JP2016182808A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of expressing a design feeling of a clear gross mat tone, and easy in manufacture.SOLUTION: A decorative sheet has a release layer 2 in a partial area of a surface of a porous base material 1 such as a fibrous base material having thermosetting resin permeability and has a thermosetting resin layer 3 in a residual part area of a surface of the porous base material 1 having no release layer 2, and is laminated on a wooden base material such as an internal facing of a building such as a wall, the ceiling and a floor, furniture or a cabinet of a light current or OA equipment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative board.

  Conventionally, a decorative board in which a porous base material such as titanium paper is impregnated with melamine resin and laminated on phenol core paper or the like is laminated on the surface of a table, counter, wall, floor or the like. A decorative board impregnated with such a melamine resin exhibits physical properties such as strength, hardness and heat resistance.

  The decorative board as described above is required to have a high-quality design, and a glossy matte design is imparted to the surface.

  A decorative board that has been hot-pressed using an embossed board with a glossy matte embossed shape on the surface (a mirrored board with a texture) is proposed as a decorative board with a glossy matte design. (For example, refer to Patent Document 1).

  However, when a glossy matte design feeling is imparted to the surface of the decorative plate described in Patent Document 1, a mirror plate that has been surface-treated only for the type of design is required, which is expensive and difficult to manufacture. There is. In addition, this decorative board has a problem that it is difficult to synchronize the embossed shape with the underlying pattern, and it is difficult to further improve the design.

  In addition, as a method of manufacturing a decorative board in which concave portions or the like synchronized with a pattern are formed, a thermosetting resin is impregnated with a thermosetting resin by providing a permeation prevention layer and a liquid repellent pattern layer on the surface of the base paper. At the same time, a manufacturing method for preventing a phenomenon in which a liquid-repellent pattern is covered with a film of a thermosetting resin has been proposed (for example, see Patent Document 2).

  However, in the manufacturing method described in Patent Document 2, it is difficult to completely prevent the thermosetting resin from being coated, and the decorative board manufactured by such a manufacturing method has a clear gloss matte tone. There is a problem that it is difficult to express a sense of design.

  Therefore, it is desired to develop a decorative board that can express a clear gloss matte design and is easy to manufacture.

JP-A-47-14273 JP 2002-166501 A

  It is an object of the present invention to provide a decorative board that can express a clear gloss matte design and is easy to manufacture.

  As a result of extensive research, the present inventors have a release layer in a partial area of the surface, and a decorative board having a thermosetting resin layer in the remaining area of the surface without the release layer. It was found that the above-described object can be achieved by adopting the structure, and the present invention has been completed.

That is, this invention relates to the following decorative board.
1. A decorative board having a release layer in a partial region of the surface and a thermosetting resin layer in a remaining region of the surface not having the release layer.
2. Item 2. The decorative board according to Item 1, wherein the thermosetting resin layer contains a melamine resin.
3. Item 3. The decorative board according to Item 1 or 2, wherein the release layer contains a curable resin.
4). Item 4. The decorative board according to Item 3, wherein the curable resin is an ionizing radiation curable resin.
5. Item 5. The decorative board according to Item 4, wherein the ionizing radiation curable resin has a weight average molecular weight of 500 or more.
6). Item having the release layer in a partial region of the surface of the porous substrate and not having the release layer, and having the thermosetting resin layer in the remaining region of the surface of the porous substrate. The decorative board in any one of 1-5.
7). Item 7. The decorative board according to item 6, further comprising a pattern layer between the porous substrate and the thermosetting resin layer and / or the release layer.
8). Item 8. The decorative board according to Item 6 or 7, wherein a phenol resin-impregnated paper is provided on a surface of the porous substrate opposite to the side having the thermosetting resin layer and the release layer.

  The decorative board of the present invention has a release layer in a partial area of the surface and a thermosetting resin layer in the remaining area of the surface that does not have a release layer. Therefore, the decorative board is separated from the thermosetting resin layer. By showing a design feeling different from the mold layer, it is possible to express a glossy matte design feeling with a clear decorative board surface.

  Further, the decorative board of the present invention having the above-described configuration is provided with a release layer in a partial region of the surface, impregnated with a thermosetting resin, heated, and coated with the release layer. Since it can manufacture by peeling off, it can manufacture easily.

It is sectional drawing which shows typically an example of the laminated constitution of the decorative board of this invention. In the manufacturing method which manufactures the decorative board of this invention, it is sectional drawing which shows an example of the state after process 1 completion | finish. In the manufacturing method which manufactures the decorative board of this invention, it is sectional drawing which shows an example of the state after process 2 completion | finish.

  The decorative board of the present invention is a decorative board having a release layer in a partial area of the surface and a thermosetting resin layer in the remaining area of the surface not having the release layer. That is, in the decorative board of the present invention, a release layer is formed in a part of the surface, and a thermosetting resin layer is formed in the remaining part of the surface where the release layer is not formed. ing.

  Hereinafter, the decorative board of the present invention 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”.

  FIG. 1 is a cross-sectional view schematically showing an example of the layer structure of the decorative board of the present invention. In FIG. 1, the decorative board of the present invention is impregnated with a thermosetting resin, and a release layer 2 and a thermosetting resin layer 3 are formed on a thermosetting porous substrate 1. Due to such a layer structure, the decorative board of the present invention shown in FIG. 1 has a surface in which the release layer 2 is formed in a partial region of the surface and the release layer 2 is not formed. The thermosetting resin layer 3 is formed in the remaining region.

  The decorative board of the present invention illustrated in FIG. 1 has the above-described configuration, so that the thermosetting resin layer 3 exhibits a glossy design feeling and the release layer 2 exhibits a mat design feeling, or heat When the curable resin layer 3 shows a mat design feeling and the release layer 2 shows a glossy design feeling, the decorative surface of the decorative board can have a clear gloss matte design feeling. Further, the decorative board of the present invention of FIG. 1 having the above configuration is provided with a release layer 2 in a partial region of the surface of the porous substrate 1, and the porous substrate 1 is impregnated with a thermosetting resin. Since it can manufacture by peeling off the thermosetting resin film which has heated and coat | covered the release layer 2, it can manufacture easily.

  Area ratio (Sa) of the area (Sa) of the region where the thermosetting resin layer is formed on the surface of the decorative board of the present invention and the area (Sb) of the region where the release layer is formed: (Sb ) Is preferably 3: 7 to 9: 1, more preferably 5: 5 to 8: 2. When the area ratio (Sa) :( Sb) is within the above range, the gloss matte design expressed by the decorative board of the present invention becomes clearer.

  The height difference between the thermosetting resin layer and the release layer is preferably 1 to 50 μm, and more preferably 2 to 30 μm. When the height difference is within the above range, the gloss matte design expressed by the decorative board of the present invention becomes clearer.

  Hereinafter, the layer structure of the decorative board of the present invention will be described. In the decorative board of the present invention, the release layer is formed in a part of the surface as described above, and the thermosetting resin layer is formed in the remaining part of the surface where the release layer is not formed. If it is, the specific configuration (layer configuration) is not limited. For example, when the decorative board of the present invention includes a porous substrate, the release layer is formed in a partial region of the surface of the porous substrate, and the release layer is not formed. In the remaining area of the surface, a configuration in which a thermosetting resin layer is formed may be mentioned.

  Hereinafter, each layer will be specifically described with the decorative board having such a layer configuration as a representative example.

(Release layer)
The release layer is formed in a partial region of the surface of the decorative board of the present invention. The release layer is separated from the thermosetting resin resin film once formed on the surface of the release layer when the thermosetting resin layer is formed in the manufacturing process of the decorative board of the present invention described later. If it has a moldability, it will not specifically limit. The release layer can be formed, for example, by applying release ink to the surface of a porous substrate or the like and curing it.

  As the resin constituting the release ink, a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin); a thermoplastic resin can be used, but a curable resin should be used. Is preferred. 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. Especially, it is preferable to use 1 or more types of a polyfunctional monomer and an oligomer. Examples of the ionizing radiation curable resin include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.

  The weight average molecular weight of the ionizing radiation curable resin is preferably 500 or more, and more preferably 1000 or more. By setting the weight average molecular weight of the ionizing radiation curable resin within the above range, the release layer is formed when the release layer is formed by applying and releasing the release ink on the surface of the porous substrate as described above. The penetration of the mold ink into the porous substrate or the like is suppressed, and the release layer can be formed more reliably.

  The weight average molecular weight of the ionizing radiation curable resin is preferably 80000 or less, and more preferably 50000 or less. By setting the weight average molecular weight of the ionizing radiation curable resin within the above range, the release layer is formed when the release layer is formed by applying and releasing the release ink on the surface of the porous substrate as described above. The increase in the viscosity of the mold ink can be suppressed, and it is difficult to apply the release ink.

  In this specification, the weight average molecular weight is a value measured using polystyrene as a standard substance by gel permeation chromatography (GPC).

  The ionizing radiation curable resin is preferably at least one selected from polyfunctional monomers and oligomers having a weight average molecular weight of 500 or more. Examples of such polyfunctional monomers or oligomers include acrylate resins such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, urethane acrylate, polyester acrylate, and epoxy acrylate.

  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, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  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 amount of the reactive silicone oil or non-reactive silicone oil used is about 0.1 to 50 parts by mass, preferably about 0.5 to 20 parts by mass, per 100 parts by mass of the resin constituting the release ink. More preferably, it is about 3-20 mass parts, More preferably, it is about 3-10 mass parts. By making the usage-amount of a reactive silicone oil or a non-reactive silicone oil into the said range, the mold release property of a mold release layer and the hardened resin film will become 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, more preferably 2 per 100 parts by mass of the resin constituting the release ink. It is about -15 mass parts, More preferably, it is about 5-15 mass parts. 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. When coloring, the thing similar to the coloring agent used with the pattern pattern layer mentioned later can be used.

  The release ink may contain a solvent for the purpose of adjusting the viscosity. Solvents 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; N-methylpyrrolidone, N , N-dimethylformamide and the like; 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. As additives, for example, ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, coupling agents, plasticizers, antifoaming agents, fillers, Examples include a thermal radical generator and an aluminum chelating agent.

  The release layer may be formed in a desired pattern on the surface of the decorative board of the present invention. Examples of the pattern for forming the release layer include a wood grain plate conduit, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.

  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.

(Thermosetting resin layer)
A thermosetting resin layer is formed in the remaining area | region where the said release layer is not formed of the surface of the decorative board of this invention. The thermosetting resin layer may cover a part of the release layer. If a portion of 50% or more of the area of the release layer is exposed and visually recognized from the surface of the decorative board, a glossy matte design feeling can be exhibited.

  As the thermosetting resin used for forming the thermosetting resin layer, conventionally known thermosetting resins can be widely used. 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 thermosetting 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.

  As a method of forming the thermosetting resin layer, for example, when the decorative board of the present invention has a porous base material, a method of impregnating the porous base material with the thermosetting resin may be mentioned. In the impregnation, the above thermosetting resin is supplied from 1) the release layer side of the porous substrate, that is, from the upper side of FIG. 1, and 2) supplied from the back side of the porous substrate, that is, from the lower 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. In addition, the said thermosetting resin should just coat | cover at least one part of a mold release layer, for example, 30% or more of the total area which a mold release layer occupies should just be coat | 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%.

  A thermosetting resin layer can be formed by heating a porous substrate impregnated with a thermosetting resin to cure the thermosetting resin. The heating temperature and the heating time are appropriately adjusted depending on the type of thermosetting resin 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.
Resin impregnation rate (mass%) = [(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 layer is not particularly limited, and the total thickness of the porous base material and the thermosetting resin during coating is preferably about 50 to 500 μm, and the porous base material after drying and thermosetting The total thickness with the conductive resin is preferably about 50 to 300 μm.

(Porous substrate)
The porous substrate is not particularly limited as long as it can be impregnated with a thermosetting resin for forming a thermosetting resin layer. An example of such a porous substrate is a permeable fibrous substrate. 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, thin paper, kraft paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, and Japanese paper are preferred in terms of impregnation with thermosetting resin. Titanium paper is more preferred.

  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.

  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.

  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.

(Pattern pattern layer)
In the decorative board of the present invention, if necessary, a pattern layer may be further formed between the porous substrate and the thermosetting resin layer and / or the release layer.

  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 on the base-material sheet | seat 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 appropriately set according to product characteristics. However, the layer thickness at the time of coating is preferably about 1 to 200 μm, and the layer thickness after drying is preferably about 0.1 to 20 μm.

(Adhesive layer)
An adhesive layer may be formed on the porous substrate or the pattern layer in order to improve the adhesion between the porous substrate or the pattern layer and the release layer and the thermosetting resin 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 board. Examples of the adhesive known in the decorative board field include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and thermosetting resins such as urethane resin. 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.

(Phenolic resin impregnated paper)
The decorative board of the present invention may be laminated with a phenol resin-impregnated paper as necessary. The phenol resin-impregnated paper is preferably laminated on the surface of the porous substrate opposite to the side on which the thermosetting resin layer and the release layer are formed.

The phenol resin impregnated paper is generally impregnated with kraft paper having a basis weight of about 150 to 250 g / m ² as a 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 this. A commercially available product can be used for the phenol resin-impregnated paper. When laminating phenol resin impregnated paper, if necessary, the back surface of the porous substrate may be subjected to corona discharge treatment, or a back surface primer layer may be formed by applying a known primer layer. .

(Back primer layer)
The back surface of the porous substrate (the surface opposite to the surface on which the pattern layer or the release layer and the thermosetting resin layer are laminated) or the back surface of the phenol resin-impregnated paper (the surface on which the porous substrate is laminated) A reverse primer layer may be provided on the opposite surface) as required. Providing the back primer layer is effective, for example, when laminating the decorative board of the present invention and the adherend.

  The back primer layer can be formed by applying a known primer to a porous substrate or phenol resin impregnated paper. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane-based resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.

Although the application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a back surface primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

  The decorative board of the present invention can express a clear gloss matte design 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 decorative plate can be laminated on a wooden base material and used for interiors of buildings such as walls, ceilings, floors, furniture, cabinets for light electrical or OA equipment, and the like. 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.

(Manufacturing method of decorative board)
Although it does not specifically limit as a manufacturing method of the decorative board of this invention, For example, when the decorative board of this invention has a porous base material, it can manufacture with the manufacturing method which has the following processes 1-3. (1) Step 1 of providing a release layer in a partial region of the surface of the porous substrate,
(2) Step 2 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; 3) Step 3 for removing the thermosetting resin film in the region covering the release layer.

(Process 1)
Step 1 is a step of providing a release layer in a partial region of the surface of the porous substrate. The above-mentioned thing can be used for the porous base material used in the said process 1. FIG. Moreover, the above-mentioned method can be used as a method of providing a release layer in a partial region of the surface of the porous substrate.

  An example of the state after completion of Step 1 is shown in FIG. In FIG. 2, the release layer 2 is provided not in the whole surface of the porous substrate 1 'but in a part of the region. By providing the release layer 2 in a part of the surface of the porous substrate 1 ′ in the step 1, the resin film 3 ′ covering the upper part of the release layer 2 can be peeled in the step 3. It is possible to form a release layer in a partial area of the surface of the decorative board, and to form a thermosetting resin layer in a remaining area of the surface where the release layer is not formed, and Unevenness can be formed on the decorative plate surface.

(Process 2)
Step 2 is a 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. The above-mentioned thing can be used for the thermosetting resin used in the above step 2. Moreover, the above-mentioned method can be used as a method of heating after impregnating the porous substrate with a thermosetting resin and coating the release layer with the thermosetting resin.

  An example of the state after completion of step 2 is shown in FIG. In FIG. 3, a thermosetting resin layer 3 is formed on a porous substrate 1 obtained by thermosetting the impregnated thermosetting resin. Further, a resin film 3 ′ obtained by thermosetting a thermosetting resin is formed on the release layer 2.

(Process 3)
Step 3 is a step of peeling off the thermosetting resin film covering the release layer. There is no particular limitation on the method for peeling the thermosetting resin film covering the release layer. For example, a method of sticking a protective film such as a masking film on the decorative plate surface, and then peeling the film, a method of buffing the surface of the thermosetting resin film, and the like can be mentioned.

  As a method of peeling the thermosetting resin film covering the release layer, the method is also a method of rubbing the resin film and polishing it with melamine sponge, steel wool, etc .; cellotape (registered trademark) on the resin film, A method of applying and peeling an adhesive tape such as a gum tape (registered trademark); After applying a resin solution such as a chlorinated rubber resin, a urethane resin, or a polyester resin previously dissolved in a solvent on the resin film and drying it Method of peeling; Method of peeling at low temperature after applying hot melt adhesive on resin film; Method of peeling after attaching resin plate, metal plate, etc. to resin film; High pressure cleaning of resin film A method of cleaning and peeling with a machine; a method of peeling a resin film with an adhesive rubber roller, an adhesive rubber sheet or the like.

  By the process 3, the decorative board of the present invention shown in FIG. 1 can be obtained. By releasing the thermosetting resin film covering the release layer, the release layer 2 is exposed as shown in FIG. In the place where the release layer 2 does not exist, the thermosetting resin layer 3 is not peeled off even by the step 3. Thereby, the mold release layer 2 is formed in a partial area of the surface, and the thermosetting resin layer 3 is formed in the remaining area of the surface where the mold release layer 2 is not formed. A decorative board can be obtained.

  The decorative board of the present invention produced by the above-described method includes a release layer formed in a partial region of the surface, and a thermosetting resin formed in the remaining region of the surface where the release layer is not formed. The layer can express a clear gloss matte design feeling. For example, in the decorative board shown in FIG. 1, the thermosetting resin layer 3 gives a glossy design feeling and the release layer 2 gives a matte design feeling, thereby expressing a clear glossy matte design feeling. can do. Further, by increasing the difference in height between the thermosetting resin layer 3 and the release layer 2, the gloss matte design feel becomes clearer.

  In Step 3, it is not necessary that all of the thermosetting resin film existing on the release layer is peeled off, and a part of the thermosetting resin film existing on the release layer remains. Also good. If 50% or more of the area of the release layer is peeled off, a glossy matte design feeling can be obtained.

  As described above, the surface of the decorative board is provided by providing a release layer on a part of the porous substrate, impregnating the thermosetting resin, heating, and then peeling off the thermosetting resin film on the release layer. Can express a vivid gloss matte design. Since the decorative board of the present invention can be manufactured by the above-described method, a surface-finished mirror plate that is necessary only for the type of design in the conventional method is not necessary, so that it can be easily manufactured and the cost can be reduced. Can be lowered. Furthermore, when the pattern layer is provided on the 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. As a result, it becomes possible to synchronize the background pattern and the gloss matte design, which was difficult with the conventional method, and it is possible to manufacture a decorative board with higher design.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
(1) Preparation of release ink Ionizing radiation curable monomer (Toagosei Co., Ltd., Aronix M400) 60 parts by mass, reactive silicone (Shin-Etsu Chemical Co., Ltd., X-22-164B) 0.6 parts by mass, and A release ink was prepared by stirring 40 parts by mass of methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) using a process homogenizer PH91 (manufactured by SMT Co., Ltd.) at a rotational speed of 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 grain pattern was printed using the release ink produced in (1) above, and irradiated with 5 Mrad of electron beam at an acceleration voltage of 165 kV to form a release layer. Since the release layer has a wood grain pattern, there are a thick portion and a thin portion, and the thickness of the release layer was 0.2 to 3 μm.

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 sheets of phenol resin-impregnated core paper (Ota Sangyo Co., Ltd., Ota Core) having a basis weight of 245 g / m ² in which a kraft paper is impregnated with a resin solution comprising a phenol resin. Is sandwiched between two mirror plates and heat-molded using a hot press machine at a pressure of 100 kg / cm ² and a molding temperature of 150 ° C. for 10 minutes to form a thermosetting resin layer containing a melamine resin. As a result, a molded article of a high-pressure melamine decorative board was obtained. At this time, a thermoset resin film was formed on the release layer.

  Next, as a peeling step, a masking tape (manufactured by Sumilon Co., Ltd .: E-207) is pasted on the surface of the high-pressure melamine decorative board, and then the pasted masking tape is peeled off to form a thermosetting resin film formed on the release layer. Was peeled off to produce a decorative board. The thickness of the thermosetting resin layer of the obtained decorative board was 30 μm, and the height difference between the release layer and the thermosetting resin layer, that is, the surface height difference of the decorative board was 5 μm.

Examples 2 to 21
A decorative board was produced in the same manner as in Example 1 except that the composition of the release ink was changed as shown in Table 1.

Comparative Example 1
A decorative board was produced in the same manner as in Example 1 except that the wood grain pattern was not printed.

Examples 22-37
Example 1 except that the resin shown in Table 3 was used as the resin constituting the release ink, and the composition of the release ink was changed as shown in Tables 6 and 7 using silica shown in Table 4 and silicone shown in Table 5. In the same manner, a decorative board was produced.

  About the decorative board of Examples 1-37 and the comparative example 1, the design feeling and the surface height difference were evaluated with the following measuring methods.

Was visually observed the surface of the design sense veneer was evaluated based on the following evaluation criteria.
◎: Glossy matt feeling is sufficiently clear, good ◯: Glossy matt feeling is clear, good △: Glossy matt feeling is not clear but can be used ×: Glossy matt feeling is not clear and cannot be used

The surface height difference of the decorative sheet was measured using a three-dimensional surface roughness measuring instrument SE-30K manufactured by Kosaka Laboratory Ltd. according to the method defined in JIS B 0601: 2013. Specifically, the area where the release layer is not formed on the decorative board surface (area where the thermosetting resin layer is formed) and the area where the release layer is formed (the thermosetting resin film is peeled off) The height difference from the part) 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 results are shown in Tables 1, 2, 6 and 7.

1. Porous substrate 1 '. Impregnated and thermoset with thermosetting resin. 1. porous substrate 2. Release layer Thermosetting resin layer 3 ′. Thermoset resin film

Claims (8)

  A decorative board having a release layer in a partial region of the surface and a thermosetting resin layer in a remaining region of the surface not having the release layer.   The said thermosetting resin layer is a decorative board of Claim 1 containing a melamine resin.   The decorative sheet according to claim 1, wherein the release layer contains a curable resin.   The decorative board according to claim 3, wherein the curable resin is an ionizing radiation curable resin.   The decorative sheet according to claim 4, wherein the ionizing radiation curable resin has a weight average molecular weight of 500 or more.   Having the release layer in a partial region of the surface of the porous substrate, and not having the release layer, and having the thermosetting resin layer in the remaining region of the surface of the porous substrate, The decorative board in any one of claim | item 1 -5.   The decorative board according to claim 6, further comprising a pattern layer between the porous substrate and the thermosetting resin layer and / or the release layer.   The decorative board according to claim 6 or 7, wherein a phenol resin-impregnated paper is provided on a surface of the porous substrate opposite to the side having the thermosetting resin layer and the release layer.

Images