JP2007098638A - Shaping sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shaping sheet capable of being subjected to dense shaping having a fine uneven shape and a high grade feeling and also superior in mold releasability, and a decorative sheet shaped from the shaping sheet. <P>SOLUTION: In the shaping sheet constituted by providing a transparent or translucent matte undercoating layer containing a mold release agent to at least the whole surface of a base material and partially providing a surface shaping layer to the undercoating layer, the surface shaping layer is formed by crosslinking and curing a layer comprising a curable resin composition containing the mold release agent and a matting agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has a delicate concavo-convex shape, enables high-quality and precise shaping, can easily control glossy and matte parts, has excellent design properties, and is separated. The present invention relates to a shaped sheet having excellent moldability and a decorative board shaped by the shaped sheet.

As building materials used as furniture, desk top plates, various types of housing equipment such as counters and doors, and interior materials, generally, decorative boards formed with synthetic resin materials, such as melamine resin decorative boards, are widely used.
Conventionally, there are two types of thermosetting resin decorative plates having a concavo-convex shape on the surface, one having a concavo-convex shape formed by an embossing die or a resin concavo-convex sheet, and one having a concavo-convex shape formed by a shaping sheet. However, when an embossing mold having a concavo-convex shape is used, it is necessary to subject the die to surface treatment such as blasting or etching, which limits the concavo-convex shape and the fineness of the pattern. Furthermore, when manufacturing a thermosetting resin decorative board, an expensive template and a spare template are required, which increases the labor and cost of preparing the decorative board, greatly increasing the manufacturing cost and making the product expensive. . Also, in the case of a resin uneven sheet, it is necessary to sandwich an aluminum foil, a polypropylene film, etc. between the mold plate and the thermosetting resin decorative board because it becomes difficult to peel off after the resin is cured. It is very difficult to form a sharp.

By the way, due to the recent trend toward consumer luxury goods, furniture, desks, interior materials, etc. have been required to have a high-class feeling, and the decorative panels used for these have a high-quality appearance. Is desired. For this reason, it is also important to impart a texture, and various methods for imparting a delicate uneven shape to a decorative board have been proposed.
For example, it is a moldable sheet provided with an uneven shape with ionizing radiation curable resin on the surface of the base sheet, and is desired by having a crosslinking density such that the uneven shape is not broken when the formed sheet is peeled off. A shaping sheet has been proposed that faithfully reproduces the pattern shape to be used and can be used repeatedly (see Patent Document 1 and Claims). However, since the step of peeling from the roll intaglio is made when producing the shaping sheet, there is a limit to the expression of the concavo-convex shape when the concave portion is thin.
In addition, this method has a problem that unevenness does not appear cleanly when the concave portion is thin. On the other hand, when there is a concave portion with a certain thickness, an uneven pattern is obtained on the surface of the substrate, but the height of the raised portion is high. There is also a problem that more convex portions are formed and the appearance and feel are not good.
In addition, a concave / convex layer is formed on the surface of the base sheet using a resin composition comprising an inorganic filler and a binder resin, and a fine concave / convex layer formed on a pattern formed of a liquid repellent resin is formed. There has been proposed a shaping sheet in which only the resin composition for use is repelled to form a concavo-convex layer (see Patent Document 2 and claims). However, because the concavo-convex layer is formed by repelling the resin composition for forming the concavo-convex layer, the lack of stability of the pattern due to the concavo-convex shape, and aging for a certain period to cure the concavo-convex layer, There is a problem that it is impossible to quickly respond to the diversifying needs of consumers because it takes a very long time to produce a shaped sheet.
JP 7-164519 A JP-A-5-92484

  Under such circumstances, the present invention has a delicate concavo-convex shape, can be given a high-class and precise shaping, and can easily control glossy and matte parts. An object of the present invention is to provide a moldable sheet having excellent design properties and excellent releasability, and a decorative board molded by the moldable sheet.

  As a result of intensive studies to achieve the above object, the present inventors have found that a transparent or translucent matte undercoat layer containing a release agent provided on the entire surface of the substrate, A molding sheet having a surface molding layer on an undercoat layer, wherein the surface molding layer uses a crosslinked and cured curable resin composition containing a release agent and a matting agent, We found that the problem could be solved. The present invention has been completed based on such findings.

That is, the present invention
(1) At least a transparent or translucent matte undercoat layer containing a release agent provided on the entire surface on a base material, and a surface shaping layer partially provided on the undercoat layer A shaping sheet, wherein the surface shaping layer is a cross-linked and cured curable resin composition containing a release agent and a matting agent,
(2) The mold sheet according to (1), wherein the mold release agent in the matte undercoat layer is reactive silicone, and the mold release agent in the surface mold layer is silicone (meth) acrylate,
(3) The moldable sheet according to (1) or (2), wherein the curable resin composition is an ionizing radiation curable resin composition,
(4) The shaping sheet according to (3), wherein the ionizing radiation curable resin composition is an electron beam curable resin composition,
(5) A decorative board formed by shaping the shaping sheet according to any one of (1) to (4) on a substrate,
(6) The molded sheet according to any one of (1) to (4) is inserted between a pressure plate and a substrate that is molded by pressing between heated pressure plates, and is molded. Decorative board,
(7) The decorative material according to (5) or (6) above, wherein the substrate is a melamine resin decorative board, and (8) The above (5) or (6), wherein the substrate is a diallyl phthalate (DAP) resin decorative board. The decorative board,
Is to provide.

  According to the present invention, it has a delicate concavo-convex shape, can be given a high-class and precise molding, can easily control glossy and matte parts, and has excellent design properties In addition, it is possible to obtain a shaped sheet having excellent releasability and a decorative board having a delicate uneven shape shaped by the shaped sheet.

The moldable sheet of the present invention comprises a transparent or translucent matte undercoat layer containing a release agent provided on the entire surface of the substrate, and a surface partially provided on the undercoat layer. It has a shaping layer, and the surface shaping layer is obtained by crosslinking and curing a curable resin composition containing a release agent and a matting agent.
The structure of the shaping sheet of this invention is demonstrated using FIG. FIG. 1 is a schematic view showing a cross-section of the shaping sheet 1 of the present invention. In the example shown in FIG. 1, a uniform uniform permeation preventive layer 5 covering the entire surface of the substrate 2, a matte undercoat layer 3, and a surface shaping layer 4 obtained by crosslinking and curing a curable resin composition are in this order. It is a laminated one. The surface shaping layer 4 is partially provided and forms a shaping sheet having a fine uneven shape as a whole.

Hereinafter, the structure of a base material and each layer is demonstrated in detail using FIG.
The base material 2 used in the present invention is not particularly limited as long as it is normally used as a base material for a shaping sheet, and various papers, plastic films, plastic sheets and the like are appropriately selected according to the use. Can do. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film.
When using these substrates, particularly plastic films or plastic sheets, as a substrate, an oxidation method or a concavo-convex method may be applied to one or both sides as desired in order to improve the adhesion to the layer provided thereon. Physical or chemical surface treatment can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In addition, the substrate may be subjected to a treatment such as forming a primer layer in order to enhance the interlayer adhesion between the substrate and each layer.

  As various papers used as the substrate, thin paper, kraft paper, titanium paper and the like can be used. These paper base materials are used to reinforce the interlaminar strength between the fibers of the paper base material or between the other layers and the paper base material, and to prevent the occurrence of scuffing, in addition to these paper base materials, acrylic resin, styrene butadiene rubber, A resin such as a melamine resin or a urethane resin may be added (resin impregnation after paper making or embedded during paper making). For example, inter-paper reinforced paper, resin-impregnated paper, and the like.

As a plastic film or a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resins, polypropylene resins, polymethylpentene resins, polyolefin resins such as olefinic thermoplastic elastomers; polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, vinyl chloride-vinyl acetate copolymer resins, ethylene -Vinyl resins such as vinyl acetate copolymer resins and ethylene-vinyl alcohol copolymer resins; Polyester resins such as polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate-isophthalate copolymer resins, polyester thermoplastic elastomers; Acrylic resins such as (meth) methyl acrylate resin, poly (meth) ethyl acrylate resin, poly (meth) butyl acrylate resin; polyamides such as nylon 6 or nylon 66 Fats; cellulose triacetate resins, cellulosic, such as cellophane resins; polystyrene resins; polycarbonate resins; polyarylate resin; or polyimide resins.
Among these, as the base material 2, a material excellent in heat resistance and dimensional stability is preferable, and among them, a polyester film such as a polyethylene terephthalate film is particularly preferable.

Although there is no restriction | limiting in particular about the thickness of the base material 2, When using the sheet | seat which uses a plastic as a raw material, thickness is about 20-150 micrometers normally, Preferably it is the range of 30-100 micrometers, and a paper base material is used. When used, the basis weight is usually about ²⁰ to 150 g / m ² , preferably 30 to 100 g / m ² .

  The permeation prevention layer 5 shown in FIG. 1 is a layer provided as desired, and the resin constituting the matte undercoat layer 3 and the curable resin constituting the surface shaping layer 4 are contained in the base material 2. It has a function of suppressing permeation, and is particularly effective when the substrate 2 is a permeable substrate such as paper or nonwoven fabric. Therefore, the penetration preventing layer 5 may be positioned between the base material 2 and the matte undercoat layer 3. Normally, a uniform and uniform layer obtained by crosslinking and curing a curable resin having adhesiveness with the resin constituting the matte undercoat layer 3 is formed between the base material 2 and the matte undercoat layer 3 as shown in FIG. Provided. This also fulfills the function of improving the adhesion between the substrate 2 and the matte undercoat layer 3. Further, the penetration preventing layer 5 is preferably provided in the case of a paper base material in order to stabilize the gloss reproducibility of the matte undercoat layer.

The shaped sheet of the present invention is characterized by having a transparent or translucent matte undercoat layer 3 containing a release agent provided on the entire surface.
The matte undercoat layer 3 is usually composed of a colorless or colored transparent ink containing a matting agent. Specifically, as a vehicle component, two liquids in which polyisocyanate is added as a curing agent to a resin having a functional group such as a hydroxyl group, a carboxyl group, or an amino group in an acrylic, polyester, acrylic urethane, or urethane resin. A curable resin is desirable. In the case where the glossy part is shaped by the matte undercoat layer 3 and the matte part is shaped by the surface shaping layer 4, the matte undercoat layer 3 does not contain a matting agent. Also good. The matting agent will be described in detail later.
The matte undercoat layer 3 contains a release agent. The release agent contained in the matte undercoat layer 3 is preferably reactive silicone, specifically, modified silicone oil side chain type, modified silicone oil both end type, modified silicone oil one end type, modified silicone oil. Examples thereof include both side-chain end-types in which the organic group to be introduced is amino-modified, epoxy-modified, mercapto-modified, carboxyl-modified, carbinol-modified, phenol-modified, methacryl-modified, or heterofunctional group-modified. The reactive silicone is fixed by a crosslinking reaction with the polyisocyanate used in the two-part curable resin. Therefore, when the decorative board of the present invention is molded by hot pressing, it does not bleed out on the surface of the decorative board, so the adhesion between the shaping sheet of the present invention and the decorative board is remarkably improved, and a fine uneven shape is formed. It becomes possible to mold the delicate design it has into a decorative material.
The addition amount is appropriately selected according to the type of silicone to be used and the like, but usually a range of 0.1 to 10 parts by mass per 100 parts by mass of the ink solid content is preferable. Within this range, silicone is not transferred to the surface shaping layer 4 during gravure printing of the surface shaping layer 4, and adhesion after crosslinking is not hindered.
Moreover, it is preferable to add a polymerization monomer or polymerizable oligomer which is an ionizing radiation curing component to the matte undercoat layer 3. The heat resistance of the matte undercoat layer 3 can be improved, and the adhesion with the surface shaping layer 4 can be improved.
In addition, various additives such as extender pigments, leveling agents, and antifoaming agents can be appropriately used for the matte undercoat layer 3.

Next, the surface shaping layer 4 is composed of a material obtained by crosslinking and curing the curable resin composition as described above. More specifically, printing is performed with a gravure printing plate on which a pattern is formed, and the surface shaping layer 4 partially provided on the undercoat layer is formed. Thereafter, the curable resin is cured to obtain a surface shaping layer.
Although there is no restriction | limiting in particular as curable resin composition which forms the surface shaping layer 4, For example, heat, such as a melamine type, a urea type, an epoxy type, a ketone type, a diallyl phthalate type, an unsaturated polyester type, a phenol type, etc. Examples thereof include a curable resin composition and an ionizing radiation curable resin composition. Among these, an ionizing radiation curable resin composition is preferable.
Here, the ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, crosslinking or curing by irradiating ultraviolet rays or electron beams. Refers to a resin composition. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions.
In order to form a surface shaping layer by printing, it is necessary to have proper printing. In order to form a pattern, it is necessary to set so that the transfer pattern will not be disturbed when transferred from a gravure plate to a shaping sheet. is there. Therefore, it is necessary to mainly use a resin having a high viscosity at room temperature. Specifically, a polymerizable oligomer or prepolymer is used as a main resin, and an extender pigment is added to improve the thixotropy of the ink. Further, solvent dilution is performed, the viscosity is lowered to a printable viscosity, a pattern is formed by printing, solvent drying is performed by heating, and crosslinking and curing is performed by a method such as heating or ionizing radiation irradiation. Further, a polyfunctional polymerizable monomer may be added in order to increase the heat resistance and the crosslinking density.
Typically, as the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and it is preferable to include a (meth) acrylate monomer.

  As the (meth) acrylate monomer, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate System oligomers and the like. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.
In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator and can provide stable curing characteristics.

The shaping sheet of the present invention is characterized in that the surface shaping layer 4 contains a release agent, and the release agent is preferably silicone (meth) acrylate. By making the surface shaping layer 4 contain a release agent, the releasability is improved and the resistance to repeated continuous use is improved.
Here, silicone (meth) acrylate refers to an acrylate or methacrylate having an ethylenically unsaturated double bond introduced at the side chain or terminal of the silicone, which reacts with the resin during curing with ionizing radiation and bonds together. Turn into. Therefore, when the decorative board of the present invention is molded by hot-press molding, it does not bleed out (does not ooze out) on the surface of the decorative board, and therefore the adhesion between the shaped sheet of the present invention and the decorative board is significantly improved. Therefore, it becomes possible to mold a delicate design having a fine uneven shape on a decorative material.

In addition, when an additive or filler such as a pearl pigment is included in the adherend, the detachment of the additive or filler contained in the adherend is suppressed in the process of manufacturing the decorative board. effective.
The amount of the silicone (meth) acrylate used is preferably in the range of about 0.1 to 10 parts by mass, more preferably in the range of about 0.5 to 5 parts by mass per 100 parts by mass of the ionizing radiation curable resin. It is. When the amount of the silicone (meth) acrylate used is 0.1 parts by mass or more, peeling between the decorative plate and the surface of the shaping sheet is sufficient, the uneven shape on the surface of the shaping sheet is maintained, and a longer period of time is maintained. Can withstand use. On the other hand, when the amount of the silicone (meth) acrylate used is 10 parts by mass or less, no repelling occurs when the ionizing radiation curable resin composition is applied to the substrate, and the coating surface is not roughened. Stability is improved.

Moreover, the shaping sheet | seat of this invention makes it essential to mix | blend a matting agent further with curable resin composition. The matting agent determines the content, particle size, particle size distribution, material, and shape in consideration of the design properties when it is molded and in relation to the matting agent contained in the matting undercoat layer. .
For example, with regard to the content, the larger the addition amount, the higher the matting effect, and the content of the matting agent in the surface shaping layer 4 is more than the content of the matting agent in the matting undercoat layer 3. If the number is relatively increased, the portion shaped by the surface shaping layer 4 is recognized as a matte portion, and the portion corresponding to the portion where the matte undercoat layer 3 is exposed is recognized as a glossy portion. On the contrary, if the content of the matting agent in the matting undercoat layer 3 is relatively increased, the portion molded by the surface molding layer 4 is recognized as a glossy portion. Specifically, the content of the matting agent is preferably controlled in the range of 0 to 15 parts by mass, and by controlling in this range, high designability by the glossy part and the matte part can be ensured. .
In the present invention, when the glossy part is shaped by the matte undercoat layer 3 and the matte part is shaped by the surface shaping layer 4, the matte undercoat layer 3 contains a matting agent. It does not have to be. Moreover, it is preferable that content of the matting agent in the surface shaping layer 4 is 0.1-15 mass parts with respect to 100 mass parts of resin compositions which comprise a surface shaping layer.

  Next, as the particle size of the matting agent, the matting effect is high within a certain range of the average particle size. Specifically, the particle size is preferably controlled within the range of 1 to 10 μm, and more preferably 1 It is preferably controlled in the range of ˜5 μm.

  The matting agent may be either inorganic fine particles or organic fine particles. Examples of the fine particles include inorganic particles such as silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass, and organic fine particles include acrylic resin, polycarbonate resin, and urethane type. Examples thereof include particles such as resin, urea resin, benzoguanamine resin, and benzoguanamine-melamine-formaldehyde condensate. Of these, silica particles are preferred because they have a high matting effect and can be easily controlled. Moreover, these fine particles may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, various additives can be mix | blended with the curable resin composition in this invention according to the desired physical property of the cured resin layer obtained. Examples of the additive include a polymerization inhibitor, an antistatic agent, an antioxidant, a leveling agent, a thixotropic agent, a coupling agent, an antifoaming agent, a filler, and a solvent.

Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.

In the present invention, the polymerizable monomer, polymerizable oligomer, and various additives, which are the above-mentioned curing components, are homogeneously mixed at predetermined ratios to prepare a liquid composed of the curable resin composition. The viscosity of this liquid should just be a viscosity which can form the pattern of uncured resin on the surface of a base material by gravure printing, and there is no restriction | limiting in particular.
In this invention, it is preferable that the thickness of the surface shaping | molding layer after the bridge | crosslinking provided partially is 1-5 micrometers.

In the present invention, the uncured resin layer thus formed is cured by irradiating it with ionizing radiation such as heat treatment, electron beam or ultraviolet ray. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

Next, the decorative board of the present invention is a decorative board formed by molding the above-mentioned shaping sheet on a base material. In particular, the decorative board has a fine uneven shape on the surface by inserting and molding the shaped sheet between a molded product molded by pressing between the heated pressure plates and the pressure plate, which is preferable. Specifically, as shown in FIG. 2, the decorative sheet 9 having a certain shape is obtained by peeling the molded sheet 1 from the decorative sheet 9 after hot pressing.
Further, the decorative board 9 of the present invention is not particularly limited as long as it is a decorative board produced using the shaped sheet of the present invention, but the surface is hard, heat resistance and stain resistance are excellent, and design properties Since a rich color pattern can be selected in this aspect, a melamine resin decorative board and a diallyl phthalate (DAP) resin decorative board are suitable. There are no particular limitations on the production of these decorative plates as long as they are publicly known and generally used, and for example, they can be obtained by the following production methods.
The melamine resin decorative board is made by laminating a melamine resin-impregnated sheet on about 4 phenol resin-impregnated core papers, and an overlay paper impregnated with melamine resin, and sandwiching it between two specular metal plates. For example, the mold sheet is inserted, heated and pressed at 7.8 MPa (80 kg / cm ² ), 160 ° C. for 20 minutes, allowed to cool to room temperature, and then the molded sheet is peeled off.
In addition, diallyl phthalate (DAP) resin decorative board is obtained by sequentially stacking diallyl phthalate resin impregnated paper on a plate-like base material, and in the same manner as the manufacturing method of the melamine resin decorative board, It is obtained by using and pressing 140 to 150 ° C., 0.98 MPa (10 kg / cm ² ) for about 5 minutes, allowing to cool to room temperature, and then peeling the shaped sheet. In any case, the decorative board has a delicate uneven shape.

The decorative board 9 of the present invention can be used by being attached to various substrates. Specifically, as shown in FIG. 3, a decorative board 9 is attached to the substrate 8 via the adhesive layer 7.
The board | substrate used as a to-be-adhered body is not specifically limited, A wood board, such as a timber, a ceramic material, a metal plate, etc. can be suitably selected according to a use.
As a metal plate, what consists of aluminum, iron, stainless steel, or copper, for example can be used, and what gave these metals by plating etc. can also be used.
Examples of wood-based boards include veneer of various materials such as cedar, firewood, firewood, pine, lawan, teak and melapie, and wood materials such as wood veneer, wood plywood, particle board, and medium density fiber board (MDF). . These can be used alone or in a laminated manner. The wooden board includes not only a wooden board but also a plastic board containing paper powder and reinforced paper having strength.
Examples of the ceramic material include ceramic building materials such as a gypsum plate, a calcium silicate plate, and a wood piece cement plate, ceramics, glass, firewood, fired tiles, plates made mainly of volcanic ash, and the like.
In addition to these, composites of various materials such as a fiber reinforced plastic (FRP) plate, a paper honeycomb on which both sides of an iron plate are attached, and a polyethylene resin sandwiched between two aluminum plates can be used as the substrate.

  In this way, the substrate 8 on which the decorative plate 9 is placed every leaf or continuously through the adhesive layer 7 is cold-pressed, hot-pressed, roll-pressed, laminator, lapping, edge pasting machine, vacuum press. The decorative plate 9 is bonded to the surface of the substrate 8 by pressing with a sticking apparatus such as the above.

The adhesive is applied using an application device such as a spray, spreader, or bar coater. As the adhesive, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenol resin-based, isocyanate-based adhesives, etc., are used alone or as a mixed adhesive obtained by arbitrarily mixing them. As needed, talc, calcium carbonate, clay, titanium white and other inorganic powders, wheat flour, wood flour, plastic powder, coloring agents, insect repellents, fungicides and the like can be added and mixed in the adhesive. . In general, the adhesive is applied to the substrate surface with a solid content of 35 to 80% by mass and an application amount of 50 to 300 g / m ² .
Adhesion of the decorative plate 9 on the substrate 8 is usually performed by forming the adhesive layer 7 on the back surface of the decorative plate 9 of the present invention and adhering the substrate 8 or applying an adhesive on the substrate 8. By a method such as attaching a decorative board 9.

  The building material manufactured as described above can be arbitrarily cut by cutting the building material and using a cutting machine such as a router or a cutter on the surface or the end portion of the building material. . And various uses, for example, interior or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, margins, surface decorative boards for fittings such as malls, kitchens, furniture or light electrical appliances, It can be used for surface decorative boards of cabinets such as OA equipment, interiors and exteriors of vehicles.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
Example 1
A primer ink (acrylic ink “EBF tuning primer” manufactured by Showa Ink Industries, Ltd.) is applied to the entire surface of the easily adhesive-treated polyester film (“A4100 (50 μm)” manufactured by Toyobo Co., Ltd.). )) Was gravure-printed to form a penetration preventing layer 5 (primer layer). A matte undercoat layer 3 having a thickness of 3 μm was formed on the entire surface by a gravure printing method using a matte clear ink (“GBS clear” manufactured by Showa Ink).
The composition of GBS clear is as follows.
Acrylic polyol 30 parts by weight Matting agent (silica average particle size 2 μm) 5 parts by weight Reactive silicone (modified at one end amino group) 1 part by weight Polyisocyanate (HMDI) 10 parts by weight Solvent (ethyl acetate / methyl isobutyl ketone (MIBK) ) = 1/1) 70 parts by mass Further, an electron beam curable resin (“REB-N” manufactured by Dainichi Seika Kogyo Co., Ltd.) is formed on the matte undercoat layer 3 so as to have a thickness of 2 μm. A reverse pattern of wood grain conduit was gravure printed on the undercoat layer. Here, the reverse plate refers to a pattern in which only the conduit portion is not printed.
The composition of REB-N is as follows.
Urethane acrylate 70 parts by weight Polyfunctional monomer (hexafunctional) 5 parts by weight Matting agent (silica average particle size 3 μm) 10 parts by weight Filler (fine silica average particle size 0.5 μm) 5 parts by weight Release agent (silicone methacrylate) 3 parts by mass Diluting solvent (isopropanol (IPA)) 20 parts by mass The viscosity during printing was 30 seconds with a Zahn Cup # 3 viscometer. Next, after drying with hot air at 80 ° C., an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 30 kGy (3 Mrad) is irradiated to cure the electron beam curable resin composition to form the surface shaping layer 4 to obtain a shaping sheet. It was.

Example 2
A sheet of melamine resin impregnated on about 4 sheets of phenol resin-impregnated core paper, and further, a laminate of approximately 35 g / m ² of impregnated melamine resin is laminated on it and sandwiched between two mirror metal plates. The shaping sheet produced in Example 1 having a concavo-convex shape was inserted, and press-pressed at 7.8 MPa (80 kg / cm ² ) and heated and pressed at 160 ° C. for 20 minutes. After allowing to cool to room temperature, the shaped sheet was peeled off to obtain a melamine resin decorative board having a delicate uneven surface.
It is a decorative board with excellent design properties in which the conduit portion, that is, the portion corresponding to the portion where the matte undercoat layer 3 is exposed is recognized as a mat portion (low gloss region), and the glossy portion and the matte portion are applied. there were.
The decorative board obtained in Example 2 was very delicate in the concavo-convex shape, and a high-quality design expression was possible. Moreover, the shaping sheet obtained by Example 1 was rich in durability, and even if molding was repeated 10 times, the surface shape and the releasability after shaping (ease of peeling) were not changed at all.

Comparative Example 1
A decorative board was obtained in the same manner as in Examples 1 and 2, except that the matting agent was not added to the electron beam curable resin composition. The gloss of the glossy part and the matte part was insufficient as compared with the decorative board of Example 2.

  According to the present invention, it has a delicate concavo-convex shape, can be given a high-class and precise molding, can easily control glossy and matte parts, and has excellent design properties In addition, it is possible to obtain a shaped sheet having excellent releasability and a decorative board having a delicate uneven shape shaped by the shaped sheet.

It is a schematic diagram which shows the cross section of the shaping sheet of this invention. It is a schematic diagram which shows the peeling process of the shaping sheet of this invention. It is a schematic diagram which shows the cross section of building materials.

Explanation of symbols

1. Molding sheet 2. Base material 3. Matte undercoat layer 4. 4. Surface shaping layer Penetration prevention layer 6. Convex shape Adhesive layer 8. Substrate 9. Veneer

Claims (8)

A molding sheet having a transparent or semi-transparent matte undercoat layer containing a release agent provided on the entire surface on a substrate and a surface mold layer partially provided on the undercoat layer The molding sheet is characterized in that the surface molding layer is obtained by crosslinking and curing a curable resin composition containing a release agent and a matting agent. The shaping sheet according to claim 1, wherein the release agent in the matte undercoat layer is reactive silicone, and the release agent in the surface shaping layer is silicone (meth) acrylate. The shaping sheet according to claim 1 or 2, wherein the curable resin composition is an ionizing radiation curable resin composition. The shaping sheet according to claim 3, wherein the ionizing radiation curable resin composition is an electron beam curable resin composition. The decorative board formed by shape | molding the shaping | molding sheet in any one of Claims 1-4 to a board | substrate. A decorative board, wherein the shaping sheet according to any one of claims 1 to 4 is inserted between a pressure plate and a substrate molded by pressing between heated pressure plates and molded. The decorative board according to claim 5 or 6, wherein the substrate is a decorative melamine resin board. The decorative board according to claim 5 or 6, wherein the substrate is a diallyl phthalate (DAP) resin decorative board.

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