Decorative sheet, resin-impregnated decorative sheet, and method for manufacturing resin-impregnated decorative sheet

Abstract

Provided is a decorative sheet for producing a resin-impregnated decorative sheet, the decorative sheet having, in order in the thickness direction, a porous base material, a design layer, and a mold release layer having a pattern shape, the 60 DEG gloss value of the mold release layer being 10 or less, and the pure water contact angle of the mold release layer being 85 DEG or more. The release layer has a Spc (arithmetic mean curvature of peak points) of 80 mm-1 or more.

Description

Technical Field

[0001] The invention relates to a decorative sheet for manufacturing a resin-impregnated decorative board, a resin-impregnated decorative board and a method for manufacturing the resin-impregnated decorative board. Background Art

[0002] Conventionally, resin-impregnated decorative boards are known, which are obtained by impregnating a porous substrate with a precursor such as a melamine resin and then curing the resin precursor. Resin-impregnated decorative boards are used for walls, furniture, floors, etc. in homes, shops, and public facilities.

[0003] Melamine decorative panels that exhibit a glossy or matte design are known. For example, Patent Document 1 discloses a decorative panel comprising a release layer synchronized with a pattern on a portion of a porous substrate surface, and a thermosetting resin layer containing a melamine resin on the remaining surface area not having the release layer. The thermosetting resin is impregnated into the porous substrate and then cured.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 6716877 Summary of the Invention

[0007] Problems that the invention aims to solve

[0008] The release layer of a decorative sheet used in the manufacture of resin-impregnated decorative panels is required to simultaneously perform two functions: 1) selectively release the cured resin layer cured by a heat and pressure process, and 2) exhibit a good gloss-matt design based on the gloss difference with the cured resin layer. However, there is still room for research in designing decorative sheets that stably balance these two functions.

[0009] The present invention is made in view of the above-mentioned actual situation, and its main purpose is to provide a decorative sheet used for manufacturing resin-impregnated decorative panels, which can selectively peel off the cured resin layer cured by a heating and pressing process, and can show a gloss matte design based on the gloss difference between the release layer and the cured resin layer.

[0010] Technical means to solve the problem

[0011] The present invention provides a decorative sheet for manufacturing a resin-impregnated decorative board, wherein the decorative sheet comprises a porous substrate, a design layer, and a release layer having a patterned shape in this order in the thickness direction, wherein the release layer has a 60° gloss value of 10 or less, a pure water contact angle of 85° or more, and an Spc (arithmetic mean curvature of the peak apex) of 80 mm. -1above.

[0012] The present invention provides a resin-impregnated decorative sheet comprising: a decorative sheet having, in this order in the thickness direction, a porous substrate, a design layer, and a patterned release layer; a core substrate disposed so as to face the porous substrate in the decorative sheet; and a cured resin layer disposed between the patterns of the release layer, thicker than the release layer, and containing a cured product of a curable resin Y; the core substrate and the porous substrate containing the cured product of the curable resin Y; the pure water contact angle of the release layer being 85° or greater; and the Spc (arithmetic mean curvature of the peak apex) of the release layer being 10 mm. -1 above.

[0013] In addition, the present invention provides a method for manufacturing a resin-impregnated decorative board, comprising: a preparation step of preparing the decorative sheet; a laminate forming step of forming a laminate comprising: (i) a core substrate, the decorative sheet, a curable resin layer containing a curable resin Y, and a release film in this order in the thickness direction; (ii) the decorative sheet is arranged such that a surface facing the porous substrate faces the core substrate; and (iii) the decorative sheet is impregnated with the curable resin Y; a heating and pressurizing step of heating and pressurizing the laminate to cure the curable resin Y and forming a cured resin layer from the curable resin layer, thereby obtaining a cured laminate; and a peeling step of peeling the release film from the cured laminate to remove the cured resin layer arranged at a position overlapping the release layer in the thickness direction, while leaving the cured resin layer arranged between patterns on the release layer.

[0014] Effects of the Invention

[0015] The present invention provides a decorative sheet capable of selectively releasing the cured resin layer cured by the heating and pressing process and expressing a glossy matte design based on the gloss difference between the release layer and the cured resin layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic cross-sectional view illustrating a decorative sheet in the present invention.

[0017] Figure 2 This is a schematic cross-sectional view illustrating a decorative sheet in the present invention.

[0018] Figure 3 This is a schematic cross-sectional view illustrating a resin-impregnated decorative board according to the present invention.

[0019] Figure 4This is a schematic cross-sectional view illustrating a method for producing a resin-impregnated decorative board using the decorative sheet of the present invention.

[0020] Figure 5 This is a schematic cross-sectional view illustrating a method for producing a resin-impregnated decorative board using the decorative sheet of the present invention.

[0021] Figure 6 This is a diagram for explaining a method for preparing a backing plate used when measuring the 60° gloss value of a release layer in Examples. DETAILED DESCRIPTION

[0022] The following describes embodiments with reference to the accompanying drawings and other figures. However, the present invention can be implemented in many different ways and is not limited to the following exemplary embodiments. Furthermore, for clarity, the drawings may schematically illustrate the widths, thicknesses, and shapes of various components, as compared to actual configurations. However, these are merely examples and should not be construed as limiting.

[0023] In this specification, when expressing the manner in which another member is arranged with respect to a certain member, when simply expressing "above" or "below", unless otherwise specified, this includes both the case in which the other member is arranged directly above or directly below in a manner in contact with the certain member, and the case in which the other member is further arranged above or below the certain member via another member. In addition, in this specification, when expressing the manner in which another member is arranged on the surface of a certain member, when simply expressing "on the surface", unless otherwise specified, this includes both the case in which the other member is arranged directly above or directly below in a manner in contact with the certain member, and the case in which the other member is further arranged above or below the certain member via another member.

[0024] A.Decorative piece

[0025] Hereinafter, the decorative sheet in the present invention will be described in detail. Figure 1 This is a schematic cross-sectional view illustrating a decorative sheet in the present invention. Figure 1 The decorative sheet 10 shown is used to manufacture a resin-impregnated decorative board and has a thickness direction D. T The present invention comprises a porous substrate 1, a design layer 2, and a release layer 3 having a patterned shape. In the present invention, the 60° gloss value of the release layer 3 is 10 or less, the pure water contact angle of the release layer 3 is 85° or more, and the Spc (arithmetic mean curvature of the peak apex) of the release layer 3 is 80 mm. -1 above.

[0026] The release layer, for example, contains a matting agent and a release agent. To improve the release layer's releasability from the cured resin layer, the industry is considering methods such as increasing the release agent content, decreasing the matting agent content, reducing the matting agent particle size, and increasing the release layer thickness. However, these methods can reduce the matting effect and degrade the glossy matte design. On the other hand, methods such as reducing the release agent content, increasing the matting agent content, increasing the matting agent particle size, and reducing the release layer thickness can improve the glossy matte design but reduce the releasability. Because the release layer's releasability from the cured resin layer and the glossy matte design are in a trade-off relationship, it's difficult to fully control these two functions simply through composition or structure. Furthermore, the manufacturing process of resin-impregnated decorative sheets involves a pressurization step, so even if the release layer exhibits a sufficient matte effect in the finished decorative sheet state, this may be lost after the pressurization step. Therefore, there is still room for research in designing decorative sheets that consistently balance these two functions.

[0027] The inventors of this case discovered that by controlling the 60° gloss value, pure water contact angle, and Spc (arithmetic mean curvature of the peak apex) of the release layer within a specific range, both the release layer's releasability from the cured resin layer and the cured resin layer's gloss matte design properties can be achieved simultaneously.

[0028] 1. Release layer

[0029] The release layer in the present invention is disposed on the surface of the design layer opposite the porous substrate and has a patterned shape. In the region of the porous substrate where the design layer is present, at least a portion of the release layer is disposed on the surface of the design layer opposite the porous substrate. In the region of the porous substrate where the design layer is not present, the porous substrate and the release layer may be in contact.

[0030] I.Characteristics

[0031] The 60° gloss value of the release layer in the present invention is 10 or less, the pure water contact angle of the release layer is 85° or more, and the Spc (arithmetic mean curvature of the peak apex) of the release layer is 80 mm. -1 As long as the release layer has the 60° gloss value, pure water contact angle, and Spc adjusted to the above-specified ranges, the cured resin layer can be selectively peeled off, and a gloss matte design based on the gloss difference with the cured resin layer can be achieved.

[0032] (1) 60° gloss value

[0033] The release layer in the present invention typically has a 60° gloss value of 10 or less, preferably 6.5 or less, more preferably 5.5 or less, and even more preferably 4.0 or less. When the 60° gloss value is within this range, the release layer imparts a matte-like design, allowing for a glossy, matte-like design. On the other hand, the 60° gloss value is, for example, 0.5 or greater, preferably 1.0 or greater, more preferably 1.2 or greater, and even more preferably 2.0 or greater.

[0034] In the present invention, the 60° gloss value of the release layer is the 60° specular glossiness measured in accordance with Method 3 of JIS Z 8741:1997, and is a value measured by the following method.

[0035] Position the decorative sheet with the release layer facing upward, and measure the 60° specular gloss from the release layer side using a gloss meter according to JIS Z8741:1997, Method 3. The 60° gloss value of the release layer is the average of the values measured at 10 random locations. At each measurement location, the release layer is positioned at the center of the gloss meter's measurement area, and the measurement is performed to confirm that the ratio of the release layer area to the measurement area is at least 30%, preferably at least 50%. This specific method can be employed as described in the Examples.

[0036] The 60° gloss value of the release layer can be adjusted by adjusting the average particle size of the matting agent, the matting agent content, and the thickness of the release layer. For example, reducing the thickness of the release layer can reduce the 60° gloss value. For example, increasing the matting agent content can reduce the 60° gloss value. For example, increasing the average particle size of the matting agent can reduce the 60° gloss value.

[0037] (2) Pure water contact angle

[0038] The pure water contact angle of the release layer in the present invention is typically 85° or greater, preferably 90° or greater, more preferably 100° or greater, and even more preferably 110° or greater. When the pure water contact angle of the release layer is within this range, the releasability of the cured resin layer is improved. Furthermore, contamination resistance is enhanced. On the other hand, the pure water contact angle of the release layer is, for example, 130° or less, preferably 125° or less.

[0039] In the present invention, the pure water contact angle of the release layer is a value obtained by measuring by the following method. That is, the decorative sheet is placed on a horizontal surface in such a way that the release layer becomes the upper surface. Next, water drops (pure water, 2.0 μL) are added to the release layer from a vertical direction relative to the horizontal surface. At this time, the water drops are not added to the boundary line between the design layer and the release layer, but are added in such a way that all the water drops are in contact with the release layer. After adding the water drops, wait for 1 second and use a contact angle meter to measure the contact angle between the release layer and pure water. The above measurement is performed at any 10 locations, and the average value is set as the pure water contact angle.

[0040] The pure water contact angle can be adjusted by the content of the release agent and the thickness of the release layer. For example, by increasing the content of the release agent, the pure water contact angle can be increased. For example, by increasing the thickness of the release layer, the pure water contact angle can be increased.

[0041] (3) Spc (arithmetic mean curvature of the peak apex)

[0042] The Spc (arithmetic mean curvature of the peak apex) of the release layer in the present invention is usually 80 mm. -1 Above, preferably 100mm -1 More than 120 mm, more preferably -1 More than, more preferably 150mm -1 By keeping the Spc of the release layer within the above range, the matte feeling of the surface will not be lost after the heating and pressing process, and the design sense of glossy matte style can be expressed. On the other hand, Spc (arithmetic mean curvature of the peak apex) is preferably 300mm -1 Below, more preferably 200mm -1 the following.

[0043] Spc (arithmetic mean curvature of the peak apex) is one of the three-dimensional surface quality parameters specified in ISO 25178. It is the average curvature (average steepness) of the top of the peak apex obtained by taking the arithmetic mean of the curvature radii of the peak apex (peak apex) of the portion classified as a peak (convex portion) in the shape image contained in the reference area. Therefore, Spc (arithmetic mean curvature of the peak apex) is the reciprocal (mm) of the radius (mm). -1 ).

[0044] As the Spc (arithmetic mean curvature of the peak apex) value increases, the curvature of the peak apex (convex portion) becomes greater (the reciprocal radius of curvature becomes smaller, and the shape of the top portion becomes steeper). On the other hand, as the Spc (arithmetic mean curvature of the peak apex) value decreases, the curvature of the peak apex (protrusion apex) becomes smaller (the reciprocal radius of curvature becomes larger, and the shape of the top portion becomes flatter).

[0045] In the present invention, Spc (arithmetic mean curvature of the peak apex) of the release layer is the average value of the following measured values, which are obtained by measuring the surface of the release layer of the decorative sheet using a laser microscope manufactured by KEYENCE Corporation, with the measurement parts selected so that the measurement parts all fall into the release layer, and measuring at any 10 parts under the following conditions.

[0046] (Measurement conditions)

[0047] Objective lens: 5x

[0048] Laser wavelength: 661nm

[0049] Measurement area of each point: 500μm×500μm

[0050] Spc can be adjusted, for example, by adjusting the average particle size of the matting agent. Specifically, by increasing the average particle size of the matting agent, Spc can be increased. In addition, by increasing the content of the matting agent, Spc can be increased.

[0051] II. Composition

[0052] (1) Resin component

[0053] The release layer contains a resin component. The resin component is typically a cured product (cross-linked structure) of a curable resin X. On the other hand, the resin component may also be a thermoplastic resin. Among them, the release layer preferably contains a cured product of a curable resin X. The reason is that a release layer with good wear resistance can be obtained. In addition, by containing a cured product of a curable resin X in the release layer, the releasability of the cured resin layer becomes better.

[0054] Examples of the curable resin X include ionizing radiation curable resins and thermosetting resins. Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet curable resins.

[0055] The ionizing radiation curable resin (ionizing radiation curable compound) is not limited as long as it is a material that undergoes a cross-linking polymerization reaction by irradiation with ionizing radiation and changes in the three-dimensional polymer structure. Examples of ionizing radiation curable resins include prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule that can be cross-linked by irradiation with ionizing radiation. In the present invention, only one ionizing radiation curable resin may be used, or two or more may be used. Among them, it is preferred to use at least one of a multifunctional monomer and an oligomer as the ionizing radiation curable resin.

[0056] Examples of ionizing radiation-curable resins include (meth)acrylate resins such as urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate; silicone resins such as siloxane; ester resins; and epoxy resins. (Meth)acrylate resins refer to acrylate resins or methacrylate resins.

[0057] The weight average molecular weight of the ionizing radiation curable resin is, for example, 500 to 80,000, or 1,000 to 50,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0058] The ionizing radiation curable resin preferably contains at least a polyfunctional monomer or oligomer having a weight average molecular weight of 500 or more. Examples of such polyfunctional monomers or oligomers include (meth)acrylate resins such as dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate.

[0059] On the other hand, examples of thermosetting resins include unsaturated ester resins, urethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine urea co-condensation resins, silicone resins, and siloxane resins.

[0060] (2) Matting agent

[0061] The release layer preferably contains a matting agent. Examples of matting agents include inorganic particles and synthetic resin particles. Examples of inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin waxes (e.g., polypropylene wax and polyethylene wax).

[0062] The average particle size of the matting agent is, for example, 0.3 μm to 10 μm, 0.5 μm to 7 μm, or 1 μm to 5 μm. The average particle size is D50 based on volume-based particle size distribution measured by laser diffraction scattering.

[0063] The content of the matting agent is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the release layer. "100 parts by mass of the release layer" means that the total solids content of the release layer is 100 parts by mass. On the other hand, the content of the matting agent is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less, relative to 100 parts by mass of the release layer.

[0064] (3) Release agent

[0065] The release layer may contain a release agent. The addition of a release agent improves releasability. Examples of release agents include silicone-based release agents such as silicone oil, wax-based release agents such as polyolefin wax, and fluorine-based release agents. Silicone oil is preferred because it exhibits excellent heat resistance during the heating and pressurizing process. Silicone oil may be either reactive or non-reactive, but reactive silicone oil is preferred because it exhibits excellent heat resistance.

[0066] Reactive silicone oils are modified silicone oils that have organic groups introduced into the side chains or ends, and have reactivity depending on the properties of the introduced organic groups. Specifically, reactive silicone oils include side chain modified silicone oils, dual-end modified silicone oils, single-end modified silicone oils, and dual-end modified silicone oils, in which the introduced organic groups are amino-modified, epoxy-modified, mercapto-modified, carboxyl-modified, methanol-modified, phenol-modified, methacrylic acid-modified, or heterofunctional group-modified. These reactive silicone oils can be used alone or in combination of two or more.

[0067] The non-reactive silicone oil is not particularly limited as long as it does not have reactive functional groups such as amino, epoxy, mercapto, carboxyl, hydroxyl, (meth)acryloyl, or allyl groups. Examples of the non-reactive silicone oil include, in addition to silicone oils containing silanone, polyether-modified silicone oils, aralkyl-modified silicone oils, fluoroalkyl-modified silicone oils, long-chain alkyl-modified silicone oils, higher fatty acid ester-modified silicone oils, higher fatty amide-modified silicone oils, and phenyl-modified silicone oils. These non-reactive silicone oils can be used alone or in combination of two or more.

[0068] The content of the release agent relative to 100 parts by mass of the release layer is, for example, 1 part by mass to 10 parts by mass, preferably 2 parts by mass to 9 parts by mass, and more preferably 3 parts by mass to 8 parts by mass.

[0069] In addition, the release layer may be colorless or colored. In the latter case, the release layer preferably contains a colorant. The colorant can be the same as the colorant used in the design layer described below.

[0070] The release layer may contain additives such as ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, coupling agents, plasticizers, defoaming agents, fillers, thermal free radical generators, and aluminum chelating agents as needed. The addition of ultraviolet absorbers or light stabilizers can improve the weather resistance of the release layer.

[0071] III.Thickness and proportion

[0072] The thickness of the release layer is not particularly limited, and is, for example, 0.1 μm to 20 μm, preferably 0.3 μm to 10 μm, and more preferably 0.5 μm to 8 μm. Figure 3The thickness T3 of the release layer 3 shown is generally the thickness of the portion of the design layer 2 that protrudes from the surface of the design layer 2 opposite the substrate 1 and does not penetrate the design layer 2. Furthermore, when the decorative sheet is viewed from the pattern thickness direction, with the area of the release layer being S1 and the area of the porous substrate being S2, the ratio of S1 to S2 (S1 / S2) is, for example, 5% or greater, or may be 10% or greater. On the other hand, S1 / S2 may be, for example, 80% or less, 70% or less, or 60% or less.

[0073] IV. Formation Method

[0074] The release layer can be obtained, for example, by applying a release layer-forming ink containing a curable resin X to the surface of the design layer opposite the porous substrate and curing it. Because a portion of the release layer-forming ink penetrates the porous substrate, the porosity of the porous substrate affects the pure water contact angle, 60° gloss value, and Spc, as shown in the following examples. Furthermore, as shown in the following examples, the composition of the release layer-forming ink (e.g., the proportion of weathering agents such as light stabilizers and UV absorbers) primarily affects the 60° gloss value and Spc. In the present invention, these effects are taken into account and the pure water contact angle, 60° gloss value, and Spc are adjusted to specific ranges, thereby achieving good releasability and good gloss matte design properties.

[0075] When the release layer-forming ink contains an electron beam-curable resin as the curable resin X, a cured product of the electron beam-curable resin is typically obtained by electron beam irradiation. Examples of electron beam sources include various electron beam accelerators, such as the Cockcroft-Walton type, the Van de Graft type, the resonant transformer type, the insulating core transformer type, the linear type, the high-frequency high-voltage accelerator type, and the high-frequency type. The energy of the electron beam is, for example, from 100 kV to 1000 kV, and may also be from 100 kV to 300 kV. The electron beam irradiation dose is, for example, from 2 Mrad to 15 Mrad.

[0076] When the release layer-forming ink contains a UV-curable resin as the curable resin X, a cured product of the UV-curable resin is typically obtained by irradiating the ink with ultraviolet light. Examples of UV light sources include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, blacklight fluorescent lamps, and metal halide lamps. The wavelength of the UV light is, for example, from 190 nm to 380 nm.

[0077] When the release layer-forming ink contains a thermosetting resin X as the curable resin, a cured product of the thermosetting resin is typically obtained by heating. The heating temperature is appropriately set depending on the type of thermosetting resin. The release layer-forming ink may contain a thermosetting resin, a curing agent such as a crosslinking agent or polymerization initiator, and a polymerization accelerator. Examples of curing agents include isocyanates, organic sulfonates, organic amines, peroxides (e.g., methyl ethyl ketone peroxide), and free radical initiators (e.g., azoisobutylonitrile).

[0078] The release layer-forming ink may contain a solvent as needed. Examples of the solvent include water; hydrocarbon compounds such as toluene and xylene; alcohol compounds such as methanol, ethanol, and methyl glycol; ketone compounds such as acetone and methyl ethyl ketone; ester compounds such as methyl formate and ethyl acetate; nitrogen-containing compounds such as N-methylpyrrolidone and N,N-dimethylformamide; ether compounds such as tetrahydrofuran and dioxane; halogenated hydrocarbon compounds such as dichloromethane and chloroform; and dimethyl sulfoxide.

[0079] V. Others

[0080] The release layer has a release property for the cured resin layer located between the release layer and the release film in the manufacturing process of the resin impregnated decorative board described below. Figure 3 In the resin-impregnated decorative board 100 shown, the release layer 3 imparts a matte design, and the cured resin layer 32 imparts a glossy design, thereby expressing a glossy matte design.

[0081] In addition, if Figure 2 As shown, the release layer 3 is preferably configured to be synchronized with the pattern of the design layer 2. "Synchronized" means that the shapes and positions of the two patterns are roughly consistent. Specifically, it means that the pattern of the release layer and the shape and position of at least a part of the pattern constituting the design layer are consistent to the extent that the realism and high-end feeling are not damaged. Figure 2 In this example, the design layer 2 includes pattern layer y1 and pattern layer y2, and the release layer 3 is synchronized with pattern layer y1. By arranging the pattern of the release layer in synchronization with the pattern of the design layer, a high-quality texture can be achieved. Alternatively, the release layer may not be arranged in synchronization with the pattern of the design layer.

[0082] 2. Design layer

[0083] The design layer in the present invention is disposed on one side of the porous substrate. The design layer preferably has a pattern.

[0084] Examples of patterns for the design layer include organic patterns, inorganic patterns, and abstract patterns. Organic patterns refer to patterns that originate from the life activities of organisms such as plants and animals. Inorganic patterns refer to patterns that do not correspond to organic patterns. Abstract patterns refer to patterns that abstractly interpret an object (such as an image existing in nature) and do not show a clear form. Examples of organic patterns include wood grain patterns, leather patterns, flower patterns, and plant patterns. Examples of inorganic patterns include stone patterns, concrete patterns, sand patterns, cloth patterns, metal patterns, tile patterns, and brickwork patterns. Examples of abstract patterns include wave patterns (such as wave patterns of ink), firework patterns, and marble patterns.

[0085] The design layer may include, for example, a pattern layer. Alternatively, the design layer may include a solid layer located closer to the porous substrate than the pattern layer. In the present invention, a pattern layer refers to a layer partially (particularly in a patterned form) formed on one side of a porous substrate. Furthermore, a solid layer refers to a layer formed entirely on one side of a porous substrate.

[0086] The design layer contains, for example, a colorant and a resin component. Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, red lead, iron blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metallic powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxychloride; fluorescent pigments; and luminescent pigments. Dyes can also be used as colorants.

[0087] Examples of the resin component include (meth)acrylic resins, ester urethane resins, acrylamide resins, ethylene oxide resins, N-vinyl pyrrolidone resins, ester resins, amide resins, vinyl acetate resins, vinyl chloride resins, urethane (meth)acrylic resins, natural rubber, and synthetic rubber. Among them, (meth)acrylic resins and urethane (meth)acrylic resins are preferred.

[0088] The resin component preferably contains a resin having one or more polar groups selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. The inclusion of such a resin having a polar group improves the permeability of the curable resin Y into the porous substrate.

[0089] The resin having polar groups contains at least one of hydroxyl group (-OH), amino group (-NH2), and carboxyl group (-COOH) as polar groups. The above polar groups may be ionized and stabilized due to the influence of solvents and other functional groups. Therefore, the above "hydroxyl group (-OH)" includes "-O -"The concept of "amino group (-NH2)" mentioned above includes "-NH3 + "The concept of "carboxyl (-COOH)" includes the ionized state of "-CO - ” concept.

[0090] Examples of resins having polar groups of one or more of hydroxyl (-OH), amino (-NH2), and carboxyl (-COOH) groups include: aqueous proteins such as casein; cellulose derivatives represented by cellulose, acetyl cellulose, nitrocellulose, hydroxypropyl cellulose, carboxymethyl cellulose, etc.; polyvinyl alcohol derivatives such as polyvinyl alcohol and polyvinyl butyral resin; amino resins such as melamine resin; (meth) acrylic resins; phenolic resins; polyacrylic polyols; natural polymers (such as polynucleotides, polypeptides, polysaccharides), etc.

[0091] The design layer in the present invention preferably comprises, as a resin having a polar group, one or more of casein, melamine-based resins, polyvinyl alcohol, polyvinyl alcohol derivatives, cellulose, and cellulose derivatives, and more preferably comprises casein. Casein can be α-casein, β-casein, γ-casein, or a mixture thereof. Casein can also be used alone or in combination with derivatives such as sodium caseinate and ammonium caseinate.

[0092] The proportion of the polar group-containing resin relative to the resin component contained in the design layer may be, for example, 20% by mass or greater, 30% by mass or greater, 40% by mass or greater, or 50% by mass or greater. On the other hand, the proportion of the polar group-containing resin may be, for example, 100% by mass or less, or 90% by mass or less. When the content of the polar group-containing resin is within the above range, the penetration of the ink of the release layer into the porous substrate can be suppressed without hindering the penetration of the curable resin Y into the porous substrate.

[0093] The design layer may contain additives such as fillers (eg, silica), extender pigments (eg, organic beads), neutralizers, surfactants, etc. as needed. The thickness of the design layer is not particularly limited, and is, for example, 0.1 μm to 20 μm.

[0094] As a method for forming the design layer, for example, a coating method using a design layer-forming ink containing a colorant, a binder resin, and a solvent (or dispersion medium) can be used. For example, the design layer can be formed by coating the design layer-forming ink on one side of a porous substrate and drying it.

[0095] Examples of the above-mentioned solvent (or dispersion medium) 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 methanol, ethanol, n-propanol, isopropanol, isobutanol, 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.

[0096] Examples of the coating method include printing. Examples of printing methods include gravure printing, lithographic printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Furthermore, examples of coating methods for forming a solid layer include various coating methods such as roll coating, doctor blade coating, air knife coating, die-mouth coating, die-lip coating, notch wheel coating, contact coating, flow coating, and dip coating.

[0097] 3.Porous substrate

[0098] The porous substrate in the present invention is a substrate impregnated with curable resin Y when manufacturing resin-impregnated decorative panels. Examples of porous substrates include permeable fibrous substrates. Examples of permeable fibrous substrates include paper, synthetic paper, non-woven fabrics, and woven fabrics. Examples of the above-mentioned paper include titanium paper, thin paper, kraft paper, cotton linter paper, cardboard, gypsum board paper, high-grade paper, coated paper, parchment, and Japanese paper. In addition, as a fibrous substrate, a vinyl wallpaper original (paper on which polyvinyl chloride resin is dry-laminated) can also be used. As other examples of fibrous substrates, non-woven fabrics or woven fabrics containing inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber can be mentioned. In addition, as other examples of fibrous substrates, non-woven fabrics or woven fabrics containing synthetic resin fibers such as polyester, vinylon, polyethylene, and polypropylene can be mentioned. Among these porous substrates, titanium paper, thin paper, kraft paper, coated paper, art paper, stencil paper, glassine paper, parchment paper, paraffin paper, and Japanese paper are preferred from the perspective of the impregnation properties of the curable resin Y. Titanium paper is particularly preferred as the porous substrate due to its excellent impregnation properties with the curable resin Y and its excellent shielding properties.

[0099] The porous substrate may be colored. For example, a colored porous substrate can be obtained by adding a colorant during the production stage of the porous substrate. For example, if the porous substrate is paper, colored paper can be obtained by adding a colorant during the papermaking stage. Examples of colorants include inorganic pigments such as titanium dioxide, carbon black, and iron oxide; organic pigments such as phthalocyanine blue; and various dyes. The amount of colorant added is appropriately adjusted depending on the desired color tone. Furthermore, the porous substrate may contain various additives, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers, as needed.

[0100] The weight per unit area of the porous substrate is not particularly limited, but is, for example, 40 g / m 2 Above and 150g / m 2 The thickness of the porous substrate is not particularly limited, and is, for example, 50 μm to 170 μm. For example, to improve the adhesion of the ink forming the design layer, the surface of the porous substrate on the design layer side may be subjected to corona discharge treatment.

[0101] 4. Decorative sheet

[0102] The decorative sheet of the present invention is used to produce a resin-impregnated decorative board. A method for producing a resin-impregnated decorative board using the decorative sheet of the present invention will be described below.

[0103] B. Resin impregnated decorative panels

[0104] Hereinafter, the resin-impregnated decorative board of the present invention will be described in detail. Figure 3 This is a schematic cross-sectional view illustrating a resin-impregnated decorative board according to the present invention. Figure 3 The resin-impregnated decorative panel 100 shown comprises: a decorative sheet 10 having, in this order in the thickness direction, a porous substrate 1, a design layer 2, and a release layer 3 having a patterned shape; a core substrate 20 arranged so as to face the porous substrate 1 in the decorative sheet 10; and a cured resin layer 32 arranged between the patterns of the release layer 3, being thicker than the release layer 3, and containing a cured product of a curable resin Y; the porous substrate containing the cured product of the curable resin Y, the pure water contact angle of the release layer 3 being within a specified range, and the Spc (arithmetic mean curvature of the peak apex) of the release layer 3 being within a specified range.

[0105] According to the resin-impregnated decorative board of the present invention, since the pure water contact angle of the release layer is greater than or equal to a predetermined value and the Spc (arithmetic mean curvature of the peak apex) of the release layer is greater than or equal to a predetermined value, the cured resin layer arranged at a position overlapping with the release layer can be easily peeled off and the gloss and matte design between the release layer and the cured resin layer can be easily obtained.

[0106] 1. Decorative sheet

[0107] The decorative sheet of the present invention includes a porous base material, a design layer, and a release layer having a pattern shape in this order in the thickness direction.

[0108] (1) Release layer

[0109] In the resin-impregnated decorative sheet of the present invention, the pure water contact angle of the release layer is typically 85° or greater, preferably 90° or greater, more preferably 100° or greater, and even more preferably 110° or greater. When the pure water contact angle of the release layer in the resin-impregnated decorative sheet falls within this range, the releasability of the cured resin layer is improved. Furthermore, stain resistance is enhanced. On the other hand, the pure water contact angle of the release layer in the resin-impregnated decorative sheet is, for example, 130° or less, preferably 125° or less.

[0110] The pure water contact angle of the release layer in the resin-impregnated decorative sheet is measured by completely removing the remaining cured resin layer on the release layer to expose the release layer, using the same method as described in detail in "A. Decorative Sheet" above. The method for removing the remaining cured resin layer on the release layer can be, for example, the same method as the tape resistance test described in the Examples.

[0111] The method for adjusting the pure water contact angle of the release layer is the same as that described in detail in the above-mentioned "A. Decorative sheet".

[0112] The Spc (arithmetic mean curvature of the peak apex) of the release layer in the resin-impregnated decorative board is 10 mm -1 Above, preferably 15mm -1 More than 20 mm, more preferably -1 More than, more preferably 40mm -1 Above, particularly preferably 60mm -1 If the Spc of the release layer is within the above range, the release layer can be given a matte design in the state of the resin-impregnated decorative board, and a glossy matte design can be expressed. On the other hand, the Spc (arithmetic mean curvature of the peak apex) of the release layer in the resin-impregnated decorative board is, for example, 140 mm. -1 Below, preferably 120mm -1 Less than, more preferably 100mm -1 the following.

[0113] In the resin-impregnated decorative sheet, the method for measuring and adjusting Spc as the release layer is the same as that described in detail in the above-mentioned "A. Decorative sheet".

[0114] The 60° gloss value of the release layer of the resin-impregnated decorative sheet is preferably 10 or less, more preferably 8 or less, and particularly preferably 7.5 or less. By having a 60° gloss value of the release layer within the above range and imparting a matte-like design through the release layer, a glossy-matte design can be achieved. On the other hand, the 60° gloss value of the release layer of the resin-impregnated decorative sheet is, for example, 2.0 or greater, preferably 3.0 or greater.

[0115] The method for measuring and adjusting the 60° gloss of the release layer in the resin-impregnated decorative sheet is the same as that described in detail in the above-mentioned "A. Decorative sheet".

[0116] (2) Porous substrate and design layer

[0117] The porous base material and the design layer in the present invention are the same as those described in detail in the above-mentioned "A. Decorative sheet." In the resin-impregnated decorative sheet, the porous base material includes a cured product of the curable resin Y.

[0118] 2. Curing resin layer

[0119] The resin-impregnated decorative sheet of the present invention includes a cured resin layer disposed between the patterns on the release layer and thicker than the release layer. The 60° gloss value of the cured resin layer is preferably greater than that of the release layer. This is because it allows for a glossy, matte-like design. The 60° gloss value of the cured resin layer can be, for example, 11 or greater, 15 or greater, or 20 or greater. Alternatively, the 60° gloss value of the cured resin layer can be, for example, 60 or less, 55 or less, or 50 or less.

[0120] In the resin-impregnated decorative board, the difference between the 60° gloss value of the release layer and the 60° gloss value of the cured resin layer is preferably 1.0 or more, more preferably 3.0 or more, because the gloss matte effect can be more clearly achieved.

[0121] In the resin-impregnated decorative board, the ratio of the 60° gloss value G32 of the cured resin layer 32 to the 60° gloss value G3 of the release layer 3 (G32 / G3) is preferably 1.2 or greater, more preferably 1.5 or greater. This is because a gloss matte effect can be more clearly achieved.

[0122] The cured resin layer contains a cured product of the curable resin Y. As the curable resin Y, a thermosetting resin is preferred. As the thermosetting resin, a wide range of thermosetting resins can be used. Examples of thermosetting resins include: melamine resins (melamine resin precursors), melamine urea co-condensate resins, unsaturated polyester resins, polyurethane resins (including two-liquid curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, guanamine resins, silicone resins, and silicone resins. Examples of methods for impregnating the thermosetting resin include: a method of immersing the decorative sheet in a bath containing a thermosetting resin; a method of applying the thermosetting resin to the decorative sheet using a coating machine such as a contact coater or a notched wheel coater; and a method of spraying the thermosetting resin onto the decorative sheet using a spray device or a shower device.

[0123] In the present invention, the thickness T of the cured resin layer 32 is 32 Thicker than the thickness T3 of the release layer 3. The surface design can be easily improved by the unevenness of the surface. The thickness T of the cured resin layer 32 There is no particular limitation, and for example, it is 1 μm or more, or 10 μm or more. On the other hand, the thickness T of the cured resin layer 32 For example, it is 500 μm or less, and may be 300 μm or less. 32 It can also be less than 30μm. By reducing the thickness T 32 , the processability when peeling the release film from the cured resin layer is improved. The thickness T of the cured resin layer 32 The thickness may be 28 μm or less, 25 μm or less, or 20 μm or less.

[0124] In this embodiment, the difference between the top of the release layer and the top of the cured resin layer (the height difference of the surface of the resin-impregnated decorative board) is, for example, preferably 0.5 μm to 45.0 μm, more preferably 2.0 μm to 35.0 μm, and even more preferably 3.0 μm to 30.0 μm. Alternatively, the difference may be 0.5 μm to 25 μm, 2.0 μm to 25 μm, or 3.0 μm to 20 μm.

[0125] 3. Core substrate

[0126] The resin-impregnated decorative board of the present invention includes a porous core substrate 20 on the surface of the decorative sheet 10 on the porous substrate 1 side (the surface of the decorative sheet 10 located on the porous substrate 1 side relative to the design layer 2). The presence of a core substrate further enhances the mechanical strength of the resin-impregnated decorative board. Examples of the core substrate 20 include phenolic resin-impregnated paper. Phenolic resin-impregnated paper is obtained by, for example, impregnating kraft paper, which serves as a core paper, with phenolic resin and drying the resulting paper. The core substrate may include a cured product of a curable resin Y.

[0127] 4. Cured products of curable resins

[0128] The porous substrate in the present invention contains a cured product of a curable resin Y. As described below, the cured product of the curable resin Y filled in the porous substrate and the cured product of the curable resin Y contained in the cured resin layer are formed from the same curable resin Y. These cured products are, for example, cured products of thermosetting resins.

[0129] The total light transmittance of the resin-impregnated decorative board of the present invention as specified in JIS K7361-1:1997 is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less.

[0130] 5. Resin impregnated decorative panels

[0131] The resin-impregnated decorative board in the present invention is used, for example, by being arranged on the surface of a substrate. Examples of the substrate include: wooden components, resin components, metal components, and ceramic components. Examples of wooden components include: wood veneer, wood plywood, plastic plywood, and wood fiberboard. Examples of wood used in wooden components include: fir, cypress, pine, and lauan. Examples of resins used in resin components include: vinyl chloride resins, (meth) acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenol resins, cellulose resins, carbonate resins, melamine resins, and rubber. Examples of metals used in metal components include: iron and aluminum. The material of the ceramic component may be ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (lightweight air-bubbled concrete).

[0132] Examples of applications for the resin-impregnated decorative board of the present invention include building materials and furniture. Building materials may be interior or exterior materials. Examples of building materials include walls, floors, ceilings, doors, and shelves. Examples of furniture include tables, desks, and cabinets.

[0133] C. Method for manufacturing resin-impregnated decorative panels

[0134] Figure 4(a) to (d) and Figure 5 (a) and (b) are schematic cross-sectional views illustrating a method for manufacturing a resin-impregnated decorative plate according to the present invention. The method for manufacturing a resin-impregnated decorative plate according to the present invention comprises the following steps: a preparation step ( Figure 4 (a)), preparing the above-mentioned decorative sheet 10; a laminate forming step ( Figure 4 (b)~ Figure 4 (d)) forming a laminate 52 as follows: (i) having a core substrate 20, a decorative sheet 10, a curable resin layer 30 containing a curable resin Y, and a release film 40 in that order in the thickness direction; (ii) being arranged so that the surface of the decorative sheet 10 on the side of the porous substrate 1 faces the core substrate 20; and (iii) being impregnated with the curable resin Y in the decorative sheet 10; a heating and pressurizing step ( Figure 5 (a)), which heats and pressurizes the laminate 52 to cure the curable resin Y, and forms a cured resin layer 31 from the curable resin layer 30, thereby obtaining a cured laminate 53; and a peeling step ( Figure 5 (b)) peeling the release film 40 from the cured laminate 53, thereby removing the cured resin layer 31 arranged at a position overlapping with the release layer 3 in the thickness direction, and leaving the cured resin layer 31 arranged between the patterns of the release layer 3.

[0135] 1. Preparation process

[0136] This step is to prepare the decorative sheet. The details of the decorative sheet are as described above.

[0137] 2. Laminated body forming process

[0138] like Figure 4 As shown in (d), this process is a process for forming the following stacked body 52, which (i) has a core substrate 20, a decorative sheet 10, a curable resin layer 30 containing a curable resin Y, and a peeling film 40 in the thickness direction, (ii) is arranged in a manner such that the surface on the side of the porous substrate 1 in the decorative sheet 10 is opposite to the core substrate 20, and (iii) the decorative sheet 10 is impregnated with the curable resin Y.

[0139] The method for forming the laminate is not particularly limited. Figure 4 As shown in (b), the decorative sheet 10 is impregnated with a curable resin Y, and a curable resin layer 30 containing the curable resin Y is formed to cover the design layer 2 and the release layer 3, thereby obtaining a precursor laminate 51 ( Figure 4 (c) Next, the release film 40 is placed on the curable resin layer 30 side of the precursor laminate, and the core substrate 20 is placed on the side opposite to the side having the release layer of the precursor laminate 51. In this way, a laminate 52 is obtained.

[0140] The details of the core base material and the curable resin Y are as described above.

[0141] In this step, for example, the decorative sheet is immersed in a curable resin composition containing curable resin Y. Preferably, the sheet is dried after the immersion. In this case, a portion of the curable resin may be cured to form a semi-cured state.

[0142] The curable resin composition is a curable resin composition containing a curable resin Y. The proportion of the curable resin Y in the curable resin composition is preferably 50% by mass or greater, more preferably 70% by mass or greater, and even more preferably 90% by mass or greater. The curable resin composition may contain water, alcohol, an organic solvent, or the like as a solvent.

[0143] Examples of release films include films comprising polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resins such as polyethylene and polypropylene; and acrylic resins. Furthermore, the release film may include a release layer comprising a cured product of an ionizing radiation-curable resin composition on the surface facing the curable resin layer.

[0144] Another method for forming the laminate in this step includes, for example, placing a core substrate facing the porous substrate in the decorative sheet, impregnating the core substrate and the porous substrate with curable resin Y, and forming a curable resin layer containing curable resin Y that covers the design layer and the release layer. Subsequently, a release film 40 is placed on the surface facing the curable resin layer. This method can also produce a laminate.

[0145] 3. Heating and pressurizing process

[0146] This step is a step of heating and pressurizing the laminate 52 to cure the curable resin Y and forming the cured resin layer 31 from the curable resin layer 30 to obtain the cured laminate 53 .

[0147] The heating temperature is, for example, 90° C. to 160° C. The heating time is, for example, 30 seconds to 30 minutes.

[0148] 4. Peeling process

[0149] This step involves peeling the release film from the cured laminate 53, thereby removing the cured resin layer 31 located at a position overlapping the release layer 3 in the thickness direction, while leaving the cured resin layer 31 located between the patterns on the release layer 3. This results in a resin-impregnated decorative sheet 100 comprising: a porous substrate 1; a design layer 2 located on one surface of the porous substrate 1; a patterned release layer 3 located on the surface of the porous substrate 1 opposite the design layer 2; and a cured resin layer 32 located between the patterns on the release layer 3 of the decorative sheet.

[0150] The resin-impregnated decorative board obtained by this method for producing a resin-impregnated decorative board can have the Spc and pure water contact angle of the release layer within the ranges described in "B. Resin-Impermeated Decorative Board" above. Consequently, a resin-impregnated decorative board can be produced in which the cured resin layer disposed at a position overlapping the release layer is well peeled off, and the gloss and matte design between the release layer and the cured resin layer is excellent.

[0151] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any technical solution having substantially the same configuration and exhibiting the same effects as the technical concept described within the scope of the claims of the present invention is included within the technical scope of the present invention.

[0152] Example

[0153] [Example 1]

[0154] (Production of decorative sheets)

[0155] Prepare paper substrate (weight per unit area 80g / m 2 Titanium base paper for building materials (PM-77P manufactured by KJ Special Paper Co., Ltd.) was used as the porous substrate. The ash content of the paper substrate was measured in accordance with JIS-P8252 and was found to be 26%. A design layer (pattern layer) with a thickness of 2 μm was partially laminated on the paper substrate by gravure printing using the following printing ink, so as to form a stone-grained design. Furthermore, the following release layer-forming ink 1 was laminated on the pattern layer in synchronization with the pattern layer, and then an electron beam of 3 Mrad was irradiated at an accelerating voltage of 165 kV to form a release layer with a thickness of 2 μm. A decorative sheet having a porous substrate, a design layer, and a release layer laminated in this order was thus manufactured.

[0156] Printing ink

[0157] • Pigments (azo, quinacridone, carbon black, etc.) 10 parts by mass

[0158] • Casein / acrylic resin 10 parts by mass

[0159] • 70 parts by weight of water

[0160] • 5 parts by mass of dipropylene glycol

[0161] • 5 parts by mass of isopropyl alcohol

[0162] <Release layer forming ink 1>

[0163] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 48 parts by mass

[0164] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0165] • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0166] • 40 parts by weight of methyl ethyl ketone

[0167] (Manufacture of melamine decorative panels)

[0168] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0169] The impregnated decorative sheet was laminated on a core substrate comprising three sheets of kraft paper impregnated with a phenolic resin solution, with a unit area weight of 245 g / m 2 A laminate is obtained by impregnating core paper with a phenolic resin (obtained by impregnating core kraft paper with a liquid uncured resin composition containing a phenolic resin), and then laminating the following release film on the impregnated decorative sheet in such a way that the release layer of the release film is in contact with the printed surface of the impregnated decorative sheet.

[0170] (Production of Release Film)

[0171] On the easily adhesive surface of a 50 μm thick PET (Polyethylene Terephthalate) film (COSMOSHINE (registered trademark) A4160 manufactured by Toyobo Co., Ltd.), a 5 g / m 2 A coating liquid containing 100 parts by mass of an ionizing radiation-curable monomer (ARONIX M-350, manufactured by Toagosei Co., Ltd.), 2 parts by mass of a reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.), 8 parts by mass of silica particles (trade name "Sylysia 450", average particle size: 8.0 μm, manufactured by Fuji Silysia Chemical Co., Ltd.), and 50 parts by mass of ethyl acetate was applied in an amount (when dry), and the mixture was irradiated with an electron beam of 5 Mrad at an accelerating voltage of 165 kV and cured to produce a release film having a release layer.

[0172] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-formed at a molding temperature of 150°C for 10 minutes to thermally cure, thereby forming a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising the cured product of the melamine resin, thereby obtaining the melamine decorative sheet of Example 1. It should be noted that when the release film was peeled off from the cured laminate, it was removed along with the cured resin layer on the release layer of the cured resin layer, leaving the cured resin layer formed in the area without the release layer.

[0173] [Example 2]

[0174] (Production of decorative sheets)

[0175] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 2 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a dose of 3 Mrad to form a 2μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0176] <Release layer forming ink 2>

[0177] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 50.6 parts by mass

[0178] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0179] •Silane coupling treated silica (particle size 2 μm) 5.4 parts by mass (9.0 parts by mass per 100 parts by mass of the total solid content)

[0180] • 40 parts by weight of methyl ethyl ketone

[0181] (Manufacture of melamine decorative panels)

[0182] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0183] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0184] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 2.

[0185] [Example 3]

[0186] (Production of decorative sheets)

[0187] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 3 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a dose of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0188] <Release layer forming ink 3>

[0189] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 45.4 parts by mass

[0190] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0191] •Silane coupling treated silica (particle size 2 μm) 10.6 parts by mass (17.7 parts by mass relative to 100 parts by mass of the total solid content)

[0192] • 40 parts by weight of methyl ethyl ketone

[0193] (Manufacture of melamine decorative panels)

[0194] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0195] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0196] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 3.

[0197] [Example 4]

[0198] (Production of decorative sheets)

[0199] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 4 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0200] <Release layer forming ink 4>

[0201] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 50.6 parts by mass

[0202] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.4 parts by mass (2.3 parts by mass per 100 parts by mass of the total solid content)

[0203] • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0204] • 40 parts by weight of methyl ethyl ketone

[0205] (Manufacture of melamine decorative panels)

[0206] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0207] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0208] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 4.

[0209] [Example 5]

[0210] (Production of decorative sheets)

[0211] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. A 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate using the aforementioned printing ink using a gravure printing method to create a stone-grained design. Furthermore, the release layer-forming ink 5 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a dose of 3 Mrad to form a 2μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0212] <Release layer forming ink 5>

[0213] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 46.6 parts by mass

[0214] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 5.4 parts by mass (9.0 parts by mass per 100 parts by mass of the total solid content)

[0215] • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0216] • 40 parts by weight of methyl ethyl ketone

[0217] (Manufacture of melamine decorative panels)

[0218] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0219] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0220] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 5.

[0221] [Example 6]

[0222] (Production of decorative sheets)

[0223] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. A 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate using the aforementioned printing ink using a gravure printing method to create a stone-grained design. Furthermore, the release layer-forming ink 6 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0224] <Release layer forming ink 6>

[0225] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 50.6 parts by mass

[0226] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0227] •Silane coupling treated silica (particle size 5 μm) 5.4 parts by mass (9.0 parts by mass relative to 100 parts by mass of the total solid content)

[0228] • 40 parts by weight of methyl ethyl ketone

[0229] (Manufacture of melamine decorative panels)

[0230] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0231] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0232] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 6.

[0233] [Example 7]

[0234] (Production of decorative sheets)

[0235] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 7 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0236] <Release layer forming ink 7>

[0237] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 45.4 parts by mass

[0238] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0239] •Silane coupling treated silica (particle size 1 μm) 10.6 parts by mass (17.7 parts by mass relative to 100 parts by mass of the total solid content)

[0240] • 40 parts by weight of methyl ethyl ketone

[0241] (Manufacture of melamine decorative panels)

[0242] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0243] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0244] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 7.

[0245] [Example 8]

[0246] (Production of decorative sheets)

[0247] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate, forming a stone-grained design. Furthermore, the release layer-forming ink 8 described below was laminated onto the pattern layer in synchronization with the previously applied pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 6μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0248] <Release layer forming ink 8>

[0249] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 45.4 parts by mass

[0250] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0251] •Silane coupling treated silica (particle size 2 μm) 10.6 parts by mass (17.7 parts by mass relative to 100 parts by mass of the total solid content)

[0252] • 40 parts by weight of methyl ethyl ketone

[0253] (Manufacture of melamine decorative panels)

[0254] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0255] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0256] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 8.

[0257] [Comparative Example 1]

[0258] (Production of decorative sheets)

[0259] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 9 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0260] <Release layer forming ink 9>

[0261] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 53.4 parts by mass

[0262] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0263] •Silane-coupled silica (particle size 2 μm) 2.6 parts by mass (4.3 parts by mass per 100 parts by mass of the total solid content)

[0264] • 40 parts by weight of methyl ethyl ketone

[0265] (Manufacture of melamine decorative panels)

[0266] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0267] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0268] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured under the conditions of a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 1.

[0269] [Comparative Example 2]

[0270] (Production of decorative sheets)

[0271] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate, forming a stone-grained design. Furthermore, the release layer-forming ink 10 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a dose of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet composed of a paper substrate, a design layer, and a release layer laminated in this order.

[0272] <Release layer forming ink 10>

[0273] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 51.4 parts by mass

[0274] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.6 parts by mass (1.0 parts by mass per 100 parts by mass of the total solid content)

[0275] •Silane coupling treated silica (particle size 2 μm) 8.0 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0276] • 40 parts by weight of methyl ethyl ketone

[0277] (Manufacture of melamine decorative panels)

[0278] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0279] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0280] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2The uncured melamine resin composition was heat-cured under the conditions of a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 2.

[0281] [Comparative Example 3]

[0282] (Production of decorative sheets)

[0283] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate, forming a stone-grained design. Furthermore, the release layer-forming ink 11 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165kV and a dose of 3 Mrad to form a 2μm thick release layer. This produced a decorative sheet composed of a paper substrate, a design layer, and a release layer laminated in this order.

[0284] <Release layer forming ink 11>

[0285] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 48 parts by mass

[0286] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0287] • Silane-coupled silica (particle size 5 μm) 8 parts by mass (13.3 parts by mass per 100 parts by mass of the total solid content)

[0288] • 40 parts by weight of methyl ethyl ketone

[0289] (Manufacture of melamine decorative panels)

[0290] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet.

[0291] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0292] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 3.

[0293] [Comparative Example 4]

[0294] (Production of decorative sheets)

[0295] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 12 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0296] <Release layer forming ink 12>

[0297] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 48 parts by mass

[0298] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0299] • Silane-coupled silica (particle size 1 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0300] • 40 parts by weight of methyl ethyl ketone

[0301] (Manufacture of melamine decorative panels)

[0302] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet.

[0303] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0304] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured under the conditions of a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 4.

[0305] [Comparative Example 5]

[0306] (Production of decorative sheets)

[0307] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate, forming a stone-grained design. Ink 1 for forming a release layer was then laminated onto the pattern layer in sync with the previously applied pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a strength of 3 Mrad to form a 6μm thick release layer. This produced a decorative sheet composed of a paper substrate, a design layer, and a release layer laminated in this order.

[0308] (Manufacture of melamine decorative panels)

[0309] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet.

[0310] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0311] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 5.

[0312] [Pure water contact angle of release layer of decorative sheet]

[0313] The pure water contact angle of the release layer in the decorative sheet obtained in Examples 1 to 8 and Comparative Examples 1 to 5 was measured by the following method. The decorative sheet was placed on a horizontal surface in such a manner that the release layer became the upper surface. Next, water drops (pure water, 2.0 μL) were added to the release layer from a vertical direction relative to the horizontal surface. At this time, the water drops were not added to the boundary between the design layer and the release layer, but were added in such a manner that all the water drops were in contact with the release layer. After adding the water droplets, wait for 1 second and use a contact angle meter (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.) to measure the contact angle between the release layer and pure water. The above measurement was performed at any 10 locations, and the average value was set as the pure water contact angle. The results are shown in Tables 1 and 2. It should be noted that the pure water contact angle of the release layer of the resin-impregnated decorative board can be measured basically by the same method as described above, but when the water droplets are added to the release layer, the water droplets are not added to the boundary between the cured resin layer and the release layer, but are added in a manner that the entire water droplet is in contact with the release layer.

[0314] [60° gloss value of release layer of decorative sheet]

[0315] The 60° gloss values of the release layers of the decorative sheets obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were measured by the following method. The decorative sheet was placed with the release layer facing upward, and the 60° specular gloss was measured from the release layer side using a gloss meter ("micro-TRI-gloss (Cat. No. 4563)", manufactured by BYK Gardner) in accordance with JIS Z 8741:1997, Method 3, using the following method.

[0316] 1) Prepare paper (Ten Color <400> A4 black manufactured by Oji F-Tex), such as Figure 6 As shown in (a), it is cut into a size of 180 mm × 60 mm.

[0317] 2) Place the gloss meter on the cut paper and take the shape of the gloss meter with a pencil ( Figure 6 (dashed box in (b)).

[0318] 3) If Figure 6 As shown in (c), a hole C of 15 mm x 9 mm is cut out in the center to make the backing plate 61.

[0319] 4) Place the prepared backing plate on the measurement sample and visually confirm that the release layer is located in the center of the cut portion (hole C). Confirm that the ratio of the area of the release layer to the area of the cut portion (hole C) is 50% or more.

[0320] 5) Be careful not to move the pad position set in 4), and place the gloss meter on the part of the matching sample to measure the 60° gloss.

[0321] 6) Repeat the steps 4) and 5) but increase the number N, and take the average of the measured values at 10 locations as the 60° gloss value of the release layer. The results are shown in Tables 1 and 2.

[0322] [Spc of release layer of decorative sheet and melamine decorative board]

[0323] The Spc (arithmetic mean curvature of the peak apex) of the release layers of the decorative sheets and melamine decorative boards obtained in Examples 1 to 8 and Comparative Examples 1 to 5 was measured using the following method. The Spc value was measured using a laser microscope (VK-X3000, manufactured by KEYENCE Corporation) under the following conditions on the release layer surface of the decorative sheets. It should be noted that Spc is the average of the values measured at 10 random locations, with the measurement points selected so that each point falls within the release layer. The results are shown in Tables 1 and 2.

[0324] (Measurement conditions)

[0325] Objective lens: 5x

[0326] Laser wavelength: 661nm

[0327] Measurement area of each point: 500μm×500μm

[0328] [Evaluation of melamine peeling properties]

[0329] Using the melamine decorative boards obtained in Examples 1 to 8 and Comparative Examples 1 to 5, a tape resistance test was performed on the region including the release layer, and melamine releasability was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2.

[0330] (Tape resistance test method)

[0331] 1) Sellotape (registered trademark) (No. 405 (industrial use), width 24 mm) manufactured by Michelbon was pulled out to a length of 15 cm to 30 cm, 5 cm of the end portion was removed, and the adhesive surfaces of the remaining portion were bonded together (this portion became the grip portion during peeling).

[0332] 2) Place the adhesive surface of the end portion on the test part and rub it from above with a cloth or the like to ensure firm adhesion.

[0333] 3) Grip the part where the adhesive surfaces are in contact with each other in 1) and stretch it hard in a 45-degree direction.

[0334] 4) The melamine layer on the adhesive surface and the surface of the test part were visually inspected and evaluated according to the standards of A, B, and C.

[0335] 5) Perform 1) to 4) at any 10 locations on the peeling layer, and judge the one with the most evaluations as melamine peeling properties. If the number of evaluations is the same, the worse result shall be adopted.

[0336] (Evaluation Criteria)

[0337] A: Almost no peeling of melamine was observed, and no melamine remained on the release layer.

[0338] B: Remarkable peeling of melamine was observed, but the melamine could be peeled off by the test.

[0339] C: No peeling of melamine was observed, and melamine remained on most of the release layer after the test.

[0340] (The test failed to remove most of the melamine on the release layer (more than 90% of the area of the release layer))

[0341] [Gloss and matte design evaluation]

[0342] The gloss and matte design properties of the melamine decorative boards obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were visually evaluated. Specifically, the decorative boards were visually observed from a distance of 50 cm under a natural color fluorescent lamp (manufactured by Panasonic Corporation, model: FLR40S•D-SDL / M) to confirm the gloss and matte design properties and the state of the matte portion (release layer).

[0343] The observers scored the gloss-matt design on a scale of 1 to 5 (1 being the worst and 5 being the best). It should be noted that if a large amount of melamine peeling residue or significant whitening is visible in and around the matte portion, and a sufficient gloss-matt design cannot be confirmed, the evaluation is scored as 1 point. If no melamine peeling residue is confirmed in the matte portion, and a sufficient gloss-matt design can be confirmed, the evaluation is scored as 5 points. The evaluation is graded. Ten observers conducted the evaluation, and the average score of all the observers was calculated. The gloss-matt design was evaluated according to the following criteria. The results are shown in Tables 1 and 2.

[0344] (Evaluation Criteria)

[0345] A: The average score when evaluating gloss and matte design is 3 points or more

[0346] B: The average score when evaluating gloss and matte design is 2 points or more and less than 3 points

[0347] C: The average score when evaluating gloss and matte design is less than 2 points

[0348] [Table 1]

[0349]

[0350] [Table 2]

[0351]

[0352] As shown in Table 1, the decorative sheets obtained in Examples 1 to 8 showed excellent melamine releasability and gloss / matte design properties. On the other hand, as shown in Table 2, the decorative sheet obtained in Comparative Example 1 had a high 60° gloss value and a low Spc value, resulting in poor gloss / matte design properties. Furthermore, the decorative sheets obtained in Comparative Examples 2 and 3 had low pure water contact angles, indicating poor melamine releasability. The decorative sheets obtained in Comparative Examples 4 and 5 had low Spc values, resulting in poor gloss / matte design properties.

[0353] [Example 9]

[0354] (Production of decorative sheets)

[0355] Prepare paper substrate (weight per unit area 80g / m 2Titanium base paper for building materials (PM-83P manufactured by KJ Special Paper Co., Ltd.) was used as the porous substrate. The ash content of the paper substrate was measured in accordance with JIS-P8252 and was found to be 18%. A design layer (pattern layer) with a thickness of 2 μm was partially laminated on the paper substrate using the gravure printing method using the above-mentioned printing ink, forming a stone-grained design. Ink 1 for forming a release layer was then laminated on the pattern layer in synchronization with the pattern layer, and then electron beam irradiation was performed at an accelerating voltage of 165 kV for 3 Mrad, thereby forming a release layer with a thickness of 2 μm. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0356] (Manufacture of melamine decorative panels)

[0357] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0358] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0359] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 9.

[0360] [Example 10]

[0361] (Production of decorative sheets)

[0362] A paper substrate (titanium base paper for building materials, PM-83P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Ink 3 for forming a release layer was then laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a dose of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0363] (Manufacture of melamine decorative panels)

[0364] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0365] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0366] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 10.

[0367] [Example 11]

[0368] (Production of decorative sheets)

[0369] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 13 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0370] <Release layer forming ink 13>

[0371] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 46.8 parts by mass

[0372] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0373] • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0374] • Hindered amine light stabilizer (Tinuvin 123, manufactured by BASF Corporation) 1.2 parts by mass (2.0 parts by mass per 100 parts by mass of the total solid content)

[0375] • 40 parts by weight of methyl ethyl ketone

[0376] (Manufacture of melamine decorative panels)

[0377] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0378] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0379] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 11.

[0380] [Example 12]

[0381] (Production of decorative sheets)

[0382] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2 μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 14 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2 μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0383] <Release layer forming ink 14>

[0384] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 45 parts by mass

[0385] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0386] • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0387] • Hindered amine light stabilizer (produced by BASF Corporation, Tinuvin 123) 3 parts by mass (5.0 parts by mass relative to 100 parts by mass of the total solid content)

[0388] • 40 parts by weight of methyl ethyl ketone

[0389] (Manufacture of melamine decorative panels)

[0390] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0391] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0392] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 12.

[0393] [Example 13]

[0394] (Production of decorative sheets)

[0395] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 15 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0396] <Release layer forming ink 15>

[0397] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 44 parts by mass

[0398] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0399] • Silane coupling treated silica (particle size 2 μm) 9 parts by mass (15.0 parts by mass relative to 100 parts by mass of the total solid content)

[0400] • Hindered amine light stabilizer (produced by BASF Corporation, Tinuvin 123) 3 parts by mass (5.0 parts by mass relative to 100 parts by mass of the total solid content)

[0401] • 40 parts by weight of methyl ethyl ketone

[0402] (Manufacture of melamine decorative panels)

[0403] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0404] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0405] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This formed a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Example 13.

[0406] [Comparative Example 6]

[0407] (Production of decorative sheets)

[0408] Prepare paper substrate (weight per unit area 100g / m 2Titanium paper (KW-1002P manufactured by KJ Special Paper Co., Ltd.) was used as the porous substrate. The ash content of the paper substrate was measured in accordance with JIS-P8252 and was found to be 36%. By gravure printing using the above-mentioned printing ink, a design layer (pattern layer) with a thickness of 2 μm was partially laminated on the paper substrate in a manner that formed a stone-grained design. Ink 1 for forming a release layer was then laminated on the pattern layer in synchronization with the pattern layer, and then an electron beam of 3 Mrad was irradiated at an accelerating voltage of 165 kV to form a release layer with a thickness of 2 μm. A decorative sheet having a porous substrate, a design layer, and a release layer laminated in this order was thus manufactured.

[0409] (Manufacture of melamine decorative panels)

[0410] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0411] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0412] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 6.

[0413] [Comparative Example 7]

[0414] (Production of decorative sheets)

[0415] A paper substrate (titanium base paper for building materials, PM-77P manufactured by KJ Specialty Paper Co., Ltd.) was prepared as a porous substrate. Using the aforementioned printing ink, a 2μm thick design layer (pattern layer) was partially laminated onto the paper substrate to form a stone-grained design. Furthermore, the release layer-forming ink 16 described below was laminated onto the pattern layer in sync with the pattern layer. Subsequently, electron beam irradiation was performed at an accelerating voltage of 165 kV and a power of 3 Mrad to form a 2μm thick release layer. This produced a decorative sheet comprising a porous substrate, a design layer, and a release layer laminated in this order.

[0416] <Release layer forming ink 16>

[0417] • Ionizing radiation curable monomer (ARONIX M-400, manufactured by Toagosei Co., Ltd.) 42 parts by mass

[0418] • Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass (6.7 parts by mass per 100 parts by mass of the total solid content)

[0419] • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass relative to 100 parts by mass of the total solid content)

[0420] • Hindered amine light stabilizer (produced by BASF Corporation, Tinuvin 123) 6 parts by mass (10.0 parts by mass relative to 100 parts by mass of the total solid content)

[0421] • 40 parts by weight of methyl ethyl ketone

[0422] (Manufacture of melamine decorative panels)

[0423] Using an impregnation device for impregnation, a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nicaregin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was prepared so that the uncured melamine resin composition had a density of 80 g / m 2 The prepared decorative sheet was impregnated with the mixture at a ratio of 1:1 (drying) and dried to produce an impregnated decorative sheet (precursor laminate).

[0424] The impregnation decorative sheet is laminated on the core substrate, and the release film is laminated on the impregnation decorative sheet so that the release layer of the release film is in contact with the printed surface of the impregnation decorative sheet to obtain a laminate.

[0425] The laminated body was sandwiched between two mirror plates and pressed with a hot press at a pressure of 100 kg / cm 2The uncured melamine resin composition was heat-cured under the conditions of a molding temperature of 150°C for 10 minutes to form a cured resin layer comprising a cured product of the melamine resin. This resulted in a cured laminate. The cured laminate was then removed from between the two mirror panels, and the release film was peeled off from the cured resin layer comprising a cured product of the melamine resin, thereby obtaining the melamine decorative board of Comparative Example 7.

[0426] [Pure water contact angle of release layer of decorative sheet]

[0427] The pure water contact angles of the release layers of the decorative sheets obtained in Examples 9 to 12 and Comparative Examples 6 and 7 were measured. The measurement method was the same as described above. The results are shown in Table 3.

[0428] [60° gloss value of release layer of decorative sheet]

[0429] The 60° gloss values of the release layers of the decorative sheets obtained in Examples 9 to 12 and Comparative Examples 6 and 7 were measured. The measurement method was the same as described above. The results are shown in Table 3.

[0430] [Spc of release layer of decorative sheet and melamine decorative board]

[0431] The Spc (arithmetic mean curvature of the peak apex) of the release layers in the decorative sheets and melamine decorative boards obtained in Examples 9 to 12 and Comparative Examples 6 and 7 was measured. The measurement method was the same as above. The results are shown in Table 3.

[0432] [Evaluation of melamine peeling properties]

[0433] Melamine releasability was evaluated using the melamine decorative boards obtained in Examples 9 to 12 and Comparative Examples 6 and 7. The evaluation criteria were the same as above. The results are shown in Table 3.

[0434] [Gloss and matte design evaluation]

[0435] The gloss and matte design properties of the melamine decorative boards obtained in Examples 9 to 12 and Comparative Examples 6 and 7 were evaluated. The evaluation criteria were the same as above. The results are shown in Table 3.

[0436] [Table 3]

[0437]

[0438] As shown in Table 3, for example, in Example 9 and Example 1 above, release layer forming ink 1 was used, but the types of porous substrates were different. Specifically, the porous substrate (PM-83P) used in Example 9 had a lower ash content than the porous substrate (PM-77P) used in Example 1, making release layer forming ink 1 less likely to penetrate. As a result, compared to Example 1, Example 9 had an increased pure water contact angle and 60° gloss value, while Spc was slightly decreased. Thus, the type of porous substrate affects the pure water contact angle, 60° gloss value, and Spc. Therefore, it is necessary to consider the type of porous substrate and adjust the pure water contact angle, 60° gloss value, and Spc to specific ranges. In the present invention, by considering the type of porous substrate and adjusting the pure water contact angle, 60° gloss value, and Spc to specific ranges, good peelability and good gloss matte design properties can be achieved. The same relationship was also confirmed between Example 10 and Example 3.

[0439] Meanwhile, in Comparative Example 6 and Example 1, both used release layer-forming ink 1, but the types of porous substrates differed. Specifically, the porous substrate (KW-1002P) used in Comparative Example 6 had a higher ash content than the porous substrate (PM-77P) used in Example 1, allowing release layer-forming ink 1 to penetrate more easily. As a result, the pure water contact angle and 60° gloss value decreased, while Spc increased, in Comparative Example 6 compared to Example 1. Thus, the type of porous substrate affects the pure water contact angle, 60° gloss value, and Spc. In Comparative Example 6, due to its low pure water contact angle, the release properties were poor.

[0440] In Examples 11 and 12, as in Example 1 above, the same porous substrate was used, but the amount of light stabilizer added to the release layer-forming ink was different. The amount of light stabilizer added does not significantly affect the pure water contact angle, but increasing the amount of light stabilizer added increases the 60° gloss value and decreases the Spc value. Thus, the presence or absence of a light stabilizer and the amount of light stabilizer added affect the 60° gloss value and Spc value. Therefore, it is necessary to consider the presence or absence of a light stabilizer and the amount of light stabilizer added, and to adjust the pure water contact angle, 60° gloss value, and Spc value within specific ranges. In the present invention, by considering the presence or absence of a light stabilizer and the amount of light stabilizer added, and adjusting the pure water contact angle, 60° gloss value, and Spc value within specific ranges, good releasability and good gloss and matte design properties can be achieved.

[0441] Meanwhile, Comparative Example 7, Example 11, and Example 12 all used the same porous substrate, but differed in the amount of light stabilizer added to the release layer-forming ink. Increasing the amount of light stabilizer added showed an increasing 60° gloss value and a decreasing Spc value. In Comparative Example 7, the high 60° gloss value resulted in poor gloss-matt design properties. Furthermore, a comparison of Example 12 and Example 13 revealed that the increased matting agent content in Example 13 resulted in a lower 60° gloss value and an increased Spc value compared to Example 12, leading to improved gloss-matt design properties.

[0442] Thus, in the present invention, for example, the following inventions are provided. [1]

[0444] A decorative sheet for making a resin-impregnated decorative board, and

[0445] The decorative sheet has a porous base material, a design layer, and a release layer having a pattern shape in order in the thickness direction.

[0446] The 60° gloss value of the release layer is less than 10,

[0447] The pure water contact angle of the release layer is 85° or more.

[0448] The Spc (arithmetic mean curvature of the peak apex) of the release layer is 80 mm. -1 above. [2]

[0450] The decorative sheet as described in [1], wherein the pure water contact angle of the release layer is 100° or more. [3]

[0452] The decorative sheet as described in [1] or [2], wherein the 60° gloss value of the release layer is 6.5 or less. [4]

[0454] The decorative sheet as described in any one of [1] to [3], wherein the Spc (arithmetic mean curvature of the peak apex) of the release layer is 120 mm -1 above. [5]

[0456] The decorative sheet according to any one of [1] to [4], wherein the release layer contains a release agent. [6]

[0458] The decorative sheet as described in [5], wherein the release agent contains reactive silicone oil. [7]

[0460] The decorative sheet according to [5] or [6], wherein the content of the release agent is 1 part by mass or more and 10 parts by mass or less relative to 100 parts by mass of the release layer. [8]

[0462] The decorative sheet according to any one of [1] to [7], wherein the release layer contains a matting agent. [9]

[0464] The decorative sheet as described in [8], wherein the matting agent contains inorganic particles.

[10]

[0466] The decorative sheet as described in [8] or [9], wherein the content of the matting agent is 5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the release layer.

[11]

[0468] The decorative sheet as described in any one of [8] to

[10] , wherein the average particle size of the matting agent is 1 μm or more and 5 μm or less.

[12]

[0470] The decorative sheet according to any one of [1] to

[11] , wherein the thickness of the release layer is 0.5 μm or more and 8 μm or less.

[13]

[0472] The decorative sheet according to any one of [1] to

[12] , wherein the release layer contains a cured product of the curable resin X.

[14]

[0474] The decorative sheet as described in

[13] , wherein the curable resin X in the release layer is an ionizing radiation curable resin.

[15]

[0476] The decorative sheet as described in any one of [1] to

[14] , wherein the resin-impregnated decorative board is a melamine decorative board.

[16]

[0478] A resin-impregnated decorative board comprises: a decorative sheet having, in order in the thickness direction, a porous base material, a design layer, and a release layer having a pattern shape;

[0479] a core substrate disposed so as to face the porous substrate in the decorative sheet; and

[0480] a cured resin layer disposed between the patterns of the release layer, thicker than the release layer, and containing a cured product of a curable resin Y;

[0481] The porous substrate comprises a cured product of the curable resin Y.

[0482] The pure water contact angle of the release layer is 85° or more.

[0483] The Spc (arithmetic mean curvature of the peak apex) of the release layer is 10 mm. -1 above.

[17]

[0485] The resin-impregnated decorative board as described in

[16] , wherein the 60° gloss value of the release layer is 10 or less.

[18]

[0487] The resin-impregnated decorative board as described in

[16] or

[17] , wherein the ratio of the 60° gloss value of the cured resin layer to the 60° gloss value of the release layer is 1.2 or more.

[19]

[0489] A method for manufacturing a resin-impregnated decorative panel comprises the following steps:

[0490] a preparation step of preparing the decorative sheet as described in any one of [1] to

[15] ;

[0491] a laminate forming step of forming a laminate comprising: (i) a core substrate, the decorative sheet, a curable resin layer containing a curable resin Y, and a release film in this order in the thickness direction; (ii) the decorative sheet is arranged such that a surface facing the porous substrate faces the core substrate; and (iii) the decorative sheet is impregnated with the curable resin Y;

[0492] a heating and pressurizing step of heating and pressurizing the laminate to cure the curable resin Y and forming a cured resin layer from the curable resin layer, thereby obtaining a cured laminate; and

[0493] The peeling step is to peel the release film from the cured laminate to remove the cured resin layer arranged at a position overlapping with the release layer in the thickness direction, while leaving the cured resin layer arranged between the patterns of the release layer.

[0494] Description of Reference Numerals

[0495] 1: porous substrate; 2: design layer; 3: matte layer; 10: decorative sheet; 20: core substrate; 30: curable resin layer; 40: release film; 100: resin-impregnated decorative board.

Claims

1. A decorative sheet for producing a resin-impregnated decorative panel, and The decorative sheet has a porous base material, a design layer, and a release layer having a pattern shape in order in the thickness direction. The 60° gloss value of the release layer is less than 10, The pure water contact angle of the release layer is greater than 85°. The Spc of the release layer, i.e. the arithmetic mean curvature of the peak apex, is 80 mm. -1 above.

2. The decorative sheet according to claim 1, wherein: The release layer has a pure water contact angle of 100° or greater.

3. The decorative sheet according to claim 1, wherein: The release layer has a 60° gloss value of 6.5 or less.

4. The decorative sheet according to claim 1, wherein The Spc of the release layer, i.e. the arithmetic mean curvature of the peak apex, is 120 mm. -1 above.

5. The decorative sheet according to claim 1, wherein The release layer contains a release agent. The decorative sheet according to claim 5 , wherein: The release agent contains reactive silicone oil.

7. The decorative sheet according to claim 5, wherein: The content of the release agent is 1 part by mass or more and 10 parts by mass or less relative to 100 parts by mass of the release layer.

8. The decorative sheet according to claim 1, wherein: The release layer contains a matting agent.

9. The decorative sheet according to claim 8, wherein: The matting agent includes inorganic particles.

10. The decorative sheet according to claim 8, wherein: The content of the matting agent is 5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the release layer.

11. The decorative sheet according to claim 8, wherein: The average particle size of the matting agent is 1 μm or more and 5 μm or less.

12. The decorative sheet according to claim 1, wherein The release layer has a thickness of 0.5 μm or more and 8 μm or less.

13. The decorative sheet according to claim 1, wherein: The release layer contains a cured product of the curable resin X.

14. The decorative sheet according to claim 13, wherein: The curable resin X in the release layer is an ionizing radiation curable resin.

15. The decorative sheet according to claim 1, wherein The resin impregnated decorative board is a melamine decorative board.

16. A resin-impregnated decorative panel comprising: A decorative sheet having a porous base material, a design layer, and a release layer having a pattern shape in this order in the thickness direction; a core substrate disposed so as to face the porous substrate in the decorative sheet; and a cured resin layer disposed between the patterns of the release layer, thicker than the release layer, and containing a cured product of a curable resin Y; The porous substrate includes a cured product of the curable resin Y. The pure water contact angle of the release layer is greater than 85°. The Spc of the release layer, i.e. the arithmetic mean curvature of the peak apex, is 10 mm. -1 above.

17. The resin-impregnated decorative board according to claim 16, wherein: The release layer has a 60° gloss value of 10 or less.

18. The resin-impregnated decorative board according to claim 16, wherein: The ratio of the 60° gloss value of the cured resin layer to the 60° gloss value of the release layer is 1.2 or more.

19. A method for manufacturing a resin-impregnated decorative panel, comprising: a preparation step of preparing the decorative sheet according to any one of claims 1 to 15; a laminate forming step of forming a laminate comprising: (i) a core substrate, the decorative sheet, a curable resin layer containing a curable resin Y, and a release film, in this order in the thickness direction; (ii) the decorative sheet is arranged such that a surface facing the porous substrate faces the core substrate; and (iii) the decorative sheet is impregnated with the curable resin Y; a heating and pressurizing step of heating and pressurizing the laminate to cure the curable resin Y and forming a cured resin layer from the curable resin layer, thereby obtaining a cured laminate; and The peeling step is to peel the release film from the cured laminate to remove the cured resin layer arranged at a position overlapping with the release layer in the thickness direction, while leaving the cured resin layer arranged between the patterns of the release layer.

Images