matte development patterns 3 and a top surface of the gross matte development pattern 3 (Fig. 2(b)), laminating a pattern layer 5, a transparent thermoplastic resin layer 6 and a surface protective layer 7 in this order on the hiding solid layer 4 (Fig. 2(c),(d)), and after lamination, irradiating the layer with infrared rays (Fig. 2(e)) and after irradiation with infrared ray, stamping an emboss plate on the surface protective layer 7 (Fig. 2(f)).SELECTED DRAWING: Figure 2

Description

[Technical Field]

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

[0002] Decorative sheets have been developed and expanded as the residential construction industry has grown. Originally, homes were built using materials suited to the characteristics of the region, such as wood and stone. However, as the housing industry has developed, industrialization has progressed, resulting in a shift from natural materials to artificial materials. In recent years, the widespread use of high-quality wood and stone has led to concerns that it could lead to deforestation and environmental problems, which has also become a factor in expanding demand for decorative sheets. For example, decorative materials in which decorative sheets are bonded to wood substrates such as plywood, MDF (medium-density fiberboard), and particle board, as well as resin substrates, inorganic non-combustible substrates, and metal substrates, are widely used (see, for example, Patent Document 1).

[0003] Furthermore, the design of decorative sheets is often designed to imitate the surfaces of wood, stone, and the like. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5045180 Summary of the Invention [Problem to be solved by the invention]

[0005] 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 far superior.

[0006] The present invention has been made in view of the above-mentioned points, and aims to provide a method for producing a decorative sheet that has a texture closer to the real thing and has excellent design properties, and a decorative sheet. [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, comprising the steps of: forming a pattern layer that is in harmony with the pattern using a predetermined material that is light-absorbent for light of a predetermined wavelength; forming a concealing layer on the pattern layer to reduce the visibility of the portion of the pattern layer that is formed from the predetermined material; stacking a pattern layer having the pattern, a transparent resin layer, and a surface protection layer on the concealing layer in this order; after the stacking step, irradiating with light having a power of light of the predetermined wavelength that is stronger than the power of light of other wavelengths; and after the irradiating with light, pressing an embossing plate for forming the embossed shape into the surface protection layer. Another aspect of the present invention is a decorative sheet having a pattern layer, which comprises a pattern layer in which a specified material that is light-absorbent for light of a specified wavelength is arranged in harmony with the pattern of the pattern layer, a concealing layer arranged on top of the pattern layer to reduce the visibility of the portion of the pattern layer formed from the specified material, and the pattern layer, a transparent resin layer, and a surface protective layer stacked in that order on top of the concealing layer, and in which an embossed portion is formed in the surface protective layer at a position that overlaps the portion formed from the specified material in a planar view. [Effects of the Invention]

[0008] According to one aspect of the present invention, a decorative sheet can be obtained that has a texture similar to the surface texture of wood, stone, and the like used in building materials and has excellent design properties. [Brief explanation of the drawings]

[0009] [Figure 1]1 is a cross-sectional view schematically showing an example of a decorative sheet produced by a decorative sheet manufacturing method according to one embodiment of the present invention. [Figure 2] 1A to 1C are process diagrams schematically illustrating an example of a procedure for producing a decorative sheet according to one embodiment of the present invention. [Figure 3] FIG. 10 is a cross-sectional view schematically showing another example of a decorative sheet produced by a method for producing a decorative sheet according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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 material for floors or building materials will be described as an example, but the present technology may also be used for decorative sheets for other parts.

[0011] The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., differ from the actual ones. Furthermore, the embodiments shown below are merely 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.

[0012] A method for manufacturing a decorative sheet according to one embodiment of the present invention is a method for manufacturing a decorative sheet having an embossed shape that matches a pattern, and includes the steps of: forming a pattern layer that matches the pattern using a specified material that is light-absorbent for light of a specified wavelength; forming a concealing layer on the pattern layer to reduce the visibility of the portion of the pattern layer that is formed from the specified material; stacking a pattern layer having the pattern, a transparent resin layer, and a surface protection layer on the concealing layer in this order; after the stacking step, irradiating with light having a power of light of the specified wavelength that is stronger than the power of light of other wavelengths; and after the irradiating with light, pressing an embossing plate for forming the embossed shape into the surface protection layer.

[0013] In addition, a decorative sheet according to another embodiment of the present invention is a decorative sheet having a pattern layer, which comprises a pattern layer in which a predetermined material that is light-absorbent for light of a predetermined wavelength is arranged in harmony with the pattern of the pattern layer, a concealing layer arranged on top of the pattern layer to reduce the visibility of the portion of the pattern layer formed from the predetermined material, and the pattern layer, a transparent resin layer, and a surface protective layer stacked in that order on top of the concealing layer, and an embossed portion is formed in the surface protective layer at a position that overlaps the portion formed from the predetermined material in a planar view.

[0014] 1, a decorative sheet 1 formed by a decorative sheet manufacturing method according to one embodiment of the present invention is formed by laminating, in this order, a colored thermoplastic resin layer 2, a pattern portion for developing a matte gloss finish 3, a solid concealing layer 4, a design layer 5, a transparent thermoplastic resin layer (transparent resin layer) 6, and a surface protective layer 7, with an embossed portion (embossed shape) 7a formed in the surface protective layer 7. The pattern portion for developing a matte gloss finish 3 is formed at a position corresponding to a pattern of the design layer 5 that is to be synchronized with the embossed portion 7a.

[0015] The concealing solid layer 4 is formed so as to cover the gaps between the matt gloss developing pattern portions 3, i.e., the side and top surfaces of the matt gloss developing pattern portions 3. Although an example has been shown in which the matt gloss developing pattern portion 3 is formed directly on the matt gloss developing pattern portion 3, the matt gloss developing solid layer 4 may be formed anywhere between the matt gloss developing pattern portion 3 and the picture layer 5, and some kind of layer may be formed between the matt gloss developing pattern portion 3 and the matt gloss developing pattern portion 3.

[0016] FIG. 1 also illustrates a case in which a primer layer 8 is provided on the surface of the colored thermoplastic resin layer 2 opposite to the surface on which the matte gloss developing pattern portion 3 is formed. [Colored thermoplastic resin layer]

[0017] Examples of materials for 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, and methacrylic acid ester. Among these, polyolefin resins are preferred in terms of environmental compatibility, processability, and cost. The grade and composition of the resin can also be selected taking into consideration ease of sheeting, printability, and suitability for bending.

[0018] The hue of the colored thermoplastic resin layer 2 can be appropriately selected as the base color of the design layer 5. The colored thermoplastic resin layer 2 can be colored, for example, by mixing or kneading a colorant such as a pigment into the thermoplastic resin during sheeting. Alternatively, a colored layer can be formed as a solid ink layer using a coating or printing method before forming the gloss / matt pattern portion 3. Note that a colorless, transparent or colored, transparent thermoplastic resin layer may be used instead of the colored thermoplastic resin layer 2. [Gloss matte pattern]

[0019] The matt gloss developing pattern portion 3 is formed from a material that is light absorbing for a predetermined wavelength, for example, a material that has infrared absorbing properties. The matt gloss developing pattern portion 3 is formed from a material that contains black ink containing carbon black, for example, a urethane-based printing ink. The matt gloss developing pattern portion 3 is positioned in harmony with the pattern of the pattern layer 5. For example, in the case of a wood grain patterned pattern layer 5, the matt gloss developing pattern portion 3 is formed in a position that overlaps with the wood grain board vessel grooves of the pattern layer 5 in a plan view. [Concealing solid layer]

[0020] The concealing solid layer 4 may be a uniformly colored solid print layer. The concealing solid layer 4 is a layer that is laminated on the colored thermoplastic resin layer 2 so as to cover the spaces between and the upper surface of the gloss matte-exhibiting pattern portions 3, thereby imparting the intended color and adjusting the color of the surface. The concealing solid layer 4 is a colored layer that contains a binder resin and a colorant dispersed in the binder resin. The binder resin and colorant can be appropriately selected from the same materials as those used for the pattern layer 5.

[0021] The concealing solid layer 4 is, for example, a printed layer, and can be formed using the same printing method as the picture layer 5. Conventional coating methods, such as gravure coating, roll coating, and spray coating, can also be used. The ink composition (coating liquid) used to form the concealing solid layer 4 is made of a material that has lower infrared absorption than the gloss matte-producing pattern portion 3, which has infrared absorption, and is composed of, for example, a mixture of a solvent and solid components such as a colorant and a binder resin. The ink composition for the concealing solid layer may also contain other components such as a stabilizer, plasticizer, catalyst, and curing agent. The solvent, colorant, and binder resin can be selected appropriately from the same materials as those used in the printing ink for the picture layer 5. When an embossment is to be formed on the surface protective layer 7, the colorant color is preferably printed in a color that matches the embossment (e.g., brown for a wood grain pattern). This matches the embossment to further enhance the design of flooring and building materials. In other words, the color of the surface of the decorative sheet 1 on the surface protection layer 7 side will correspond to the color of the concealing solid layer 4 and the pattern layer 5, so by selecting the color of the concealing solid layer 4 and the pattern of the pattern layer 5 so as to conceal the color of the pattern portion 3 for expressing gloss matte, the design of the decorative sheet 1 can be further improved. Since the solvent eventually evaporates, the concealing solid layer 4 is formed mainly from solid components such as colorants, binder resins, etc. The thickness of the concealing solid layer 4 may be any thickness that can conceal the gloss matte-exhibiting pattern portion 3 and form an embossment. [Picture layer]

[0022] The design layer 5 is a printed layer on which a design pattern is printed to impart design to the decorative sheet 1. Known printing methods can be used to form the design layer 5. The printing method is not particularly limited, but gravure printing is preferred considering productivity and design quality. For example, if the colored thermoplastic resin layer 2 is available in a rolled state, printing to form the design layer 5 can be performed using a roll-to-roll printing device. Other printing methods include offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, and transfer printing from a transfer sheet. When using such printing methods, the design pattern of the design layer 5 can be formed by multicolor printing using the usual process colors of yellow, red, blue, and black, or by multicolor printing using special colors, in which plates of the individual colors that make up the design pattern are prepared.

[0023] Furthermore, the pattern of the pattern layer 5 may be any pattern, taking into consideration the design of the flooring or fittings. For example, a marble grain pattern can be used to evoke the image of a stone floor such as marble. For example, various wood grains or cork can be used as the pattern for a wood-based design. In addition to patterns of natural materials, artificial patterns based on these motifs or geometric patterns can also be used. Other examples of patterns include wood grain patterns composed of spring wood and autumn wood regions and vessels in the cross section of tree rings, leather (grain) patterns, stone grain patterns on the surface of stone materials such as marble, granite, and sandstone, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, geometric shapes, letters, symbols, abstract patterns, floral patterns, landscapes, characters, and the like.

[0024] Printing ink is a mixture of a solvent and solid components such as a colorant and a binder resin.

[0025] Examples of solvents 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 solvents may be used alone or in combination of two or more.

[0026] Examples of binder resins 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 chlorine-based resins include polyvinyl chloride resins such as polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, and vinyl chloride-vinyl acetate-(meth)acrylic copolymers, as well as polypropylene chloride and chlorinated polypropylene. Here, (meth)acrylic means acrylic or methacrylic. The binder resin may be a single type or a combination of two or more types.

[0027] 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 colorants may be used alone or in combination of two or more.

[0028] Here, the solvent contained in the printing ink will eventually volatilize, so the design layer 5 is formed mainly from solid components such as colorants and binder resins.

[0029] The printing ink may also contain other components such as stabilizers, plasticizers, catalysts, and curing agents. The printing ink may be selected based on the printing method. It is particularly preferable to select the ink taking into consideration its adhesion to the solid concealing layer 4, its printability, and its weather resistance as a flooring material or fitting. The thickness of the pattern layer 5 can be adjusted appropriately, taking into consideration the decorative properties 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 typically 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.

[0030] To improve the adhesion between the design layer 5 and the transparent thermoplastic resin layer 6, an adhesive layer (not shown) may be provided on the surface of the design layer 5 that comes into contact with the transparent thermoplastic resin layer 6. By strengthening this adhesion, the decorative sheet 1 can be given the ability to be bent to conform to 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. Alternatively, the adhesive resin may be adhered to the design layer 5 with 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).

[0031] Furthermore, a glittering layer (not shown) may be provided between the picture layer 5 and the transparent thermoplastic resin layer 6 in order to suitably impart design effects such as a sense of depth and brightness to the decorative sheet 1. The glittering layer (not shown) preferably contains a glittering pigment and a binder resin. Examples of glittering pigments include pearlescent pigments and metallic pigments. In particular, pearlescent pigments are preferred because they can prevent a decrease in the light transmittance of the glittering layer and therefore do not impair the visibility of the picture layer 5.

[0032] Pearl pigments are pigments that can impart pearlescent luster. Examples include base particles whose surfaces are coated with a metal oxide. The base particles are preferably scaly particles such as mica. Examples of metal oxides include oxides of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium. The metal oxides may be used alone or in combination. 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 flakes such as basic lead carbonate, lead hydrogen arsenate, and bismuth oxide chloride; fish scale powder, shell fragments, and pearl fragments.

[0033] Examples of metallic 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 metallic pigments may be used alone or in combination of two or more.

[0034] From the viewpoint of providing excellent design effects, for example, when forming the glittering layer using gravure printing, the average particle diameter 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 diameter 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, "average particle diameter" refers to the value that can be determined as the mass average value D50 in particle size distribution measurement using laser light diffraction method.

[0035] Examples of binder resins include thermoplastic resins and cured products of curable resin compositions, with the cured products of curable resin compositions being preferred from the viewpoint of durability. Examples of cured products of 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 thermosetting resin compositions are preferred.

[0036] Examples of thermosetting resin compositions used in the glossy layer include polyester resin compositions, epoxy resin compositions, polyurethane resin compositions, aminoalkyd resin compositions, melamine resin compositions, guanamine resin compositions, urea resin compositions, and thermosetting acrylic resin compositions. These thermosetting resin compositions include monomers and / or prepolymers that constitute each resin, and a curing agent that is added as needed. The ionizing radiation-curable resin composition used in the glossy layer can be the same as the ionizing radiation-curable resin composition of the surface protective layer 7 described below.

[0037] The content of the glittering pigment in the glittering layer is preferably 10 to 90 parts by mass, and more preferably 50 to 80 parts by mass, relative to 100 parts by mass of the binder resin. By setting the content of the glittering pigment to 10 parts by mass or more, it is possible to impart a sufficient glossy appearance, and by setting it to 90 parts by mass or less, it is possible to prevent impairment of the visibility of the design layer described below. From the same viewpoint, the thickness of the glittering layer is preferably 1 μm to 30 μm, and more preferably 5 μm to 20 μm.

[0038] The glittering layer can be formed into any pattern depending on the design desired. Examples include wood grain, leather, stone, sand, tile, brickwork, fabric, geometric shapes, letters, symbols, abstract patterns, floral patterns, landscapes, and characters. It is preferable that the arbitrary pattern have shading to further enhance the design effect. Shading may be formed by varying the size or thickness of the halftone dots, but it is preferable to form it by varying the density of the halftone dots (i.e., the size of the halftone dots is uniform and the shading is formed by the density of the halftone dots).

[0039] The glittering layer can be formed, for example, by applying a coating liquid containing a glittering pigment and a binder resin using a general-purpose printing method such as gravure printing. When the shade of the glittering layer is formed by the density of halftone dots, the halftone dots on the printing plate can be formed using an FM (frequency modulation) screen. [Transparent thermoplastic resin layer]

[0040] The transparent thermoplastic resin layer 6 is a resin layer that provides thickness and depth for design purposes, as well as protecting the design layer 5 and imparting good surface properties to improve the weather resistance and abrasion resistance of the decorative sheet 1. Materials that can be used for the transparent thermoplastic resin layer 6 include, for example, vinyl chloride resin, acrylic resin, and polyolefin-based resin (polypropylene resin, polyethylene resin). In particular, polyolefin-based resins are preferred, taking into consideration environmental compatibility, processability, and cost. Furthermore, the grade and composition of the resin can be selected taking into consideration not only environmental compatibility, processability, and cost, but also ease of sheeting, printability, and suitability for bending. When selecting a material for bending, it is important to consider the prevention of whitening or cracking at the bent portion.

[0041] A lamination method can be used as a method for forming the transparent thermoplastic resin layer 6. Furthermore, 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 co-extruded to form them simultaneously. [Surface protective layer]

[0042] The surface protective layer 7 is a layer that imparts surface properties such as abrasion resistance to the decorative sheet 1. The surface protective layer 7 also adjusts the surface gloss of the decorative sheet 1. The surface protective layer 7 may be a single layer or multiple layers. 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 cured using a known coating device, heat drying device, or ionizing radiation irradiation device depending on the type of curable resin.

[0043] The surface protective layer 7 is mainly composed of a curable resin. That is, 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 total resin is 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 needed.

[0044] Examples of materials that can be used for the surface protection layer 7 include ionizing radiation-curable resins and two-component curable urethane-based resins. The ionizing radiation-curable resins are not particularly limited. For example, transparent resins primarily composed of prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds in the molecule that can undergo polymerization and crosslinking reactions upon exposure to ionizing radiation such as ultraviolet rays or electron beams can be used. These prepolymers or monomers can be used alone or in combination. Specific examples of prepolymers or monomers include compounds containing radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, and cationically polymerizable functional groups such as epoxy groups in the molecule. Polyene / thiol-based prepolymers, which are combinations of polyene and polythiol, are also preferred. Here, the term "(meth)acryloyl group" refers to an acryloyl group or a methacryloyl group.

[0045] 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.

[0046] Furthermore, 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 monomer 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.

[0047] 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 vinyl ethers and aromatic vinyl ethers.

[0048] Examples of polyene-based prepolymers include those obtained by adding allyl alcohol to both ends of polyurethanes made from diols and diisocyanates, and examples of thiol-based prepolymers include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

[0049] The ionizing radiation may be, for example, electromagnetic waves or charged particles having energy sufficient to cause a curing reaction of molecules in an ionizing radiation-curable resin (composition). Examples of the curing reaction include crosslinking and curing reactions. The ultraviolet light source may be, for example, 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. The wavelength of the ultraviolet light is preferably, for example, 190 nm or more and 380 nm or less. The electron beam source may be, for example, an electron beam accelerator such as a Cockcroft-Walton type, a Van de Graaf type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, or a high-frequency type. In particular, those capable of irradiating electrons having an energy of 100 keV or more and 1000 keV or less (more preferably, an electron having an energy of 100 keV or more and 300 keV or less) are preferred.

[0050] The two-component curing urethane resin is not particularly limited. For example, a resin containing a polyol component having OH groups as a base component and an isocyanate component as a curing agent component can be used. Examples of the polyol component having OH groups include acrylic polyol, polyester polyol, polyether polyol, and epoxy polyol. Examples of the isocyanate component include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. [Embossed part]

[0051] An embossed portion 7a having a concave-convex pattern is formed on the surface of the surface protection layer 7 to impart a given design. Examples of the concave-convex pattern include the vessel grooves of a wood grain board, the concave-convex surface of a stone slab (such as a cleavage plane of granite), the texture of a cloth surface, a matte finish, a sand grain, a hairline, and a linear groove. The concave-convex pattern of the embossed portion 7a is provided so that it matches the design of the design layer 5.

[0052] The concave-convex 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. [Primer layer]

[0053] The primer layer 8 is a base layer that improves adhesion and corrosion resistance between the colored thermoplastic resin layer 2 and 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 gloss matte-exhibiting pattern portion 3. The primer layer 8 is formed using, for example, polyester resin, organic additives, pigments, etc. The primer layer 8 may contain an anti-rust pigment to improve corrosion resistance. The thickness of the primer layer 8 is, for example, in the range of 1 μm to 10 μm. [Method for manufacturing decorative sheet]

[0054] Next, an example of a method for producing a decorative sheet according to this embodiment will be described with reference to FIG.

[0055] First, a colored thermoplastic resin layer 2 is formed. For example, it is formed using PBT (polybutylene terephthalate resin) to a thickness of 50 μm (FIG. 2(a)). Next, a pattern portion 3 for expressing gloss and matte is formed. For example, using a urethane-based black ink containing carbon black, the pattern portion 3 for expressing gloss and matte is formed at a predetermined position on the surface of the colored thermoplastic resin layer 2 in harmony with the picture layer 5.

[0056] Next, a concealing solid layer 4 is formed on the colored thermoplastic resin layer 2 containing the matt gloss developing pattern portions 3, filling the gaps between the matt gloss developing pattern portions 3 and covering their upper surfaces (FIG. 2(b)). The concealing solid layer 4 is formed using, for example, a urethane-based printing ink. At this time, the color of the concealing solid layer 4 is selected so that the matt gloss developing pattern portions 3 are less visible when the decorative sheet 1 after production is viewed from the surface protective layer 7 side. The matt gloss developing pattern portions 3 and the concealing solid layer 4 formed so as to fill the gaps between the matt gloss developing pattern portions 3 form a pattern layer.

[0057] Next, a pattern layer 5 is printed on the concealing solid layer 4, and a transparent thermoplastic resin layer 6, for example, made of PP (polypropylene) having a thickness of 38 μm, is laminated on the pattern layer 5 (FIG. 2(c)). Subsequently, a surface protection layer 7 is laminated on the transparent thermoplastic resin layer 6 (FIG. 2(d)).

[0058] Then, infrared rays (irradiation light) are irradiated so that the entire laminate in which these layers are stacked is irradiated (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 protection layer 7 (FIG. 2(f)).

[0059] Here, the matte gloss developing pattern portion 3 is formed of black ink having infrared absorbing properties. Therefore, when infrared rays are irradiated onto the entire laminate including the surface protective layer 7, 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 matte gloss developing pattern portion 3 in a planar view, compared to the portion not overlapping with the matte gloss developing pattern portion 3. In other words, after infrared irradiation, the transparent thermoplastic resin layer 6 and the surface protective layer 7 have portions that are more likely to soften and portions that are less likely to soften. Therefore, when an embossing plate is pressed onto the surface protective layer 7 in this state, unevenness is more likely to form in the softened portion, and unevenness is less likely to form in the less softened portion, so unevenness is more likely to form in the softened portion, i.e., the portion that overlaps with the matte gloss developing pattern portion 3 in a planar view. Therefore, an embossed portion 7a having an uneven shape that is in harmony with the matte gloss developing pattern portion 3 is more likely to be formed only in the portion of the surface protective layer 7 that overlaps with the matte gloss developing pattern portion 3 in a planar view.

[0060] Next, a primer layer 8 is formed on the surface of the colored thermoplastic resin layer 2 opposite to the surface on which the gloss matte developing pattern portion 3 is formed (FIG. 2(g)). This forms the decorative sheet 1 shown in FIG.

[0061] The timing for pressing the embossing plate onto the surface protection layer 7 after infrared irradiation is not limited to immediately after infrared irradiation, but may be any timing that allows pressing the plate onto the surface of the surface protection layer 7 to selectively form an uneven shape in the portion softened by infrared irradiation. In addition, other processes may be included between the process of forming the surface protection layer 7 and the process of performing infrared irradiation, as long as the infrared irradiation is performed while the surface protection layer 7 is formed.

[0062] [Effects of this embodiment] (1) According to the manufacturing method of the decorative sheet 1 of this embodiment, after irradiating the entire laminate including the surface protective layer 7 with infrared rays, an embossing plate is pressed onto the surface protective layer 7, thereby embossing the transparent thermoplastic resin layer 6 and the surface protective layer 7 in the areas that overlap with the gloss matte-exhibiting pattern portion 3 in a plan view. In other words, embossed portions can be easily formed only in desired positions without having to precisely position the area where the embossing plate is pressed onto the surface protective layer 7. As a result, a decorative sheet with excellent design properties can be easily obtained. (2) Furthermore, a concealing solid layer 4 is provided on the upper surface of the matte gloss developing pattern portion 3, and the color of the concealing solid layer 4 is selected so that the visibility of the matte gloss developing pattern portion 3 is reduced when the decorative sheet 1 is viewed from the surface protective layer 7 side. Therefore, although a high-concentration black ink with infrared absorption properties is used for the matte gloss developing pattern portion 3, it is possible to prevent the matte gloss developing pattern portion 3 from being visible when the decorative sheet 1 is viewed from the surface protective layer 7 side. Therefore, even without using a dark color pattern for the design layer 5, it is possible to prevent the matte gloss developing pattern portion 3 containing black ink from being visible, and as a result, it is possible to employ a light-colored pattern for the design layer 5, and it is possible to prevent the restriction on pattern expression caused by the design layer 5 caused by the provision of the matte gloss developing pattern portion 3. Furthermore, a concealing solid layer 4, a picture layer 5, a transparent resin layer 6, and a surface protective layer 7 are laminated in this order on top of a gloss matte-exhibiting pattern portion 3 made of a highly concentrated black ink with infrared absorption properties, and an embossed portion 7a is formed at a position on the surface protective layer 7 that overlaps with the gloss matte-exhibiting pattern portion 3 when viewed in plan. This reduces the visibility of the gloss matte-exhibiting pattern portion 3 made of black ink, and suppresses the impact that the gloss matte-exhibiting pattern portion 3, which is useful in the manufacturing process of the decorative sheet 1, has on the appearance of the decorative sheet 1, resulting in a decorative sheet 1 with a highly attractive design in which the picture of the picture layer 5 and the embossed portion 7a are in harmony.

[0063] (3) Furthermore, since the pattern portion 3 for producing the gloss matte effect 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 produce a gloss matte effect in harmony with the pattern. (4) Furthermore, by providing the surface protection layer 7 with irregularities, a glossy matte finish is achieved, which prevents the glossy matte pattern from coming off. Therefore, for example, a harmonious glossy matte finish can be achieved even in flooring materials.

[0064] [Modification] (1) In the above embodiment, the concealing solid layer 4 is laminated on the colored thermoplastic resin layer 2 so as to fill the gaps between the matt gloss developing pattern portions 3, but this is not limited to this. As shown in Fig. 3, a concealing portion 4' made of the same material as the concealing solid layer 4 may be formed only on the upper surface of the matt gloss developing pattern portion 3, and a pattern layer 5' may be provided so as to fill the gaps between the laminate of the matt gloss developing pattern portion 3 and the concealing portion 4' and to cover the upper surface of the concealing portion 4'. (2) Furthermore, since the concealing solid layer 4 plays a role in reducing the visibility of the pattern portion 3 for revealing gloss matte, the portion laminated on top of the layer formed by the pattern portion 3 for revealing gloss matte must be a color that can reduce the visibility of the pattern portion 3 for revealing gloss matte. However, the portion laminated on top of the pattern portion 3 for revealing gloss matte does not necessarily have to be formed from a material that has lower light absorption properties against infrared rays than the pattern portion 3 for revealing gloss matte.

[0065] (3) In the above embodiment, a material containing black ink is used as the matte gloss pattern portion 3, and infrared radiation is applied to partially soften the transparent thermoplastic resin layer 6 and the surface protective layer 7. However, the present invention is not limited to this. The transparent thermoplastic resin layer 6 and the surface protective layer 7 may be partially softened by using a material containing any ink made of a component that is optically absorbing to light of a predetermined wavelength, and a light source that irradiates light of the predetermined wavelength. [Example]

[0066] A laminate was prepared comprising a colored thermoplastic resin layer 2 made of a 50 μm-thick PBT layer, a gloss matte-exhibiting pattern portion 3 pattern-printed with black ink made of urethane-based printing ink, a concealing solid layer 4 solid-printed with white urethane-based printing ink, a design layer 5, a transparent thermoplastic resin layer 6 made of a 38 μm-thick PP layer, and a surface protective layer 7 primarily composed of an acrylic resin composition. A plurality of laminates with gloss matte-exhibiting pattern portions 3 of different image density levels were prepared by solid printing with black ink using printing plates with varying image density levels. The image density levels were 0%, 20%, 40%, 60%, 70%, 80%, and 90%. The image density level referred to here refers to the dot area ratio (the percentage of the area occupied by dots in the image).

[0067] The transparent thermoplastic resin layer 6 was formed by laminating it onto the pattern layer 5, and after forming the surface protective layer 7, the laminate was heated with an infrared heater, and then an embossing roll was pressed against the surface protective layer 7 to form an embossed portion 7a, and a primer layer 8 was further formed to obtain the decorative sheet 1.

[0068] Comparative examples were prepared in the same manner as in the examples except that no concealing solid layer 4 was provided. For each of the decorative sheets 1 having different image density levels, a decorative sheet without a concealing solid layer 4 was formed, and this was used as a comparative example. 〔evaluation〕

[0069] The color difference, glossiness, and glossiness difference were obtained for each of the decorative sheets 1 with different image density levels and the decorative sheet as a comparative example. The methods described below were used for obtaining the data. The results are shown in Table 1. [Color difference measurement]

[0070] The color difference was measured for each decorative sheet 1 having different image density levels and a decorative sheet as a comparative example. Specifically, the color difference ΔE relative to a standard plate was calculated using a color difference meter CR-400 manufactured by Konica Minolta Japan, Inc. [Gloss measurement]

[0071] After the embossing process, the specular gloss of the surface protective layer 7 was measured at an incident angle of 85° using a micro-TRI-gloss manufactured by BYK. [Difference in gloss]

[0072] The difference in glossiness between the decorative sheet 1 when the image density level was 0% and the decorative sheet 1 when the image density level was other than that, and the difference in glossiness between the decorative sheet as a comparative example when the image density level was 0% and the decorative sheet as a comparative example when the image density level was other than that, obtained by glossiness measurement, were determined. The presence or absence of gloss matte was confirmed based on the difference in glossiness. [Table 1] 〔result〕

[0073] As shown in Table 1, when the image density level is 20% or higher, it was confirmed that by providing a solid concealing layer 4 on top of the black ink of the matte gloss developing pattern portion 3, it is possible to reduce the color difference, i.e., it is possible to conceal the matte gloss developing pattern portion 3. In particular, in the case of a decorative sheet 1 with an image density of 90%, which provides a high matte gloss developing effect for the matte gloss developing pattern portion 3, it was confirmed that the color difference was significantly reduced and the matte gloss developing pattern portion 3 could be concealed.

[0074] At the same image density level, the difference in glossiness between the decorative sheet 1 and the decorative sheet of the comparative example is relatively small, and it was confirmed that the effect on glossiness is relatively small when the concealing solid layer 4 is provided. In particular, it was confirmed that the higher the image density level, the smaller the effect on glossiness when the concealing solid layer 4 is provided, and that when the image density level is 90%, the effect on glossiness when the concealing solid layer 4 is provided is the smallest.

[0075] Furthermore, in order to obtain a gloss matte effect, it is preferable that the difference in gloss between the decorative sheet 1 when the image density level is 0% and the decorative sheet 1 when the image density level is other than this is 5 or more, and it was confirmed that when the decorative sheet 1 has an image density level of 60% or more (image density level of 60% to 90%), the gloss difference is 5 or more, and a gloss difference equal to or greater than that of the decorative sheet of the comparative example not provided with the concealing solid layer 4 is obtained. In other words, it was confirmed that a sufficient gloss matte effect can be obtained. Furthermore, when the image density levels are 20% and 40%, the gloss difference is less than 5, so although the obtained gloss matte effect is somewhat weak, it was confirmed that a gloss difference can be obtained and a gloss matte effect can be obtained.

[0076] From the above, it was confirmed that by providing the concealing solid layer 4 on the gloss matte-exhibiting pattern portion 3, it is possible to prevent the gloss matte-exhibiting pattern portion 3 containing black ink from being visible when the decorative sheet 1 is viewed from the surface protective layer 7 side, and it is possible to achieve a gloss level equivalent to that achieved when the concealing solid layer 4 is not provided, i.e., it is possible to obtain a gloss matte effect equivalent to that achieved when the concealing solid layer 4 is not provided. In particular, it was confirmed that the higher the image density of the concealing solid layer 4, the greater the gloss difference that can be obtained, and the greater the gloss matte effect that can be obtained. [Explanation of symbols]

[0077] 1...Decorative sheet 2...Colored thermoplastic resin layer 3 Gloss Matte Pattern 4. Concealing solid layer 5. Picture layer 6 Transparent thermoplastic resin layer 7 Surface protective layer 7a Embossed part 8 Primer layer

Claims

1. A method for producing a decorative sheet having an embossed shape that matches a pattern, comprising: forming a pattern layer in sync with the image using a predetermined material that is optically absorbing to light of a predetermined wavelength; forming a concealing layer on the pattern layer to reduce the visibility of a portion of the pattern layer formed of the predetermined material; a step of laminating a pattern layer having the pattern, a transparent resin layer, and a surface protective layer in this order on the concealing layer; a step of irradiating the substrate with irradiation light having a power of the predetermined wavelength stronger than the power of the light of other wavelengths after the laminating step; a step of pressing an embossing plate for forming the embossed shape onto the surface protective layer after the step of irradiating with the irradiation light; A method for manufacturing a decorative sheet, comprising:

2. 2. The method for manufacturing a decorative sheet according to claim 1, wherein the predetermined material is formed by containing black ink containing carbon black, and the irradiated light is infrared light.

3. 3. The method for producing a decorative sheet according to claim 1, wherein the concealing layer is formed on the entire surface of the pattern layer.

4. A decorative sheet having a pattern layer, a pattern layer in which a predetermined material having light absorption properties for light of a predetermined wavelength is arranged in synchronization with the pattern of the pattern layer; a concealing layer disposed on the pattern layer to reduce the visibility of a portion of the pattern layer formed of the predetermined material; the pattern layer, the transparent resin layer, and the surface protective layer laminated in this order on the concealing layer; Equipped with A decorative sheet characterized in that an embossed portion is formed in the surface protective layer at a position that overlaps the portion formed of the predetermined material in a plan view.

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