Decorative sheet and resin-impregnated decorative sheet

Abstract

The present invention provides a decorative sheet for use in the production of a resin-impregnated decorative sheet, the decorative sheet comprising: a porous base material; a white solid layer that is disposed on the entire surface of one surface of the porous substrate and contains a white pigment; a pattern layer partially disposed on the surface of the white solid layer on the opposite side from the porous substrate; and a mold release layer which is arranged on the surface of the pattern layer on the opposite side from the white solid layer and has a pattern shape, the white solid layer has a blank region not covered by the pattern layer, the # imgabs0 # value in the blank region is 93.0 or more, and the ash content contained in the decorative sheet is 20.0 mass% or more and 40.0 mass% or less.

Description

Technical Field

[0001] The present invention relates to a decorative sheet and a resin impregnated decorative board for manufacturing a resin impregnated decorative board. Background Art

[0002] Conventionally, there has been known a resin impregnated decorative board obtained by impregnating a precursor such as a melamine resin (uncured resin) into a porous substrate and then curing the resin precursor. The resin impregnated decorative board can be used for walls, furniture, floors, etc. of houses, stores, public facilities, etc. In particular, there is a high demand for designs with a white tone such as marble, and when expressing a white design, a white substrate is usually used.

[0003] There is known a melamine decorative board that exhibits a design sense of a glossy matte tone. For example, Patent Document 1 discloses a decorative board having a release layer in a part of the surface of a porous substrate, and in the remaining area of the surface of the porous substrate without the release layer, while having a thermosetting resin layer, the thermosetting resin is impregnated into the porous substrate and cured. The porous substrate is a fibrous substrate, and the height difference between the thermosetting resin layer and the release layer is 5 μm or more.

[0004] Prior Art Documents

[0005] Patent Documents

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

[0007] Problems to be Solved by the Invention

[0008] In the method described in Patent Document 1, it is described that: the thermosetting resin layer exhibits a glossy design sense, the release layer exhibits a matte design sense, or the thermosetting resin layer exhibits a matte design sense, and the release layer exhibits a glossy design sense, whereby a distinct glossy matte tone design sense can be expressed on the surface of the decorative board. It is expected to provide a white resin impregnated decorative board with a glossy matte design that cannot be expressed in conventional products by applying this method to a white porous substrate.

[0009] However, white porous substrates such as titanium white paper (Japanese: チタン紙) usually contain white pigments such as titanium oxide, so there are many gaps between the papers, and the ink of the release layer responsible for expressing the glossy matte design will penetrate into the porous substrate, making it difficult to express the glossy matte design. On the other hand, in a porous substrate where the function of the release layer can be fully exerted, the content of the white pigment is insufficient and a white design cannot be expressed. Therefore, in conventional decorative sheets for manufacturing resin impregnated decorative boards, it is difficult to obtain a resin impregnated decorative board that can express a white design and stably express a glossy matte design.

[0010] The present invention has been made in view of the above-mentioned problems, and a main object of the present invention is to provide a decorative sheet of a resin-impregnated decorative plate capable of expressing a white design and stably expressing a glossy matte design.

[0011] Means for solving problems

[0012] The present invention provides a decorative sheet for manufacturing a resin-impregnated decorative plate, the decorative sheet comprising: a porous substrate; a white solid layer (Japanese: white beta layer), which is disposed on the entire surface of one surface of the porous substrate and contains a white pigment; a pattern layer, which is partially disposed on the surface of the white solid layer opposite to the porous substrate; and a release layer, which is disposed on the surface of the pattern layer opposite to the white solid layer and has a pattern shape, the white solid layer having a blank area not covered by the pattern layer, and the blank area The value is 93.0 or more, and the ash content contained in the decorative sheet is 20.0 mass % or more and 40.0 mass % or less.

[0013] In addition, the present invention provides a resin-impregnated decorative plate, which comprises: the decorative sheet; a core substrate arranged to face the porous substrate in the decorative sheet; and a cured resin layer arranged in the blank area and containing a cured product of a curable resin Y; the core substrate and the porous substrate contain the cured product of the curable resin Y, and the curable resin layer is formed by measuring the curable resin Y in the blank area through the cured resin layer. In the case of the above The value is 88.0 or above.

[0014] Effects of the Invention

[0015] In the present invention, an effect of being able to provide a decorative sheet of a resin-impregnated decorative plate capable of obtaining a design that can express white and stably express a glossy matte design is achieved. 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 resin-impregnated decorative plate in the present invention.

[0018] Figure 3 (a) to (e) are schematic cross-sectional views illustrating a method for producing a resin-impregnated decorative board using the decorative sheet of the present invention.

[0019] Figure 4 (a) to (c) are schematic diagrams of containers and lids used in the evaluation of permeability in Examples.

[0020] Figure 5 (a) to (e) are diagrams for explaining the method for evaluating the impregnation properties in Examples.

[0021] Figure 6 (a) to (h) are schematic plan views illustrating white solid layers in the present invention. DETAILED DESCRIPTION

[0022] Hereinafter, the embodiments will be described with reference to the accompanying drawings, etc. However, the present invention can be implemented in many different ways and is not limited to the contents of the embodiments described below. In addition, in order to make the description clearer, the drawings schematically show the width, thickness, and shape of each part compared to the actual form, but this is only an example and is not to be interpreted as limiting.

[0023] In this specification, when expressing a method of arranging other components on a certain component, if it is simply expressed as "on..." or "under...", unless otherwise specified, the following two cases are included: a case where the other component is arranged directly above or directly below the certain component in a manner of contacting the certain component; and a case where the other component is arranged above or below the certain component with another component further interposed therebetween. In addition, in this specification, when expressing a method of arranging other components on the surface of a certain component, if it is simply expressed as "on...", unless otherwise specified, the following two cases are included: a case where the other component is arranged directly above or directly below the certain component in a manner of contacting the certain component; and a case where the other component is arranged above or below the certain component with another component further interposed therebetween.

[0024] A.Decorative sheet

[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 has: a porous substrate 1; a white solid layer 2, which is disposed on the entire surface of one side of the porous substrate 1 and contains a white pigment; a pattern layer 3, which is partially disposed on the surface of the white solid layer 2 opposite to the porous substrate 1; and a release layer 4, which is disposed on the surface of the pattern layer 3 opposite to the white solid layer 2 and has a pattern shape. In the present invention, the white solid layer 2 has a blank area X that is not covered by the pattern layer 3, and the blank area X has a white pigment. The value is 93.0 or more. In addition, the ash content contained in the decorative sheet 10 is 20.0 mass % or more and 40.0 mass % or less.

[0026] As described above, it is difficult to obtain a resin-impregnated decorative sheet that can express a white design and a glossy matte design in the conventional resin-impregnated decorative sheet manufacturing. The inventors of the present invention have found that when visually observing the resin-impregnated decorative sheet, if In the color system If the value is above the specified value, a white feeling can be obtained. In addition, the curable resin (melamine resin, phenol resin, diallyl phthalate resin, polyester resin, etc.) impregnated into the decorative sheet is mostly a colored resin or a translucent resin, which may hinder the whiteness of the decorative sheet. Therefore, it is found that in order to ensure sufficient white design in the decorative board, the decorative sheet needs to ensure a higher white design ( value).

[0027] In the case of ordinary decorative paper, a method of coating the entire surface of the substrate with white ink to obtain a white design can also be considered, but in order to ensure the resin impregnation of the porous substrate, the decorative sheet used to make the resin-impregnated decorative board is usually not coated with ink on the entire surface.

[0028] The decorative sheet of the present invention is formed by providing a decorative sheet having a white solid layer on the entire surface of one surface of a porous substrate within the range of the resin impregnation of the porous substrate and having an ash content of a predetermined ratio or more, so that the blank area X of the white solid layer 2 not covered by the pattern layer 3 can be reduced. Therefore, by using the decorative sheet of the present invention, a resin-impregnated decorative board expressing a white design can be obtained.

[0029] Furthermore, the decorative sheet of the present invention can suppress the ink of the release layer responsible for expressing the glossy matte design from penetrating into the porous substrate by having an ash content of a predetermined ratio or less, so that the glossy matte design can be expressed stably.

[0030] 1. Composition of decorative sheets

[0031] (1) value

[0032] The decorative sheet of the present invention has a blank area where the white solid layer is not covered by the pattern layer, and the blank area Color system The value is 93.0 or more. With such a decorative sheet, a resin-impregnated decorative plate capable of expressing a white design can be manufactured as described later. The value is more preferably 94.5 or more, and particularly preferably 95.0 or more. If such a decorative sheet is used, even in the manufacturing process of the resin-impregnated decorative board When the value is reduced, a resin-impregnated decorative plate capable of expressing a white design can also be produced. The value is, for example, 97.0 or less, or may be 96.0 or less.

[0033] “ The "color system" refers to the color system standardized by CIE (International Commission on Illumination) and adopted in JIS Z 8781-4:2013. It should be noted that In the color system, brightness is expressed as Values ​​are expressed as hue and saturation. value, Value representation. The value essentially indicates whiteness, and the closer it is to 100, the higher the whiteness, and the closer it is to 0, the lower the whiteness.

[0034] Blank area Color system The value is the average value of the values ​​measured at 5 locations on the surface of the blank area using CM-3700A manufactured by Konica Minolta. The primary color measurement area is a circle with a diameter of 25.4 mm (area 506.71 mm 2 ).

[0035] like Figure 1 As shown, the blank area X refers to the area of ​​the white solid layer 2 that is not covered by the pattern layer 3, and more specifically, refers to the area that is not covered by the pattern layer 3 and the release layer 4. It should be noted that it is also possible to assume that a part of the release layer 4 protrudes from the area where the pattern layer 3 is arranged when viewed in the thickness direction. In this case, the area covered by the colorless and transparent release layer 4 and not covered by the pattern layer 3 can also be called a blank area.

[0036] (2) Ash content

[0037] In the present invention, the ash content contained in the decorative sheet is 20.0% by mass or more, preferably 22.0% by mass or more. The above ash content is similar to the content of inorganic substances such as white pigments in the decorative sheet, mainly in the porous substrate. If the ash content is too little, even if a white solid layer containing white pigments is provided, a white design cannot be expressed. On the other hand, the above ash content is 40.0% by mass or less, preferably 30.0% by mass or less. If the ash content is too much, a glossy matte design cannot be stably expressed.

[0038] The ash content in the present invention is a value measured by the following measurement method and measurement conditions.

[0039] <Measurement method>

[0040] Cut out about 5 mg of the measurement sample from the decorative sheet. Use the following thermogravimetric / differential thermal simultaneous analysis device, under the following conditions, raise the temperature from room temperature to 30°C at a heating rate of 10°C / min, and keep it at 30°C for 15 minutes. Thereafter, raise the temperature to 120°C at a heating rate of 10°C / min, and keep it at 120°C for 30 minutes. Thereafter, raise the temperature to 600°C at a heating rate of 10°C / min, and keep it at 600°C for 30 minutes. Thus, the measurement sample is ashed.

[0041] <Measurement Equipment and Mechanical Conditions>

[0042] Device: DTG-60A (TG-DTA)

[0043] Atmosphere gas: air

[0044] Gas flow rate: 175[ml / min]

[0045] Initial mass: about 5 mg (cut out decorative piece)

[0046] Heating program

[0047] Room temperature → heating (10℃ / min) → 30℃, keep for 15min → heating (10℃ / min) → 120℃, keep for 30min → heating (10℃ / min) → 600℃, keep for 30min → end

[0048] The ash content in the present invention is expressed as a percentage of the mass of the sample after being kept at 600°C for 30 minutes relative to the mass of the sample after being kept at 120°C for 30 minutes in the above-mentioned temperature rise sequence as shown in the following calculation formula.

[0049] <Calculation formula>

[0050] Ash content (%) = (mass of sample after holding at 600°C for 30 minutes [mg] / mass of sample after holding at 120°C for 30 minutes [mg]) × 100

[0051] 2. Components of decorative sheets

[0052] The decorative sheet of the present invention comprises at least a porous substrate, a white solid layer, a pattern layer and a release layer.

[0053] (1) Release layer

[0054] The release layer in the present invention is at least partially disposed on the surface of the pattern layer opposite to the white solid layer and has a pattern shape. The release layer has a release property to the cured resin layer between the release layer and the release film in the manufacturing process of the resin-impregnated decorative board described later. By having such a release property, for example, in the decorative sheet manufactured using the present invention, Figure 3In the resin-impregnated decorative board 100 shown in (e), the cured resin layer 32 imparts a glossy design, and the release layer 4 imparts a matte design, thereby expressing a vivid glossy-matte color design.

[0055] In addition, the release layer is preferably configured in synchronization with the pattern of the pattern layer. "Synchronization" means that the shapes and positions of the two patterns as objects are roughly consistent. Specifically, the pattern of the release layer is consistent with the shape and position of the pattern of at least a part of the pattern constituting the pattern layer to the extent that the sense of reality and the sense of luxury are not impaired. By configuring the pattern of the release layer in synchronization with the pattern of the pattern layer, a high texture can be obtained.

[0056] The demoulding layer contains a resin component. The resin component is typically a cured product (cross-linked structure) of a curable resin. It should be noted that in the present invention, the curable resin in the demoulding layer is sometimes referred to as a curable resin X. On the other hand, the resin component can be a thermoplastic resin. Among them, the demoulding layer is preferably a cured product containing a curable resin. This is because a demoulding layer with good wear resistance can be obtained. In addition, since the demoulding layer contains a cured product of a curable resin, the demoulding property to the cured resin layer is good.

[0057] 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.

[0058] Ionizing radiation curable resin (ionizing radiation curable compound) is not limited as long as it is a material that produces a cross-linking polymerization reaction by irradiation of ionizing radiation and is converted into a three-dimensional polymer structure. As ionizing radiation curable resin, for example, prepolymers, oligomers and monomers having polymerizable unsaturated bonds or epoxy groups that can be cross-linked by irradiation of ionizing radiation can be listed in the molecule. In the present invention, only one ionizing radiation curable resin can be used, or more than two can be used. Among them, as the ionizing radiation curable resin, it is preferred to use at least one of a multifunctional monomer and an oligomer.

[0059] Examples of the ionizing radiation curable resin 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.

[0060] 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.

[0061] The ionizing radiation curable resin preferably contains at least a multifunctional monomer or oligomer having a weight average molecular weight of 500 or more. Examples of such multifunctional 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.

[0062] On the other hand, examples of thermosetting resins include unsaturated ester resins, urethane resins (including two-component curable polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine urea polycondensation resins, silicone resins, and siloxane resins.

[0063] The release layer may contain a matting agent. Examples of the matting agent include inorganic particles and synthetic resin particles. Examples of the inorganic particles include silicon oxide, aluminum oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of the 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).

[0064] The average particle size of the matte agent is, for example, 0.3 μm or more and 10 μm or less, 0.5 μm or more and 7 μm or less, or 1 μm or more and 5 μm or less. The average particle size is D50 based on volume-based particle size distribution measured by laser diffraction scattering method. The content of the matte agent is, for example, 5 parts by mass or more and 40 parts by mass or less, and may be 10 parts by mass or more and 35 parts by mass or less relative to 100 parts by mass of the resin component of the release layer.

[0065] The release layer may also contain a release agent. By adding a release agent, the release property is improved. Examples of the release agent include silicone-based release agents such as silicone oil, wax-based release agents such as polyolefin wax, and fluorine-based release agents. Examples of silicone oil include reactive silicone oil and non-reactive silicone oil.

[0066] Reactive silicone oil refers to a silicone oil that has a reactivity according to the nature of the introduced organic group in a modified silicone oil having an organic group introduced into a side chain or a terminal. As reactive silicone oil, specifically, there can be cited: in a modified silicone oil side chain type, a modified silicone oil both-end type, a modified silicone oil single-end type, a modified silicone oil side chain both-end type, etc., the introduced organic group is an amino-modified, epoxy-modified, mercapto-modified, carboxyl-modified, methanol-modified, phenol-modified, methacrylic-modified, heterogeneous functional group-modified, etc. Reactive silicone oils can be used alone or in combination of two or more.

[0067] As long as the non-reactive silicone oil is a silicone oil without reactive functional groups such as amino, epoxy, thiol, carboxyl, hydroxyl, (meth) acryloyl, and allyl, there is no particular restriction. As the non-reactive silicone oil, for example, in addition to silicone oils containing polysiloxane, there can also be cited: 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 acid amide-modified silicone oils, phenyl-modified silicone oils, etc. These non-reactive silicone oils can be used alone or in combination of two or more.

[0068] The content of the release agent is, for example, 0.1 parts by mass to 50 parts by mass, 0.5 parts by mass to 20 parts by mass, 3 parts by mass to 20 parts by mass, or 3 parts by mass to 10 parts by mass, relative to 100 parts by mass of the resin component of the release layer.

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

[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, defoamers, fillers, thermal free radical generators, aluminum chelating agents, etc. as needed. The thickness of the release layer is not particularly limited, and is, for example, 0.1 μm or more and 20 μm or less.

[0071] 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 pattern layer opposite to the white solid layer and curing it. Examples of the coating method include printing methods. Examples of the printing method include gravure printing, offset printing, screen printing, soft printing, electrostatic printing, and inkjet printing.

[0072] When the ink for forming the release layer contains an electron beam curable resin, a cured product of the electron beam curable resin is usually obtained by irradiating an electron beam. As an electron beam source, for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, Dynamitron type, and high frequency type can be listed. As the energy of the electron beam, for example, it is 100 kV or more and 1000 kV or less, and can be 100 kV or more and 300 kV or less. The irradiation amount of the electron beam is, for example, 2 Mrad or more and 15 Mrad or less.

[0073] When the ink for forming the release layer contains an ultraviolet curable resin, a cured product of the ultraviolet curable resin is usually obtained by irradiating ultraviolet rays. Examples of ultraviolet light sources include ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps. The wavelength of ultraviolet light is, for example, 190 nm or more and 380 nm or less.

[0074] When the ink for forming the release layer contains a thermosetting resin, a cured product of the thermosetting resin is usually obtained by heating. The heating temperature is appropriately set according to the type of the thermosetting resin. In addition to the thermosetting resin, the ink for forming the release layer may also contain a curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator. Examples of the curing agent include isocyanates, organic sulfonates, organic amines, peroxides (e.g., methyl ethyl ketone peroxide), and free radical initiators (azoisobutyronitrile).

[0075] The ink for forming the release layer may contain a solvent as required. 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.

[0076] (2) Pattern layer

[0077] The pattern layer in the present invention is partially (especially in a pattern) arranged on the surface of the white solid layer opposite to the porous substrate. Examples of the pattern in the pattern layer include stone patterns, sand patterns, tile patterns, wood patterns, brick patterns, cloth patterns, leather patterns, geometric figures, characters, symbols, abstract patterns, and floral patterns.

[0078] The pattern layer contains, for example, a colorant and a resin component (binder resin). Examples of the colorant 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; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxychloride; fluorescent pigments; and luminous pigments. Dyes can be used as colorants.

[0079] Examples of the resin component include ester carbamate resins, acrylamide resins, (meth) acrylic resins, ethylene oxide resins, N-vinyl pyrrolidone resins, ester resins, amide resins, vinyl acetate resins, vinyl chloride resins, carbamate (meth) acrylic resins, amino resins, phenolic resins, natural polymers (e.g., polynucleotides, polypeptides, polysaccharides), natural rubbers, and synthetic rubbers. The resin component may be water-soluble or fat-soluble.

[0080] The pattern layer preferably contains a resin having a polar group as a resin component. This is because the resin impregnation into the porous substrate is good. Examples of polar groups include hydroxyl (-OH), amino (-NH2), carboxyl (-COOH), etc. The above polar groups may be ionized and stabilized due to the influence of solvents and other functional groups. Therefore, the above "hydroxyl (-OH)" includes "-O - ", the above "amino group (-NH2)" includes "-NH3 + ", "carboxyl (-COOH)" includes "-COO - ” concept.

[0081] The resin having a polar group is preferably a resin that is dissolved or dispersed in water, methanol or ethanol. This is because the uncured resin such as a hydrophilic melamine resin has good impregnation. Here, "dissolved or dispersed in water, methanol or ethanol" means that the following test is performed and a specific standard is satisfied. That is, referring to JISK8001: 2017 3.2, the following operation is performed.

[0082] 1) Prepare 100 ml of water, methanol or ethanol as solvent.

[0083] 2) 0.1 g (0.1 ml in the case of liquid) of each resin was added to each of the above solvents at 20°C ± 5°C.

[0084] 3) Shake vigorously for 30 seconds every 5 minutes.

[0085] 4) After 30 minutes, the mixture was vigorously shaken for 30 seconds and then left to stand for 1 minute. If the following phenomena could not be visually observed, it was judged as "dissolved or dispersed".

[0086] There is precipitation of solids at the bottom of the container.

[0087] Phase separation of solvent and resin (oil droplets) occurs on the solvent surface, in the solvent, or at the bottom of the container.

[0088] Examples of the resin having a polar group include aqueous proteins such as casein, cellulose, cellulose derivatives represented by acetylcellulose, 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, phenol resins, acrylic polyols, natural polymers (e.g., polynucleotides, polypeptides, polysaccharides), etc.

[0089] The pattern layer in the present invention preferably contains at least one of casein, melamine resin, polyvinyl alcohol, polyvinyl alcohol derivatives, cellulose and cellulose derivatives as the resin having a polar group, and more preferably contains casein. As casein, α-casein, β-casein, γ-casein or a mixture thereof can be used. In addition, as casein, derivatives represented by sodium caseinate and ammonium caseinate can also be used alone or in combination.

[0090] The pattern layer may contain fillers (eg, silicon oxide), extender pigments (eg, organic beads), neutralizers, surfactants and other additives as necessary. The thickness of the pattern layer is not particularly limited, and is, for example, 0.1 μm to 20 μm.

[0091] As a method for forming the pattern layer, for example, a coating method using a pattern layer forming ink containing a colorant, a binder resin and a solvent (or a dispersion medium) can be cited. For example, the pattern layer can be obtained by coating the pattern layer forming ink on the surface of the white solid layer opposite to the porous substrate and drying it.

[0092] Examples of the 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.

[0093] Examples of the coating method include printing methods, and examples of the printing methods include gravure printing, offset printing, screen printing, soft printing, electrostatic printing, and inkjet printing.

[0094] (3) White solid layer

[0095] The white solid layer in the present invention is arranged so as to cover the entire surface of one surface of the porous substrate. The entire surface of one surface of the porous substrate refers to an area of ​​90% or more based on the portion of one surface of the porous substrate that functions as a decorative sheet. The white solid layer can be arranged so as to cover 95% or more of the portion of one surface of the porous substrate that functions as a decorative sheet, or can be arranged so as to cover 100%.

[0096] The “white solid layer is arranged to cover the entire surface of one surface of the porous substrate” will be described in more detail using some examples. Figure 6 As shown in (a), when the white solid layer 2 completely covers the porous substrate 1 when viewed from the thickness direction, the white solid layer 2 is arranged so as to cover the entire surface of the porous substrate 1 (100% of the portion functioning as a decorative sheet). Figure 6 As shown in (b), when both ends of the porous substrate 1 are exposed from the white solid layer 2 when viewed from the thickness direction, the both ends do not function as decorative sheets. Therefore, the entire surface of the porous substrate 1 is defined except for the area that does not function as a decorative sheet. Figure 6 In (b), the white solid layer 2 is arranged so as to cover the entire surface of the porous substrate 1 (100% of the portion functioning as a decorative sheet). Figure 6 As shown in (c), when the entire periphery of the outer edge of the porous substrate 1 is located outside the outer edge of the white solid layer 2 when viewed from the thickness direction, the area of ​​the porous substrate 1 exposed from the white solid layer 2 does not function as a decorative sheet. Therefore, the entire surface of the porous substrate 1 is defined except for the area that does not function as a decorative sheet. Figure 6 In (c), the white solid layer 2 is arranged so as to cover the entire surface of the porous base material 1 (100% of the portion functioning as a decorative sheet).

[0097] On the other hand, Figure 6 In (d), when viewed in the thickness direction, the entire surface of the porous substrate 1 functions as a decorative sheet. On the other hand, there is a region α where the white solid layer 2 is not formed (for example, an uncoated portion produced for the purpose of design expression) further inside the outer edge of the white solid layer 2. In this case, when the total area of ​​the region α is less than 10% relative to the surface of the porous substrate 1 (the portion that functions as a decorative sheet), it can be considered that "the white solid layer is arranged in a manner that covers the entire surface of one surface of the porous substrate". In addition, in Figure 6In (e), when viewed in the thickness direction, the entire surface of the porous substrate 1 functions as a decorative sheet. On the other hand, there is a region α where the white solid layer 2 is not formed (for example, an uncoated portion produced for the purpose of design expression) in a manner that divides the white solid layer 2. In this case, when the total area of ​​the region α is less than 10% relative to the surface of the porous substrate 1 (the portion that functions as a decorative sheet), it can be considered that "the white solid layer is arranged in a manner that covers the entire surface of one surface of the porous substrate." Similarly, in Figure 6 In (f), when viewed in the thickness direction, the entire surface of the porous substrate 1 functions as a decorative sheet. On the other hand, there is a region α where the white solid layer 2 is not formed. In this case, when the total area of ​​the region α is less than 10% relative to the surface of the porous substrate 1 (the portion that functions as a decorative sheet), it can be said that "the white solid layer is arranged so as to cover the entire surface of one surface of the porous substrate".

[0098] In addition, if Figure 6 As shown in (g), when both ends of the porous substrate 1 are exposed from the white solid layer 2 when viewed from the thickness direction, the both ends do not function as decorative sheets. Therefore, the entire surface of the porous substrate 1 is defined except for the area that does not function as a decorative sheet. Figure 6 In (g), there is a region α where the white solid layer 2 is not formed (for example, an uncoated portion produced for the purpose of design expression) further inside the outer edge of the white solid layer 2. In this case, when the total area of ​​the region α is less than 10% of the portion of the surface of the porous substrate 1 that functions as a decorative sheet, it can be considered that "the white solid layer is arranged so as to cover the entire surface of one surface of the porous substrate". In addition, if Figure 6 As shown in (h), when the entire periphery of the outer edge of the porous substrate 1 is located outside the outer edge O1 of the white solid layer 2 when viewed from the thickness direction, the area of ​​the porous substrate 1 exposed from the white solid layer 2 outside the outer edge O1 does not function as a decorative sheet. Therefore, the entire surface of the porous substrate 1 is defined except for the area that does not function as a decorative sheet. Figure 6 As shown in (h), when the outer edge O2 of the white solid layer 2 has a complex shape, the outer edge O1 of the quadrilateral is set so that the area of ​​the white solid layer 2 becomes the largest. Figure 6 In (h), there is a region α where the white solid layer 2 is not formed. In this case, when the total area of ​​the region α is less than 10% of the portion of the surface of the porous substrate 1 that functions as a decorative sheet, it can be considered that "the white solid layer is arranged so as to cover the entire surface of one surface of the porous substrate".

[0099] The white solid layer contains a white pigment. Although not particularly limited, examples of the white pigment include titanium oxide, calcium carbonate, zinc oxide, barium sulfate, silicon oxide, and the like. Among them, titanium oxide and calcium carbonate are preferred. In the present invention, titanium oxide is particularly preferred in terms of good whiteness and masking properties. The proportion of the white pigment in the white solid layer is, for example, 50% by mass or more, preferably 60% by mass or more. On the other hand, the proportion of the white pigment is, for example, 95% by mass or less, preferably 90% by mass or less.

[0100] The white solid layer contains, in addition to the white pigment, for example, a resin component, an additive, and a solvent (or a dispersion medium). The resin component, additive, and solvent (or a dispersion medium) may be the same as those exemplified in the pattern layer.

[0101] In addition, the white solid layer preferably contains a resin having a polar group as a resin component. This is because the resin impregnation property in the porous substrate is good. As the resin having a polar group, the same resin as the resin having a polar group exemplified in the pattern layer can be cited.

[0102] The white solid layer in the present invention preferably contains any one or more of casein, melamine resin, polyvinyl alcohol, polyvinyl alcohol derivatives, cellulose and cellulose derivatives as the resin having a polar group, and more preferably contains casein. As casein, α-casein, β-casein, γ-casein or a mixture thereof can be used. In addition, as casein, derivatives represented by sodium caseinate and ammonium caseinate can also be used alone or in combination.

[0103] In addition, when observing the decorative sheet from the thickness direction, the ratio (S2 / S1) of the area S2 of the blank area (area not covered by the pattern layer) in the white solid layer to the entire area S1 of the white solid layer is, for example, 5% or more, and can be 10% or more. When the above ratio (S2 / S1) is within the above range, the design effect based on the blank area can be fully obtained. On the other hand, the above ratio (S2 / S1) is, for example, 95% or less, can be 80% or less, or can be 70% or less.

[0104] In the area exposed from the release layer when observed from the thickness direction, the pure water contact angle is preferably lower. The area exposed from the release layer when observed from the thickness direction refers to an area where a white solid layer is formed and a release layer is not formed. The surface of the area exposed from the release layer can be the surface of the white solid layer or the surface of the pattern layer. This is because the impregnation of uncured resins such as hydrophilic melamine resins is good. The pure water contact angle is obtained by the following method. That is, the decorative sheet is placed on a horizontal plane so that the release layer side becomes the upper surface. Secondly, water drops (pure water, 2.0 μL) are dripped onto the white solid layer from a direction perpendicular to the horizontal plane. At this time, the water drops do not drip onto, for example, the boundary between the white solid layer and the release layer, and all water drops drip in a manner that contacts the area exposed from the release layer. After the water drops drip, 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 white solid 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. The pure water contact angle may be 80.0° or less, 70.0° or less, or 60.0° or less. On the other hand, the pure water contact angle may also be 0°. That is, pure water can completely penetrate the decorative sheet.

[0105] In the present invention, the wettability of the region exposed from the release layer is preferably high because the uncured resin such as the hydrophilic melamine resin has good permeability. The wettability is determined by the following method.

[0106] 1) Tension testers (manufactured by Pacific Chemical Co., Ltd.) with dynamometers of 40 mN / m, 46 mN / m, 50 mN / m, 54 mN / m, 60 mN / m, 67 mN / m, and 70 mN / m were prepared respectively.

[0107] 2) Use a tension tester to draw a line of more than 30 cm on the surface of the decorative sheet. At this time, do not draw the line only on the release layer, but make the line part include the area exposed from the release layer.

[0108] 3) After drawing the line, let it stand for 2 seconds and wipe the surface with a dry cloth. After that, visually check whether there is ink stain or discoloration caused by the tension tester in the blank area. Perform this operation 3 times at 1 dyne.

[0109] 4) Carry out the above-mentioned operations 2) and 3) respectively with each prepared dynamometer.

[0110] 5) The dyne number at which ink marks or discoloration were observed in the results of 4) above (including the case where ink marks or discoloration were observed once out of three times) with the largest value was determined as the wettability of the decorative sheet.

[0111] The wettability is, for example, 50 mN / m or more, 54 mN / m or more, or 60 mN / m or more. On the other hand, the wettability is, for example, 70 mN / m or less.

[0112] The ratio of the resin having polar groups to the resin component contained in the white solid layer is, for example, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more. On the other hand, the ratio of the resin having polar groups is, for example, 100% by mass or less, or 90% by mass or less. If the content of the resin having polar groups is within the above range, the penetration of the ink of the release layer into the porous substrate can be further suppressed without hindering the penetration of the uncured resin into the porous substrate.

[0113] In addition, the white solid layer may also have other resins as resin components in addition to the above-mentioned resins having polar groups. Examples of other resins include: (meth) acrylic resins, ester carbamate resins, acrylamide resins, ethylene oxide resins, N-vinyl pyrrolidone resins, ester resins, amide resins, vinyl acetate resins, vinyl chloride resins, carbamate (meth) acrylic resins, natural rubber, and synthetic rubber. Among them, (meth) acrylic resins and carbamate (meth) acrylic resins are preferred.

[0114] The thickness of the white solid layer is not particularly limited, and is, for example, 1 μm or more, preferably 2 μm or more, and may be 3 μm or more. If the thickness of the white solid layer is within the above range, it has excellent whiteness. On the other hand, it is preferably 8 μm or less, and may be 6 μm or less. If the thickness of the white solid layer is within the above range, the resin impregnation into the porous substrate is good. The thickness of the white solid layer is the average value of the thickness measured at 10 locations by observing the cross section obtained by cutting the decorative sheet in the thickness direction using an optical microscope.

[0115] The coating weight (basis weight) of the white solid layer is not particularly limited, but is, for example, 1.0 g / m 2 Above, preferably 2.0g / m 2 Above, can be 3.0g / m 2 If the coating amount of the white solid layer is greater than the above value, a white solid layer having excellent whiteness can be obtained. On the other hand, the coating amount (basis weight) of the white solid layer is preferably 10 g / m 2 Below, can be 8g / m 2 When the coating amount of the white solid layer is less than or equal to the above value, the resin impregnation property into the porous base material is good.

[0116] In the present invention, the 75° gloss value of the blank area (area not covered by the pattern layer) of the white solid layer is, for example, 6.0 or more, preferably 8.0 or more, and more preferably 10.0 or more. If the 75° gloss value of the blank area of ​​the white solid layer is within the above range, it is easy to obtain a resin-impregnated decorative plate that can express a white design. On the other hand, the 75° gloss value is, for example, 25.0 or less, preferably 20.0 or less. If the 75° gloss value of the blank area of ​​the white solid layer is within the above range, it is possible to prevent the obstruction of melamine impregnation caused by the white solid layer and maintain good processability.

[0117] In the present invention, the 75° gloss value of the blank area of ​​the white solid layer is the 75° specular gloss measured in accordance with Method 2 of JIS Z 8741:1997, and is a value measured by the following method.

[0118] The decorative sheet was placed with the release layer side facing upward, and the 75° specular gloss was measured from the release layer side using a gloss meter in accordance with Method 2 of JIS Z 8741:1997.

[0119] The 75° gloss value of the blank area of ​​the white solid layer is the average of the measured values ​​of any 10 locations of the blank area (area not covered by the pattern layer). At each measurement location, the blank area of ​​the white solid layer is located at the center of the measurement area of ​​the gloss meter, and the measurement is performed after confirming that the ratio of the area of ​​the blank area is 50% or more of the area of ​​the measurement area.

[0120] The 75° gloss value of the blank area of ​​the white solid layer can be increased, for example, by increasing the thickness of the white solid layer, and can be decreased by decreasing the thickness of the white solid layer.

[0121] As a method for forming the white solid layer, for example, a coating method using a white solid layer ink containing a white pigment, a resin component, an additive, and a solvent (or a dispersion medium) can be cited. For example, the white solid layer is obtained by coating the white solid layer ink on one surface of a porous substrate and drying it.

[0122] Examples of the 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.

[0123] In addition, various coating methods such as roller coating, blade coating, air knife coating, die-mouth coating, die-lip coating, notch wheel coating, kiss coating, flow coating, and dip coating can be cited as coating methods for forming the white solid layer. Various coating methods such as gravure printing can be cited as printing methods.

[0124] The white solid layer may be arranged to cover the entire surface of one surface of the porous substrate by one coating, or may be arranged to cover the entire surface of one surface of the porous substrate by multiple coatings. In the latter case, the layer formed by one coating may have a pattern.

[0125] (4) Porous substrate

[0126] The porous substrate in the present invention is a substrate impregnated with an uncured resin (curable resin Y) such as a thermosetting resin when manufacturing a resin-impregnated decorative board. As a porous substrate, for example, a fibrous substrate with permeability can be cited. As a fibrous substrate with permeability, for example, paper, synthetic paper, non-woven fabrics, and woven fabrics can be cited. As the above-mentioned paper, for example, titanium dioxide paper, thin paper, kraft paper, short lint paper, cardboard, gypsum board paper, high-grade paper, coated paper, parchment paper, and Japanese paper can be cited. In addition, as a fibrous substrate, a vinyl wallpaper original sheet (obtained by dry laminating a polyvinyl chloride resin on paper) can also be used. 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 cited. Among these porous substrates, titanium dioxide paper, thin paper, kraft paper, coated paper, coated paper, sulfuric acid paper, glass paper, parchment paper, paraffin paper, and Japanese paper are preferred in terms of the impregnation of thermosetting resins. In the present invention, the above From the viewpoint of the value, titanium white paper is preferred. Furthermore, titanium white paper is excellent in the impregnation property of the curable resin Y.

[0127] The porous substrate may also be colored. For example, a porous substrate colored in white may be obtained by mixing a white pigment in the manufacturing stage of the porous substrate. For example, when the porous substrate is paper, white paper colored in white may be obtained by mixing a white pigment such as titanium dioxide in the papermaking stage. In addition, the amount of the white pigment mixed is not particularly limited as long as it is an amount that is a proportion of the above-mentioned ash content. In particular, the white pigment used in the porous substrate constituting the decorative sheet of the present invention requires a function for adjusting the whiteness of the entire porous substrate and a function for adjusting the permeability of the porous substrate. In the present invention, in order to obtain the above-mentioned The type and amount of white pigment are set in such a way that the above ash content is within a specified range, that is, in such a way that the permeability of the porous substrate is adjusted. In addition, the porous substrate may also contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers as needed.

[0128] The basis weight 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, in order to improve the adhesion of the ink forming the white solid layer, the surface of the porous substrate on the white solid layer side may be subjected to corona discharge treatment.

[0129] 3. Decorative sheet

[0130] The blank area of ​​the decorative sheet of the present invention In the color system The value is preferably 4.5 or less, and more preferably 4.0 or less. With such a decorative sheet, a resin-impregnated decorative plate with high whiteness and suppressed yellow tint can be obtained. The value is, for example, 3.0 or more.

[0131] The decorative sheet in the present invention is used to manufacture a resin-impregnated decorative board. Since the resin-impregnated decorative board will be described below, the description is omitted here.

[0132] When the decorative sheet of the present invention is subjected to an impregnation test using melamine resin, the impregnation amount of the decorative sheet with melamine resin is, for example, 35 g / m 2 Above, can be 45g / m 2 On the other hand, the impregnation amount of the melamine resin of the decorative sheet is, for example, 80 g / m 2 Below, can be 60g / m 2 The details of the impregnation test will be described in the examples described later.

[0133] B. Resin impregnated decorative panels

[0134] Hereinafter, the resin-impregnated decorative board of the present invention will be described in detail. Figure 2 This is a schematic cross-sectional view illustrating a resin-impregnated decorative plate in the present invention. Figure 2The resin-impregnated decorative plate 100 shown in the figure comprises: the decorative sheet 10 described above; a core substrate 20 disposed so as to face the porous substrate 1 in the decorative sheet; and a cured resin layer 32 disposed in the blank region X and containing a cured product of a curable resin Y. The core substrate 20 and the porous substrate 1 contain a cured product of the curable resin Y. The resin-impregnated decorative plate 100 of the present invention is measured in the blank region X through the cured resin layer 32. In case of value, The value is 88.0 or above.

[0135] Since the resin-impregnated decorative board of the present invention includes the decorative sheet, it is possible to express a white design and stably express a glossy matte design.

[0136] 1. Decorative sheet

[0137] The details of the decorative sheet are as described above.

[0138] 2. Core substrate

[0139] The resin-impregnated decorative board of the present invention has 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 based on the white solid layer 2). As the core substrate 20, for example, phenol resin-impregnated paper can be cited. The phenol resin-impregnated paper is, for example, paper obtained by impregnating kraft paper as a core paper with a phenol resin and drying it.

[0140] 3. Cured product of curable resin and cured resin layer

[0141] The core substrate and the porous substrate in the present invention contain a cured product of a curable resin Y. The resin-impregnated decorative plate has a cured resin layer disposed in the blank area. As described later, the cured product of the curable resin filled in the core substrate and the porous substrate and the cured product of the curable resin contained in the cured resin layer are formed of the same curable resin Y. These cured resins are, for example, cured products of thermosetting resins described later.

[0142] The thickness of the cured resin layer is not particularly limited, and may be, for example, 1 μm or more, or 10 μm or more, and may be, for example, 500 μm or less, or 300 μm or less.

[0143] 4. value

[0144] The resin impregnated decorative plate of the present invention is measured in the blank area X through the cured resin layer 32. In case of value, The value is 88.0 or more, and may be 90.0 or more. The value is not particularly limited, and may be, for example, 92.0 or less, or 91.0 or less.

[0145] 5. Manufacturing method

[0146] Figure 3 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.

[0147] First, if Figure 3 (a) and Figure 3 As shown in (b), a thermosetting resin is impregnated into the porous substrate 1 of the above-mentioned decorative sheet 10 via the white solid layer 2, and a thermosetting resin layer 30' containing a thermosetting resin and covering the white solid layer 2, the pattern layer 3 and the release layer 4 is formed. As a thermosetting resin, a thermosetting resin can be widely used. As a thermosetting resin, there can be listed: melamine resin (melamine resin precursor), melamine-urea condensation resin, unsaturated polyester resin, polyurethane resin (also including two-component curing polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, guanamine resin, silicon resin, polysiloxane resin. Examples of methods for impregnating the decorative sheet 10 with the thermosetting resin include: a method of immersing the decorative sheet 10 in a bath containing the thermosetting resin; a method of applying the thermosetting resin to the decorative sheet 10 by a coater such as a contact coater or a notch wheel coater; and a method of blowing the thermosetting resin onto the decorative sheet 10 by a spray device or a shower device.

[0148] In addition, if Figure 3 As shown in (c), a release film 40 is arranged on the surface side of the thermosetting resin layer 30' opposite to the white solid layer 2, and a core substrate 20 is arranged 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 with respect to the white solid layer 2), thereby producing a first laminate 51'. In addition, the release film may have a peeling layer containing a cured product of an ionizing radiation curable resin composition on the surface opposite to the thermosetting resin layer.

[0149] Secondly, if Figure 3 As shown in (d), the first laminate 51' is heated and pressurized to cure the thermosetting resin, and the cured resin layer 31' is formed from the thermosetting resin layer 30' to produce the second laminate 52'. The heating temperature is, for example, 90°C or more and 160°C or less. In addition, the heating time is, for example, 30 seconds or more and 30 minutes or less. In addition, by applying pressure, the smoothness of the release film 40 is reflected on the surface of the cured resin layer 31'.

[0150] Secondly, if Figure 3As shown in (e), the release film 40 is peeled off from the second laminate 52', and the cured resin layer 31' between the release layer 4 and the release film 40 is also peeled off toward the release film 40 side. At this time, the cured resin layer 31' that is not peeled off toward the release film 40 side becomes the glossy layer 32. Thus, a resin-impregnated decorative board 100 having a porous substrate 1, a white solid layer 2 arranged on the entire surface of one surface of the porous substrate 1, a pattern layer 3 partially arranged on the surface of the white solid layer 2 opposite to the porous substrate 1, a release layer (matte layer) 4 arranged on the surface of the pattern layer 3 opposite to the white solid layer 2 and having a pattern shape, and a cured resin layer (glossy layer) 32 arranged in a blank area of ​​the decorative sheet can be obtained.

[0151] The resin-impregnated decorative board in the present invention is used, for example, by being arranged on the surface of a substrate. As a substrate, for example, wooden components, resin components, metal components, and ceramic components can be listed. As wooden components, for example, wooden veneers, wooden plywood, plastic plywood, and wooden fiberboard can be listed. As wood for wooden components, for example, cedar, cypress, pine, and lauan can be listed. As resins for resin components, for example, 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 can be listed. As metals for metal components, for example, iron and aluminum can be listed. The material of the ceramic component can be ceramics such as glass and ceramics, can be non-cement ceramic materials such as gypsum, and can also be non-ceramic (Japanese: non-ceramic kiln industry) materials such as ALC (lightweight air-bubbled concrete).

[0152] Examples of uses of the resin-impregnated decorative board of the present invention include building materials and furniture. Building materials may be interior materials or exterior materials. Examples of building materials include walls, floors, ceilings, doors, and sheds. Examples of furniture include tables, desks, and cabinets.

[0153] The present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative only, and embodiments having substantially the same configuration and exhibiting the same functions and effects as the technical concept described in the scope of the claims of the present invention are all within the technical scope of the present invention.

[0154] Example

[0155] [Example 1]

[0156] (Manufacture of decorative sheets)

[0157] Prepare basis weight 80g / m 2Titanium white paper (PM-77P manufactured by KJ Special Paper Co., Ltd.) was used as a porous substrate, and a white solid layer having a thickness of 2 μm was formed on the entire surface of one surface of the porous substrate by gravure printing using a printing ink for forming a white solid layer having the following composition. Furthermore, a pattern layer having a stone pattern was formed on the surface of the white solid layer opposite to the porous substrate using a printing ink for forming a pattern layer having the following composition.

[0158] <Printing ink for forming white solid layer>

[0159] · White pigment (titanium oxide) 40 parts by mass

[0160] Casein / acrylic resin (mass ratio 45:55) 10 parts by mass

[0161] 40 parts by weight of water

[0162] 5 parts by mass of dipropylene glycol

[0163] 5 parts by mass of isopropyl alcohol

[0164] <Pattern layer forming ink>

[0165] Pigment (azo, quinacridone, carbon black, etc.) 10 parts by mass

[0166] Casein / acrylic acid (mass ratio 45:55) 10 parts by mass

[0167] 70 parts by weight of water

[0168] 5 parts by mass of dipropylene glycol

[0169] 5 parts by mass of isopropyl alcohol

[0170] Using PROCESS HOMOGENIZER PH91 (manufactured by SMT Co., Ltd.), 60 parts by mass of an ionizing radiation curable monomer (ARONIX M400 manufactured by Toagosei Co., Ltd.), 0.6 parts by mass of a reactive silicone (X-22-164B manufactured by Shin-Etsu Chemical Co., Ltd.), and 40 parts by mass of methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) were stirred at a rotation speed of 2000 rpm for 1 hour to prepare an ink for forming a mold release layer.

[0171] Furthermore, the ink for forming the release layer is applied to the pattern layer in synchronization with the stone pattern of the pattern layer, and an electron beam of 3 Mrad is irradiated at an acceleration voltage of 165 kV, thereby forming a release layer with a thickness of 2 μm having a pattern shape. Thus, a decorative sheet having a porous substrate, a white solid layer, a pattern layer, and a release layer having a pattern shape is manufactured in sequence. It should be noted that, when observed from the thickness direction, the ratio (S2 / S1) of the area S2 of the blank area (the area not covered by the pattern layer) to the entire area S1 of the white solid layer is adjusted to be greater than 50% and less than 60%, including the embodiments and comparative examples described later.

[0172] (Production of release film)

[0173] A coating liquid containing 100 parts by mass of an ionizing radiation curable monomer, 2 parts by mass of a reactive silicone, 8 parts by mass of silicon oxide, and 50 parts by mass of ethyl acetate was applied at a rate of 5 g / m 2 The film was applied in an amount of 100 μm (dry) on the adhesive surface of a 50 μm thick polyethylene terephthalate film (COSMOSHINE (registered trademark) A4160 manufactured by Toyobo Co., Ltd.) and cured by irradiating an electron beam of 5 Mrad at an accelerating voltage of 165 kV. Thus, a release film having a cured resin layer was produced.

[0174] (Production of melamine decorative panels)

[0175] The produced decorative sheet was impregnated with a liquid uncured melamine resin composition containing 60 parts by mass of an uncured melamine resin (water-soluble methylol melamine resin, Nikaresin S-260 manufactured by Nippon Carbide Industries, Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol using an impregnation device so that the ratio of the uncured melamine resin composition was 80 g / m 2 (drying), and drying it to produce an impregnated decorative sheet.

[0176] The impregnated decorative sheet is laminated on 3 sheets of kraft paper impregnated with phenolic resin liquid. The basis weight is 245 g / m 2 The phenol resin-impregnated core paper (obtained by impregnating a liquid uncured resin composition containing a phenol resin into a core kraft paper) is then laminated on the release layer side of the impregnated decorative sheet so that the cured resin layer of the release film is in contact with the printed surface of the impregnated decorative sheet, thereby obtaining a first laminate. The laminate is sandwiched between two mirror panels and heated using a hot press at a pressure of 100 kg / cm 2 The molded product (second laminate) was heat molded under the conditions of 150° C. for 10 minutes. In the molded product, a melamine resin layer containing cured melamine resin was formed between the release layer and the release film.

[0177] By peeling off the release film from the cured resin layer containing the cured product of the melamine resin, the portion of the cured resin layer covered with the release layer is removed. In the portion where the release layer is not provided, the unpeeled cured resin layer remains as a glossy layer. Thus, a melamine decorative board is obtained.

[0178] [Example 2]

[0179] A decorative sheet was produced in the same manner as in Example 1, except that the thickness of the white solid layer was set to 6 μm, thereby obtaining a melamine decorative board.

[0180] [Example 3]

[0181] A decorative sheet was produced in the same manner as in Example 1, except that the thickness of the white solid layer was set to 1 μm, thereby obtaining a melamine decorative board.

[0182] [Example 4]

[0183] A decorative sheet was produced in the same manner as in Example 1, except that the porous substrate was changed to KW801P manufactured by KJ Specialty Paper Co., Ltd., to obtain a melamine decorative board.

[0184] [Example 5]

[0185] A decorative sheet was produced in the same manner as in Example 1, except that the porous substrate was changed to PM-79P manufactured by KJ Special Paper Co., Ltd., to obtain a melamine decorative board.

[0186] [Comparative Example 1]

[0187] A decorative sheet was produced in the same manner as in Example 1, except that the white solid layer was not formed, thereby obtaining a melamine decorative board.

[0188] [Comparative Example 2]

[0189] A decorative sheet was produced in the same manner as in Example 1, except that the printing ink of the white solid layer was changed to a transparent ink (not containing titanium oxide), thereby obtaining a melamine decorative board.

[0190] [Comparative Example 3]

[0191] A decorative sheet was produced in the same manner as in Example 1, except that the porous substrate was changed to PM-28P manufactured by KJ Special Paper Co., Ltd., to obtain a melamine decorative board.

[0192] [Comparative Example 4]

[0193] A decorative sheet was produced in the same manner as in Example 1, except that the porous substrate was changed to KSH801P manufactured by KJ Special Paper Co., Ltd., to obtain a melamine decorative board.

[0194] [Ash content determination]

[0195] The ash content of the decorative sheet produced as described above was measured by the above method. The results are shown in Table 1.

[0196] [evaluate]

[0197] (Decorative sheets and melamine decorative panels Value and value)

[0198] The blank area of ​​the decorative sheet obtained by the above method is measured. In the color system Value and The value of the blank area of ​​the melamine decorative board measured through the cured resin layer In the color system Value and The results are shown in Table 1.

[0199] (75° gloss value of decorative sheet)

[0200] The 75° gloss value of the blank area of ​​the decorative sheet produced in the above-mentioned manner was measured. The results are shown in Table 1.

[0201] (Pure water contact angle)

[0202] The pure water contact angle of the region exposed from the release layer of the decorative sheet produced as described above was measured by the above method.

[0203] [Measurement of Wettability]

[0204] The wettability of the region exposed from the release layer of the decorative sheet produced as described above was measured by the above method.

[0205] (White design evaluation)

[0206] The white design of the obtained melamine decorative board was evaluated by visual observation. The evaluation used separately prepared reference melamine decorative board 1 and reference melamine decorative board 2 as the reference of whiteness.

[0207] The reference melamine decorative board 1 was prepared by impregnating titanium white paper (manufactured by KJ Special Paper Co., Ltd., PM-77P) with an uncured melamine resin composition in the same manner as in Example 1 (Production of melamine decorative board) and hot pressing. The reference melamine decorative board 2 was prepared by impregnating titanium white paper (manufactured by KJ Special Paper Co., Ltd., KW801P) with an uncured melamine resin composition in the same manner as in Example 1 (Production of melamine decorative board) and hot pressing.

[0208] The observers visually compared the reference melamine decorative board 1 and the reference melamine decorative board 2 with the decorative boards produced in the examples and comparative examples. Each reference decorative board used was scored on a 5-point scale of 1 to 5 (3 points equal to the reference, 1 point for the lowest white design, and 5 points for the highest white design). Ten observers were assigned to each test, and the average score of all observers was calculated. The white design was evaluated according to the following criteria.

[0209] Evaluation benchmark

[0210] A: When either standard melamine decorative board 1 or 2 was used, the average score was 3 points or more.

[0211] B: The average score was less than 3 points when the standard melamine decorative board 2 was used, but the average score was 3 points or more when the standard melamine decorative board 1 was used.

[0212] C: When either of the standard melamine decorative boards 1 and 2 was used, the average score was less than 3 points, and red or yellow was observed.

[0213] (Gloss and matte design evaluation)

[0214] The glossy matte design of the obtained melamine decorative board was visually evaluated. Specifically, the obtained decorative board was visually observed from a position 50 cm apart under a light source of natural color fluorescent lamp color rendering AA (manufactured by Panasonic Co., Ltd., model: FLR40S·D-SDL / M) to confirm the glossy matte design and the state of the matte part (release layer).

[0215] The observers rated the glossy matte design on a 5-point scale of 1 to 5 (1 is the worst and 5 is the best). It should be noted that the case where most of the melamine peeling residue or significant whitening was observed in the matte part and the vicinity, and the glossy matte design could not be confirmed was rated as 1 point, and the case where the melamine peeling residue was not confirmed in the matte part and the glossy matte design could be confirmed was rated as 5 points, and the evaluation was graded in this way. Ten observers conducted the evaluation respectively, and the average score of all the observers was calculated, and the glossy matte design was evaluated according to the following criteria.

[0216] Evaluation benchmark

[0217] A: The average score for glossy and matte design is 3 points or more

[0218] B: The average score for glossy and matte design is 2 points or more and less than 3 points

[0219] C: The average score for glossy and matte design is less than 2 points

[0220] (Permeability Evaluation)

[0221] The impregnation properties of the produced decorative sheets were evaluated by the following method.

[0222] 1) A circular sample with a radius of 2 cm is cut out from the decorative sheet, and the mass of the sample (mass of the sample before the test) is measured.

[0223] 2) Figure 4 (a) is a schematic cross-sectional view of a container used in the permeability evaluation. Figure 4 (b) and (c) are schematic cross-sectional views and schematic three-dimensional views of the lid of the container. Figure 4 As shown, a polyethylene container (internal volume of about 300 ml) 51 having a first opening O1 is prepared. Figure 4 (a)), and a cover 52 (which can be fixed to the container 51 and has a second opening O2) Figure 4 (b) Figure 4 (c)). It should be noted that the shape of the first opening is a circle with a diameter of 3 cm (impregnation area of ​​about 0.0007 m 2 ).like Figure 5 As shown in (a), 100 g of uncured melamine resin U (obtained by dissolving 60 g of water-soluble methylol melamine resin (Nikaresin S-260 manufactured by Carbide Japan) in 40 g of pure water) is placed inside a container 51. Next, a sample S is arranged so as to cover the first opening O1. Next, the container 1 and the cover 52 are fixed by using a cover 52 to set the sample S. At this time, the sample S is set so that the surface on the white solid layer side faces the inside of the container.

[0224] 3) If Figure 5 As shown in (b), the container 51 is turned over to allow the sample S to be impregnated with the uncured material U of the melamine resin.

[0225] 4) After 30 seconds, if Figure 5 As shown in (c), the container 51 is turned over again and the sample S is quickly taken out.

[0226] 5) If Figure 5 As shown in (d), the unimpregnated melamine resin 54 remaining on the surface of the sample S on the white solid layer side is scraped off with a metal plate 53.

[0227] 6) If Figure 5 As shown in (e), after the sample S was dried at 80°C for 1 minute, the mass was measured again (mass of the sample after the test).

[0228] The melamine resin impregnation amount (g / m 2 ) and evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0229] Melamine resin impregnation amount (g / m 2 ) = {mass of sample after test (g) - mass of sample before test (g)} / opening area of ​​container (m 2 )

[0230] Evaluation benchmark

[0231] A: The impregnation amount of melamine resin is 45g / m 2 above

[0232] B: Melamine resin impregnation amount is 35g / m 2 Above and less than 45g / m 2

[0233] C: The impregnation amount of melamine resin is less than 35g / m 2

[0234] [Table 1]

[0235]

[0236] As shown in Table 1, the decorative sheets of Examples 1 to 5 can produce melamine decorative boards with good white design and glossy matte design. On the other hand, the white design of the melamine decorative board produced using a decorative sheet without a solid layer as in Comparative Example 1 is low. The white design of the melamine decorative board produced using a decorative sheet with a transparent solid layer without white pigment as in Comparative Example 2 is also low. Although Comparative Example 3 is provided with a white solid layer, the ash content of the decorative sheet is low, so the white design of the melamine decorative board is low. In Comparative Example 4, since the ash content of the decorative sheet is high, the ink used for the release layer will penetrate, so the glossy matte design is low.

[0237] Thus, in the present invention, for example, the following inventions are provided. [1]

[0239] A decorative sheet used for manufacturing a resin-impregnated decorative board.

[0240] The above-mentioned decorative sheet has:

[0241] Porous substrate;

[0242] A white solid layer disposed on the entire surface of one surface of the porous substrate and containing a white pigment;

[0243] A pattern layer partially disposed on a surface of the white solid layer opposite to the porous substrate; and

[0244] a release layer disposed on the surface of the pattern layer opposite to the white solid layer and having a pattern shape,

[0245] The white solid layer has a blank area not covered by the pattern layer.

[0246] In the blank area above The value is 93.0 or above.

[0247] The ash content in the decorative sheet is 20.0 mass % or more and 40.0 mass % or less. [2]

[0249] The decorative sheet as described in [1], wherein the white pigment contains at least one of titanium oxide and calcium carbonate. [3]

[0251] The decorative sheet according to [1] or [2], wherein the thickness of the white solid layer is 1 μm or more and 8 μm or less. [4]

[0253] The decorative sheet as described in any one of [1] to [3], wherein the porous substrate comprises titanium white paper. [5]

[0255] The decorative sheet as described in any one of [1] to [4], wherein the ash content in the decorative sheet is 22.0 mass % or more and 30.0 mass % or less. [6]

[0257] The decorative sheet as described in any one of [1] to [5], wherein the blank area of ​​the decorative sheet The value is below 4.50. [7]

[0259] The decorative sheet as described in any one of [1] to [6], wherein the 75° gloss value of the blank area of ​​the decorative sheet is 6.0 or more. [8]

[0261] The decorative sheet according to any one of [1] to [7], wherein the pure water contact angle of the region of the decorative sheet exposed from the release layer when viewed in the thickness direction is 80.0° or less. [9]

[0263] The decorative sheet according to any one of [1] to [8], wherein the decorative sheet has a wettability of 50 mN / m or more in a region exposed from the release layer when viewed in the thickness direction.

[10]

[0265] The decorative sheet as described in any one of [1] to [9], wherein the white solid layer contains a resin component, and the resin component includes a resin having a polar group.

[11]

[0267] The decorative sheet as described in

[10] , wherein the ratio of the resin having a polar group to the resin component contained in the white solid layer is 20 mass % or more and 100 mass % or less.

[12]

[0269] The decorative sheet as described in any one of [1] to

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

[13]

[0271] The decorative sheet as described in any one of [1] to

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

[14]

[0273] The decorative sheet as described in

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

[15]

[0275] The decorative sheet as described in

[14] , wherein the ionizing radiation curable resin is an electron beam curable resin.

[16]

[0277] A resin impregnated decorative board, comprising:

[0278] A decorative sheet as described in any one of [1] to

[15] ;

[0279] a core substrate arranged to face the porous substrate in the decorative sheet;

[0280] a cured resin layer disposed in the blank area and containing a cured product of a curable resin Y;

[0281] The core substrate and the porous substrate include a cured product of the curable resin Y.

[0282] The blank area is measured through the cured resin layer. In the case of the above The value is 88.0 or above.

[0283] Description of Reference Numerals

[0284] 1: Porous substrate

[0285] 2: White solid layer

[0286] 3: Pattern layer

[0287] 4: Release layer

[0288] 10:Decorative piece

[0289] 20: Core substrate

[0290] 30: Thermosetting resin layer

[0291] 40: Release film

[0292] 100: Resin impregnated decorative board

Claims

1. A decorative sheet for use in the manufacture of a resin-impregnated decorative panel, The decorative sheet has: Porous substrate; a white solid layer disposed on the entire surface of one surface of the porous substrate and containing a white pigment; A pattern layer partially disposed on a surface of the white solid layer opposite to the porous substrate; and a release layer, which is disposed on the surface of the pattern layer opposite to the white solid layer and has a pattern shape, The white solid layer has a blank area not covered by the pattern layer, The blank area The value is 93.0 or above. The ash content in the decorative sheet is 20.0 mass % or more and 40.0 mass % or less.

2. The decorative sheet according to claim 1, wherein: The white pigment includes at least one of titanium oxide and calcium carbonate.

3. The decorative sheet according to claim 1, wherein: The thickness of the white solid layer is 1 μm or more and 8 μm or less.

4. The decorative sheet according to claim 1, wherein: The porous substrate includes titanium white paper.

5. The decorative sheet according to claim 1, wherein: The ash content contained in the decorative sheet is 22.0 mass % or more and 30.0 mass % or less.

6. The decorative sheet according to claim 1, wherein: The blank area of ​​the decorative sheet The value is below 4.

50.

7. The decorative sheet according to claim 1, wherein: The 75° gloss value of the blank area of ​​the decorative sheet is greater than 6.

0.

8. The decorative sheet according to claim 1, wherein: The decorative sheet has a pure water contact angle of 80.0° or less in a region exposed from the release layer when viewed in a thickness direction.

9. The decorative sheet according to claim 1, wherein: The decorative sheet has a wettability of 50 mN / m or more in a region exposed from the release layer when viewed in a thickness direction.

10. The decorative sheet according to claim 9, wherein: The white solid layer further contains a resin component, and includes a resin having a polar group as the resin component.

11. The decorative sheet according to claim 10, wherein: The ratio of the resin having a polar group to the resin component contained in the white solid layer is 20 mass % or more and 100 mass % or less.

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

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 is an ionizing radiation curable resin.

15. The decorative sheet according to claim 14, wherein: The ionizing radiation curable resin is an electron beam curable resin.

16. A resin-impregnated decorative panel comprising: The decorative sheet according to any one of claims 1 to 15; a core substrate disposed so as to face the porous substrate in the decorative sheet; and a cured resin layer disposed in the blank area and containing a cured product of a curable resin Y, The core substrate and the porous substrate include a cured product of the curable resin Y, The blank area is measured through the cured resin layer. In the case of value, the The value is 88.0 or above.

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