JP2017052264A - Method for producing decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of simply and inexpensively producing a decorative sheet imparting designability by applying a texture on a surface.SOLUTION: There is provided a method for producing a decorative sheet which comprises: a first step of providing a release layer on a part of a porous substrate; a second step of impregnating a thermosetting resin into the porous substrate and coating the release layer with the thermosetting resin, followed by heating to thermally cure the thermosetting resin; and a third step of peeling a thermally cured resin film in a region coating the upper surface of the release layer.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a decorative board.

  Generally, a melamine decorative board whose surface layer is melamine resin-impregnated paper and whose core layer is phenol resin-impregnated paper has excellent physical properties such as strength, hardness, heat resistance, etc. It is preferably used.

  A melamine decorative board is manufactured by hot-press molding the above melamine resin-impregnated paper and phenol resin-impregnated paper. Conventionally, when a texture is given to the surface of a melamine decorative board, It has been performed by placing an embossed template (mirror plate with texture) on the surface of the resin-impregnated paper and performing hot-pressure molding (for example, Patent Document 1).

  However, this method is costly because only the type of design requires a surface-treated mirror plate.

JP-A-47-14273

  The subject of this invention is providing the method which can manufacture the decorative board which gave the design feeling by giving a texture to the surface simply and cheaply.

  As a result of intensive studies to develop a method for easily producing a decorative board having a design feeling by applying a texture to the surface, the present inventors have provided a release layer on a part of the porous substrate, It has been found that the above problem can be solved by peeling the thermoset resin in the region covering the release layer after impregnating the thermoset resin and heating. The present invention has been completed based on such findings.

That is, this invention concerns on the manufacturing method of the following decorative board.
1. A first step of providing a release layer on a part of the porous substrate;
A second step of impregnating the porous base material with a thermosetting resin and coating the release layer with the thermosetting resin, followed by heating to thermoset the thermosetting resin; and A method for manufacturing a decorative board, comprising a third step of peeling off a thermally cured resin film in a region covering the layer.
2. Item 2. The method for manufacturing a decorative board according to Item 1, wherein the thermosetting resin contains a melamine resin.
3. Item 3. The method for manufacturing a decorative board according to Item 1 or 2, wherein the porous substrate contains titanium paper.
4). Item 4. The method for producing a decorative board according to any one of Items 1 to 3, wherein the release layer contains a curable resin.
5). Item 5. The method for producing a decorative board according to Item 4, wherein the curable resin is an ionizing radiation curable resin.
6). After the release layer is coated with the thermosetting resin in the second step, the molding sheet is thermoset in a state where the molding sheet is laminated on the thermosetting resin, and the molding sheet is formed in the third step. The manufacturing method of the decorative board in any one of said claim | item 1-5 which peels the thermosetting resin film of the area | region which has coat | covered the said release layer by peeling.
7). The manufacturing method of the decorative board of said claim | item 6 whose peeling weight at the time of peeling the said shaping sheet is 0.1-10 N / inch.
8). Item 8. A shaped sheet used in the method for producing a decorative board according to Item 7, wherein a curable resin layer is laminated on a base sheet.

  According to the present invention, since a mirror-finished surface plate that has conventionally been required only for the type of design is no longer necessary, it is possible to easily and inexpensively manufacture a decorative plate that has been given a texture by applying a texture to the surface. .

It is sectional drawing which shows an example of the state after the 1st process completion | finish of the manufacturing method of this invention. It is sectional drawing which shows an example of the state after the 2nd process completion | finish of the manufacturing method of this invention. It is sectional drawing which shows an example of the decorative board after the 3rd process completion | finish of the manufacturing method of this invention. It is a cross-sectional schematic diagram explaining the measuring method of the peeling weight in an Example.

The method for producing the decorative board of the present invention comprises:
A first step of providing a release layer on a part of the porous substrate;
A second step in which the porous substrate is impregnated with a thermosetting resin and the release layer is coated with the thermosetting resin, and then the thermosetting resin is thermoset by heating; and the release A third step of peeling the thermosetting resin film in the region covering the layer is included.

  Hereinafter, each step will be described. In the present invention, the surface is a so-called “front surface”, and when the decorative board of the present invention is used by being laminated on a phenol resin-impregnated paper or a wooden substrate, It is a surface on the opposite side to the surface to be contacted, and is a surface that is visually recognized after lamination. In the present specification, the direction of the surface may be referred to as “front” or “upper”, and the opposite side may be referred to as “back” or “lower”.

(1) 1st process The 1st process is a process of providing a mold release layer in a part on a porous substrate.

  The porous substrate is not particularly limited as long as it can be impregnated with the thermosetting resin used in the second step. Examples of such a base material include a permeable fibrous base material. As the fibrous base material having permeability, a sheet-like material such as paper, synthetic paper, and non-woven fabric can be used. Paper used as the porous substrate is thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper original fabric, high-quality paper, coated paper with sol or dry lamination of polyvinyl chloride resin on paper Examples include paper, parchment paper, and Japanese paper. The paper-like sheet is a sheet of inorganic fiber such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, or carbon fiber; made of synthetic resin fiber such as polyester, vinylon, polyethylene, or polypropylene Nonwoven fabrics or woven fabrics can be used. Of these porous substrates, titanium paper is preferable from the viewpoint of impregnation with a thermosetting resin.

  The porous substrate may be colored. In this case, it can be colored by blending a coloring material (pigment or dye) at the production stage of the porous substrate, for example, at the papermaking stage if the porous substrate is paper. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. These can be selected from one or more known or commercially available ones. Further, the blending amount of the colorant may be set as appropriate according to the desired hue. Alternatively, the coloring of the porous base material can be performed by adding the above-described coloring material to the thermosetting resin and impregnating the porous base material in the second step.

  Various additives such as a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer are added to the porous substrate as necessary. It may be included.

The basis weight of the porous substrate is not particularly limited, and is preferably about 40 to 150 g / m ² . The thickness of the porous substrate can be set as appropriate depending on the use of the final product, the method of use, etc., but generally it is preferably 50 to 170 μm.

  The porous substrate may have a design such as a pattern. In order to enhance the design of the decorative board, the porous substrate preferably has a design such as a pattern. The design can be provided, for example, by forming a pattern layer on the porous substrate.

  When the pattern layer is formed on the porous substrate, the type of pattern in the pattern layer is not limited. For example, a wood grain pattern, a leather pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a geometric figure, a character, a symbol, an abstract pattern, and the like can be given.

  The method for forming the pattern layer is not particularly limited. For example, an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin is used. What is necessary is just to form in the porous base material surface by the printing method. As the ink, an aqueous composition can be used from the viewpoint of reducing the VOC of the sheet. When the pattern layer is provided by printing or the like, a solid print layer can be provided on the surface of the porous substrate before that.

  Examples of the colorant used in the ink include inorganic pigments such as carbon black, titanium white, zinc white, petal, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, and isoindolinones. Examples thereof include organic pigments such as pigments and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  As binder resin, in addition to polyester urethane resin treated with hydrophilicity, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, casein resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can be used. The said binder resin can be used individually or in combination of 2 or more types.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Chlorinated organic solvents; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to the product characteristics. The layer thickness during coating is about 1 to 200 μm, and the layer thickness after drying is about 0.1 to 20 μm.

  In order to improve the adhesion between the porous substrate or the pattern layer and the release layer, an adhesive layer may be formed on the porous substrate or the pattern layer. The adhesive layer is preferably a transparent adhesive layer, and the transparent adhesive layer includes any of colorless and transparent, colored and transparent, and translucent.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet. Examples of known adhesives in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives can be used individually by 1 type or in combination of 2 or more types. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

  If necessary, the porous substrate may be subjected to corona discharge treatment on the surface (front surface) in order to improve the adhesion of the ink for forming the pattern layer or the like. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method.

  A release layer is provided on a part of the porous substrate. The release layer can be formed, for example, using a release ink on the porous substrate.

  The resin constituting the release ink is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin). In particular, from the viewpoint of scratch resistance due to high surface hardness, convex shape retention, productivity, etc., the release ink preferably contains an ionizing radiation curable resin, and the resin constituting the release ink is an ionizing radiation curable resin. More preferably.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethanes), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  A method for forming a release layer using a release ink containing a thermosetting resin is, for example, by applying a solution of a thermosetting resin on a porous substrate by a coating method such as a roll coating method or a gravure coating method. And a method of drying and curing.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or epoxy group that can be cross-linked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when it is cured by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator (sensitizer).

  Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation-curable resins.

  The ionizing radiation curable resin preferably contains a polyfunctional polymerizable monomer in order to increase heat resistance and crosslinking density.

  The release ink preferably contains silicone oil for the purpose of imparting releasability. Examples of the silicone oil include reactive silicone oil and non-reactive silicone oil.

  The reactive silicone oil refers to a modified silicone oil having an organic group introduced into the side chain or terminal and having reactivity depending on the nature of the organic group to be introduced. As the reactive silicone oil, specifically, in the modified silicone oil side chain type, modified silicone oil both end type, modified silicone oil one end type, modified silicone oil side chain both end type, etc., the organic group to be introduced is amino-modified. , Epoxy modification, mercapto modification, carboxyl modification, carbinol modification, phenol modification, methacryl modification, heterogeneous functional group modification, and the like. These reactive silicone oils can be used alone or in admixture of two or more.

  The non-reactive silicone oil is not particularly limited as long as it is a silicone oil having no reactive functional group such as amino group, epoxy group, mercapto group, carboxy group, hydroxy group, (meth) acryloyl group, and allyl group. Non-reactive silicone oils include, for example, silicone oils composed of polysiloxanes, 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, and higher grades. Examples include fatty acid amide-modified silicone oil and phenyl-modified silicone oil. These non-reactive silicone oils can be used alone or in admixture of two or more.

  The reactive silicone oil or non-reactive silicone oil is oriented on the surface of the curable resin when the release ink is cured, and exhibits releasability.

  The usage-amount of the said reactive silicone oil or non-reactive silicone oil is about 0.1-50 mass parts per 100 mass parts of curable resin, Preferably it is about 0.5-10 mass parts. By making the usage-amount of reactive silicone oil or non-reactive silicone oil into the said range, peeling with a mold release layer and the cured resin film becomes enough.

  It is preferable that the release ink further contains an extender pigment. By containing the extender, thixotropy can be imparted to the ink, and the shape of the ink is maintained when the release layer is printed using a plate. The extender is not particularly limited, and examples thereof include silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, and magnesium carbonate. Among these, silica, which is a material having a high degree of freedom in material design and excellent in design properties, whiteness, and coating stability as an ink, is preferable, and fine powder silica is particularly preferable.

  The content of these extender pigments in the ink is about 0.1 to 20 parts by mass, preferably about 0.5 to 15 parts by mass, per 100 parts by mass of the curable resin. By making the usage-amount of extender the said range, while being able to provide sufficient thixotropy to ink, the effect which provides the expression of a protruding shape and a fine uneven surface is acquired.

  The release ink may be colorless or colored. In the case of coloring, the same colorants as those used in the above-described pattern layer can be used.

  The release ink may contain a solvent for the purpose of adjusting the viscosity. Solvents include 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; N-methylpyrrolidone, N, N -Nitrogen-containing compounds such as dimethylformamide; ether compounds such as terahydrofuran and dioxane; halogenated hydrocarbon compounds such as methylene chloride and chloroform; dimethyl sulfoxide and the like. These solvent can be used individually by 1 type or in mixture of 2 or more types. The amount of the solvent in the release ink can be appropriately set according to the viscosity of the ink.

  In the release ink, conventionally known additives can be blended depending on the desired physical properties to be obtained. Examples of additives include ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, acid value inhibitors, leveling agents, coupling agents, plasticizers, antifoaming agents, and fillers. , Thermal radical generators, aluminum chelating agents and the like.

  The thickness of the release layer is not particularly limited, and the layer thickness at the time of coating is about 1 to 100 μm, and the layer thickness after drying is about 0.1 to 20 μm.

  Here, it is preferable to set the adhesiveness between the release layer and the cured resin film formed in the second step to be weaker than the adhesiveness between the porous substrate and the release layer. Thereby, only the cured resin film formed on the release layer can be peeled from the release layer while the release layer and the porous substrate are in close contact with each other in the third step.

  An example of the state after the first step is shown in FIG. In FIG. 1, the release layer 2 is provided not on the entire porous substrate 1 but on a part thereof. By providing the release layer 2 on a part of the porous substrate 1, only the resin film 3 formed on the release layer 2 in the third step can be peeled off. Unevenness can be formed.

(2) Second Step In the second step, the thermosetting resin is impregnated with the thermosetting resin and the release layer is covered with the thermosetting resin, and then the thermosetting resin is heated. It is a process of thermosetting.

  Conventionally known thermosetting resins can be widely used as the thermosetting resin. Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. Examples include urea cocondensation resins, silicon resins, polysiloxane resins, and the like. In the present invention, it is preferable to use a melamine resin having heat resistance and stain resistance and high hardness.

  A curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, and the like can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins or polyurethane resins, organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  A porous substrate is impregnated with the thermosetting resin. In the impregnation, the thermosetting resin is supplied from 1) the release layer side of the porous substrate, that is, from the upper side of FIG. Or 3) by supplying from both sides of 1) and 2) above. This method is not particularly limited. For example, a method of immersing from a surface on which a release layer of a porous substrate is formed in a bath containing a thermosetting resin or the opposite surface; a coater such as a kiss coater or a comma coater By applying the thermosetting resin to the surface of the porous substrate on which the release layer is formed, the opposite surface, or both of these surfaces; spraying the thermosetting resin with a spray device, a shower device, etc. Examples thereof include a surface on which a release layer of the material is formed, a surface opposite to the surface, or a method of spraying on both surfaces.

  The thermosetting resin is impregnated in the porous substrate, but is not impregnated in the release layer and covers the release layer. The thermosetting resin only needs to cover at least a part of the release layer. For example, 30% or more of the total area occupied by the release layer may be covered with the thermosetting resin. The covering ratio of the thermosetting resin in the entire area of the release layer is preferably about 50 to 100%.

  Thereafter, the porous substrate impregnated with the thermosetting resin is heated to cure the thermosetting resin. The heating temperature and the heating time are appropriately adjusted depending on the type of thermosetting resin and curing agent used. For example, in the case of an isocyanate curable unsaturated polyester resin and a urethane curable polyurethane resin, it is about 1 to 5 days at about 40 to 60 ° C., and in the case of a polysiloxane resin, about 1 to 30 minutes at about 80 to 150 ° C. In the case of a melamine resin, it is about 90 to 160 ° C. and about 30 seconds to 30 minutes. When curing the thermosetting resin, pressure may be applied if necessary.

The resin impregnation rate in the porous substrate can be appropriately adjusted according to the intended performance of the decorative board, the thickness of the porous substrate, and the like. The resin impregnation rate is preferably about 30 to 200%, more preferably about 50 to 150%. The resin impregnation rate is calculated by the following formula.
Impregnation rate (%) = [weight of porous substrate after impregnation−weight of porous substrate before impregnation / weight of porous substrate before impregnation] × 100

  The thickness of the thermosetting resin film formed on the porous substrate is not particularly limited, and the combined thickness of the porous substrate and the thermosetting resin during coating is about 50 to 500 μm, after drying The total thickness of the porous substrate and the thermosetting resin is about 50 to 300 μm.

After impregnating the thermosetting resin and before heating, if necessary, a phenol resin-impregnated core paper can be laminated on the back surface of the porous substrate. Phenol resin impregnated core paper is generally impregnated with kraft paper having a basis weight of about 150 to 250 g / m ² as core paper so that the impregnation rate is about 45 to 60% and dried at about 100 to 140 ° C. It is a paper manufactured by making it. A commercial item can be used for a phenol resin impregnation core paper. When laminating the phenol resin-impregnated core paper, if necessary, the back surface of the porous substrate may be subjected to a corona discharge treatment or a back surface primer layer may be formed by applying a known primer layer. Good.

  Moreover, after impregnating a thermosetting resin, before heating, if necessary, the gloss of the surface of the thermosetting resin film can be adjusted. For example, thermosetting is performed in a state where a gloss-adjusted shaping sheet is laminated on a thermosetting resin, and an embossing template (a mirror-finished plate with a texture) is installed on the thermosetting resin to perform thermosetting. Thus, the gloss of the surface of the thermosetting resin film can be adjusted. After that, by removing the thermosetting resin film in the region covering the release layer in the third step, the part of which the gloss is adjusted by the fine unevenness by shaping on the decorative plate surface, and the release layer It is possible to easily obtain a melamine decorative board having a three-dimensional and deep design including a deep mat design portion obtained by peeling off the heat-cured resin in the region above the substrate.

  An example of the state after the end of the second step is shown in FIG. On the porous substrate 1 ′ and the release layer 2 on which the impregnated thermosetting resin is thermoset, a resin film 3 on which the thermosetting resin is thermoset is formed.

(3) Third Step The third step is a step of peeling off the thermoset resin film in the region covering the release layer.

  The method of peeling the thermosetting resin film in the region covering the release layer is not particularly limited. For example, a method of attaching a protective film such as a masking film, a cellophane tape, an adhesive tape such as a gum tape, a shaping sheet, etc. to the decorative board surface, and then peeling the film at the same time; buffing the decorative board surface; Method of peeling with silkworm, cotton cloth, scourer, melamine sponge, steel wool, high pressure washer, adhesive tape, adhesive rubber roller, adhesive rubber sheet, etc .; such as chlorinated rubber resin, urethane resin, polyester resin previously dissolved in solvent Examples include a method in which a resin solution is applied and dried and then peeled; a method in which a hot melt adhesive is applied and then peeled off at a low temperature; a method in which a resin plate or a metal plate is attached and then peeled.

  When the gloss of the surface of the resin film is adjusted in the second step, the surface of the decorative plate is peeled off by removing the heat-cured resin film in the region covering the release layer using the above method. A melamine with a three-dimensional and deep design with a gloss-adjusted part by fine irregularities by molding and a deep mat design part obtained by peeling the thermosetting resin in the area above the release layer A decorative board is easily obtained.

  Moreover, when peeling the thermosetting resin of the area | region on a mold release layer using an adhesive tape, a masking tape, a shaping sheet, etc., it is preferable to use what adjusted the peeling weight with a resin film. For example, in the case of a thermosetting film of melamine, it is preferable to adjust the peel weight of the shaped sheet or the like to 0.1 to 10 N / inch. When the peel weight is less than 0.1 N / inch, it is difficult to peel off the melamine thermoset film, and when the peel weight is 10 N / inch, the release sheet or the like may be cut off, or the thermoset film in a region other than on the release layer. May be peeled off. By using a shaping sheet or the like whose peel weight is adjusted to 0.1 to 10 N / inch, the heat-cured resin film in the region covering the release layer can be easily removed.

  Molded sheets with a peel weight adjusted to 0.1 to 10 N / inch can be laminated and thermoformed on the thermosetting resin before thermosetting the resin film in the second step. is there. In this case, removing the shaping sheet after thermosetting corresponds to the peeling step (third step). A decorative board having a sufficient design property can be obtained simply by removing the shaping sheet after thermosetting (without performing the process of attaching and peeling the above-mentioned masking tape or the like).

  As the shaped sheet in which the peel weight of the resin film in the third step is adjusted to 0.1 to 10 N / inch, various sheets can be used regardless of whether it is a single layer or multiple layers. As such a shaping sheet, a mode in which a curable resin layer is laminated on a base sheet and the surface used on the curable resin layer side in contact with the thermosetting resin film is preferably exemplified. The base sheet constituting the shaping sheet is not particularly limited as long as it is a sheet, and examples thereof include paper, non-woven fabric, and a thermoplastic resin sheet. Among these, a thermoplastic resin sheet is preferable as the base sheet, and a polyester resin sheet such as polyethylene terephthalate is particularly preferable from the viewpoint of heat resistance when the resin film is thermoset in the second step. It does not specifically limit as thickness of a base material sheet, Usually, it is about 10-200 micrometers. Moreover, as a curable resin layer which comprises a shaping sheet, it is preferable that it is a cured layer of the composition containing ionizing radiation curable resin. By using an ionizing radiation curable resin as the curable resin layer of the shaping sheet, it becomes easy to adjust the peel weight of the melamine from the thermosetting film to 0.1 to 10 N / inch. As the ionizing radiation curable resin used for the shaping sheet, the same materials as those mentioned in the section of the release layer in the first step can be used. Moreover, the composition containing ionizing radiation curable resin may contain components, such as extender, suitably for the purpose of adjusting peel weight. The thickness of the curable resin layer is usually about 1 to 30 μm.

  An example of the decorative board obtained in the third step is shown in FIG. The release layer is exposed as shown in FIG. 3 by peeling the thermosetting resin film in the region covering the release layer. Since the heat-cured resin film at the part where the release layer does not exist is not peeled off, the surface of the decorative board after peeling is a part (part without the release layer) 3a covered with the heat-cured resin film, The heat cured resin film is peeled off, and there is a portion 2 where the release layer is exposed (portion where the release layer is present), and a design difference can be obtained due to the difference in height between the two. For example, in the decorative board shown in FIG. 3, the part 3a covered with the thermosetting resin film gives a glossy design feeling, and the part 2 where the release layer is exposed gives a matte design feeling.

  Note that it is not necessary to peel off all of the thermosetting resin film existing on the release layer, and a part of the thermosetting resin film existing on the release layer may remain. A design feeling can be obtained if 50% or more of the area of the release layer is peeled off.

  Thus, a release layer is provided on a part of the porous substrate, 1) from the release layer side of the porous substrate, 2) from the back surface side of the porous substrate, or 3) the above By supplying thermosetting resin from both sides of 1) and 2), impregnating the porous base material with the thermosetting resin and coating the release layer with the thermosetting resin, and then heating. A decorative board having a sufficient surface texture can be easily produced by thermally curing the thermosetting resin and peeling off the heat-cured resin in the region above the release layer. According to this method, since the surface-treated mirror plate that is necessary only for the type of design in the conventional method is not required, the cost can be reduced. Furthermore, when a pattern layer is provided on a porous substrate, it is possible to print the release layer in synchronization with the pattern of the pattern layer by creating the pattern layer and the release layer by printing. Become. Thereby, it becomes possible to synchronize the pattern and texture of the foundation | substrate which were difficult with the conventional method, and can manufacture a decorative board with higher design property.

  The decorative board produced by the production method of the present invention has a sufficient texture on the surface and is a decorative board with high design properties. The decorative board can be used for various purposes after being subjected to a predetermined molding process. For example, the above-mentioned decorative board or a laminate of phenolic resin-impregnated core paper laminated on the back of the decorative board is laminated on a wooden substrate, and the interior of a building such as a wall, ceiling, floor, furniture, or light electrical or OA equipment It can be used for cabinets. Specific examples of wood base materials include veneer, wood veneer, wood plywood, particle board, and medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. , Chip boards, or composite substrates on which chip boards are laminated. It is preferable to use wood plywood, particle board, or medium density fiberboard (MDF) as the wood substrate.

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
(1) Production of release ink Ionizing radiation curable monomer (Toagosei Co., Ltd., Aronix (registered trademark) M400) 60 parts by mass, reactive silicone (Shin-Etsu Chemical Co., Ltd., X-22-164B) 0.6 Using a process homogenizer PH91 (manufactured by SMT Co., Ltd.), the number of rotations is 4,000 parts by mass, silica (Fuji Silysia Chemical Co., Ltd., Silicia 320) 4.8 parts by mass, and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) 40 parts by mass. A release ink was obtained by stirring at 2000 rpm for 1 hour.

(2) Manufacture of decorative board Using white titanium paper (KJ Special Paper Co., Ltd., KW-1002P) with a basis weight of 100 g / m ² as the base paper, design printing ink (DIC Graphics Co., Ltd., Ode SPTI) After printing the pattern, the wood pattern was printed using the release ink produced in (1) above, and irradiated with an electron beam of 5 Mrad at an acceleration voltage of 165 kV.

Next, a thermosetting resin composed of 50 parts by mass of melamine formaldehyde resin, 45 parts by mass of water, and 5 parts by mass of isopropyl alcohol is used at a rate of 100 g / m ² (when dried) using an impregnation apparatus for impregnation. The impregnated decorative sheet was obtained by impregnation as described above and drying. This impregnated decorative sheet is laminated on four phenol resin impregnated core papers (DL-25, manufactured by Ota Sangyo Co., Ltd.), the laminate is sandwiched between two mirror plates, and a pressure of 100 kg / cm is used using a hot press machine. ² and heat molding at a molding temperature of 150 ° C. for 10 minutes,
A molding of a high-pressure melamine decorative board was obtained.

  Next, as a peeling process, a masking tape (manufactured by Sumilon Co., Ltd .: E-207) was attached to the surface of the high-pressure melamine decorative board, and then the attached masking tape was peeled off.

Example 2
(1) Manufacture of a shaping sheet A 50 μm thick PET film (Cosmo Shine (registered trademark) A4100 (50 μm) manufactured by Toyobo Co., Ltd.), an ionizing radiation curable monomer (Aronix (registered trademark) manufactured by Toagosei Co., Ltd.) ) M350) 100 parts by weight, reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164B) 2 parts by weight, silica (Fuji Silysia Chemical Co., Ltd., Silicia 450) 8 parts by weight, and ethyl acetate 50 parts by weight The mold forming sheet coating ink was coated at 5 g / m ² (during drying), irradiated with 5 Mrad electron beam at an acceleration voltage of 165 kV, and cured to obtain a mold sheet.

(2) Production of decorative board An impregnated decorative sheet produced in the same manner as in Example 1 was laminated on four sheets of phenol resin-impregnated core paper (DL-25, manufactured by Ota Sangyo Co., Ltd.), and further on the impregnated decorative sheet. The laminate obtained by placing the shaping sheet produced in (1) above on the sheet so that the printing surface of the shaping sheet is in contact with the printing surface of the impregnated decorative sheet is sandwiched between two mirror plates, and pressure is applied using a hot press. Heat molding was performed at 100 kg / cm ² and a molding temperature of 150 ° C. for 10 minutes, and a mirror plate and a shaping sheet were removed to obtain a molded article of a high-pressure melamine decorative board.

  Next, a decorative tape was obtained by applying a masking tape (manufactured by Sumilon Co., Ltd .: E-207) to the surface of the high-pressure melamine decorative plate and removing the applied masking tape.

Comparative Example 1
A melamine decorative board of Comparative Example 1 was obtained in the same manner as in Example 1 except that the peeling step of Example 1 was not performed.

Comparative Example 2
A melamine decorative board of Comparative Example 2 was obtained in the same manner as in Example 1 except that the release ink of Example 1 was not printed.

  About the decorative board of Examples 1 and 2 and Comparative Examples 1 and 2, the design feeling and the surface height difference were evaluated as follows. The peel weight was also measured.

The design feeling was judged visually by the following evaluation criteria.
◎: Sufficient surface texture and three-dimensional and deep gloss matte feeling, very good ○: Sufficient surface texture, good x: Low surface texture, unusable

  The surface height difference was measured using a three-dimensional surface roughness measuring device SE-30K manufactured by Kosaka Laboratory Ltd. according to the method defined in JIS B 0601: 2013. Specifically, the difference in height between the part without the release layer on the decorative board surface (the part covered with the thermosetting resin film) and the part with the release layer (the part where the thermosetting resin film peeled off) Was measured. The maximum height roughness (Rz) of the surface was used as a parameter for the surface height difference. The average values at 10 locations are shown in Table 1.

  The peel weight is a value measured using a Tensilon universal material testing machine RTC-1250A manufactured by Orientec Co., Ltd., and a specific measuring method is as follows. After applying a masking tape (Sumilon Co., Ltd .: E-207) cut to a width of 1 inch on the surface of the decorative board, a part of the masking tape is peeled off and the masking tape is peeled off as shown in FIG. One end (lower part) was fixed to a testing machine. The weight when the masking tape peeled 180 ° was peeled off at a speed of 100 mm / min in the upper direction (arrow direction) was measured. Note that the reference numerals in FIG. 4 are the same as those in FIGS.

  According to the method of Example 1, a decorative board having a sufficient surface texture can be easily produced. Furthermore, according to the method of Example 2, which includes adjusting the gloss of the surface of the resin film, the surface of the decorative melamine board is coated with a portion of the fine uneven design covered with the film of the thermosetting resin. A decorative board having a deep gloss mat design in which no deep concave portions are mixed is obtained.

Example 3
(1) Manufacture of shaped sheet A shaped sheet having the composition described in Example 3 in Table 2 below on the easily adhesive surface of a 50 μm thick PET film (Cosmo Shine (registered trademark) A4100 (50 μm) manufactured by Toyobo Co., Ltd.) A forming sheet was obtained by coating 5 g / m ² (during drying) of the coating ink, applying 5 Mrad electron beam at an acceleration voltage of 165 kV, and curing.

(2) Production of decorative board An impregnated decorative sheet produced in the same manner as in Example 1 was laminated on four sheets of phenol resin-impregnated core paper (DL-25, manufactured by Ota Sangyo Co., Ltd.), and further on the impregnated decorative sheet. In addition, the laminate on which the shaping sheet produced in the above (1) is placed is sandwiched between two mirror plates, using a hot press machine at a pressure of 100 kg / cm ² and a molding temperature of 150 ° C. for 10 minutes. The high pressure melamine decorative board was obtained by heat-molding and removing the mirror surface plate and the shaping sheet.

Examples 4-10
A melamine decorative board was obtained in the same manner as in Example 3 except that the composition of the coating ink for the shaping sheet of Example 3 was changed to the compositions of Examples 4 to 10 in Table 2 below.

Comparative Example 3
A melamine decorative board was obtained in the same manner as in Example 3 except that the composition of the coating ink for the shaping sheet of Example 3 was changed to the composition of Comparative Example 3 in Table 2 below.

  About the decorative board of Examples 3-10 and the comparative example 3, peeling weight and the surface height difference were evaluated as follows.

  In the above-mentioned (2) process of manufacturing the decorative board, the peeling weight is obtained by removing the specular board by heat molding, and then cutting the shaped sheet into a 1-inch width and peeling off a part thereof. 2 and the same method as in Comparative Examples 1 and 2.

The design property was determined visually by the following evaluation criteria.
○: There is a feeling of gloss mat, good △: The gloss mat feeling is not clear, but it can be used ×: The gloss mat feeling is small and cannot be used

Purple light (registered trademark) UV1700B: UV curable urethane acrylate resin KARAYAD PET-30: Radiation curable resin Solvein (registered trademark) A: Vinyl chloride vinyl acetate copolymer resin Nipsil E220A: Silica X-22-164A: Reactive silicone MEK : Methyl ethyl ketone

  Before thermosetting the resin film, the method of Examples 3 to 10 in which the shaping sheet with the peel weight adjusted to the range of 0.1 to 10 N / inch is laminated on the thermosetting resin and thermoformed. According to this, it is possible to obtain a decorative board having a sufficient designability (gross matte feeling) simply by removing the specular plate and the shaping sheet after thermosetting.

1. Porous substrate 1 ′. 1. A porous substrate impregnated and thermoset with a thermosetting resin 2. Release layer Thermoset resin film 3a. Thermoset resin film 3 ′. 3. Thermosetting resin film peeled off by masking tape or shaping sheet Masking tape or shaping sheet

Claims (8)

A first step of providing a release layer on a part of the porous substrate;
A second step of impregnating the porous base material with a thermosetting resin and coating the release layer with the thermosetting resin, followed by heating to thermoset the thermosetting resin; and A method for manufacturing a decorative board, comprising a third step of peeling off a thermally cured resin film in a region covering the layer.   The manufacturing method of the decorative board of Claim 1 with which the said thermosetting resin contains a melamine resin.   The manufacturing method of the decorative board of Claim 1 or 2 with which the said porous base material contains titanium paper.   The manufacturing method of the decorative board in any one of Claims 1-3 in which the said mold release layer contains curable resin.   The method for producing a decorative board according to claim 4, wherein the curable resin is an ionizing radiation curable resin.   After the release layer is coated with the thermosetting resin in the second step, the molding sheet is thermoset in a state where the molding sheet is laminated on the thermosetting resin, and the molding sheet is formed in the third step. The manufacturing method of the decorative board in any one of Claims 1-5 which peels the thermosetting resin film of the area | region which has coat | covered the said mold release layer by peeling.   The manufacturing method of the decorative board of Claim 6 whose peeling weight at the time of peeling the said shaping sheet is 0.1-10 N / inch.   The shaping sheet used for the manufacturing method of the decorative board of Claim 7 formed by laminating | stacking a curable resin layer on a base material sheet.