JP2023006943A - Resin composition for decorative plate, decorative sheet, and decorative plate - Google Patents

Abstract

To provide a resin composition for a decorative plate which enables manufacture of a decorative plate that has incombustibility, and satisfies at least one of excellent releasability from a mirror surface plate after hot-press molding, and synchronism when subjected to emboss processing.SOLUTION: A resin composition for a decorative plate contains a diallyl phthalate-based resin, a polyfunctional compound and aluminum hydroxide, wherein an average particle diameter of the aluminum hydroxide is 3 μm or less.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a decorative board resin composition, a decorative sheet, and a decorative board. More particularly, the present invention relates to a decorative board resin composition, a decorative sheet using the decorative board resin composition, and a decorative board comprising the decorative sheet.

Conventionally, on the surfaces of tables, counters, walls, floors, etc., a resin-impregnated layer such as impregnated paper obtained by impregnating a paper base material such as titanium paper with a thermosetting resin such as diallyl phthalate resin is applied on the base material. After lamination, a mirror plate is placed on the resin-impregnated layer and subjected to thermocompression molding to cure the thermosetting resin. The surface of the decorative sheet may be subjected to high-gloss treatment, low-gloss treatment (matte treatment), embossing, or the like for the purpose of imparting a sense of quality or desired patterns. Among them, a decorative board using a diallyl phthalate-based resin is known as a decorative board having weather resistance, natural texture, heat resistance, chemical resistance, and dimensional stability.

By superimposing a substrate having an uneven shape on the surface of the decorative board, an uneven shape is formed on the surface of the resin-impregnated layer, and embossing can be performed. When the resin-impregnated layer contains a color pigment, when embossed, the convex portions of the resin-impregnated layer become darker, and the concave portions become lighter. ) is expressed (see, for example, Patent Document 1).

In addition, the decorative board is sometimes required to be flame-retardant or non-combustible from the viewpoint of disaster prevention. BACKGROUND ART A decorative board is known in which a flame retardant such as aluminum hydroxide is blended in a resin-impregnated layer for the purpose of imparting flame retardancy or non-combustibility to the decorative board (see, for example, Patent Documents 2 to 4).

JP-A-5-147050 JP 2011-79870 A Japanese Patent Application Laid-Open No. 2009-234200 JP 2006-35839 A

However, when aluminum hydroxide is added to the resin-impregnated layer in such an amount that the resin-impregnated layer is sufficiently incombustible, the resin-impregnated layer is stuck to the mirror plate that is superimposed on the resin-impregnated layer during thermocompression molding for molding the decorative plate. , there is a problem that it becomes difficult to release the mirror plate.

In addition, when aluminum hydroxide is added to a resin-impregnated layer containing a coloring pigment and embossed, the color depth (synchronization) corresponding to the thickness of the resin-impregnated layer may not be developed.

Accordingly, an object of the present invention is to provide a nonflammable decorative board that exhibits at least one of excellent releasability from a mirror plate after thermocompression molding and excellent synchronism when embossed. An object of the present invention is to provide a resin composition for a decorative board that can obtain a decorative board that satisfies the requirements.

The present inventors have made intensive studies to achieve the above objects, and found that aluminum hydroxide having an average particle size within a specific range is added to a resin composition for a decorative board containing a diallyl phthalate-based resin and a polyfunctional compound. A decorative board having noncombustibility by blending the decorative board, which satisfies at least one of excellent releasability from a mirror plate after hot-press molding and excellent synchronism when embossed. I found that I can get The present invention has been completed based on these findings.

That is, the present invention provides a resin composition for a decorative board, comprising a diallyl phthalate-based resin, a polyfunctional compound, and aluminum hydroxide, wherein the aluminum hydroxide has an average particle size of 3 μm or less.

The resin composition for a decorative board may contain a coloring pigment.

The resin composition for a decorative board may contain magnesium hydroxide.

The content of aluminum hydroxide is preferably 5 to 90 parts by mass with respect to a total of 100 parts by mass of the diallyl phthalate-based resin and the unsaturated polyester-based resin.

Further, the present invention includes a resin-impregnated layer containing an impregnated base material and a thermosetting resin composition impregnated in the impregnated base material, wherein the thermosetting resin composition is the resin composition for a decorative board or its Provided is a decorative sheet that is a cured product.

It is preferable that the resin-impregnated layer has the resin composition for a decorative sheet on the surface thereof which is to be the side of the mirror plate during thermocompression molding.

The decorative sheet may have an embossed shape on the surface of the resin-impregnated layer.

The present invention provides a decorative board comprising a base material and the decorative sheet provided on at least one surface of the base material.

The surface of the resin-impregnated layer opposite to the substrate may have an embossed shape.

According to the resin composition for a decorative board of the present invention, the decorative board is a nonflammable decorative board, has excellent releasability from the mirror plate after hot-press molding, and has excellent synchronism when embossed. It is possible to obtain a decorative laminate that satisfies at least one of these requirements.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one Embodiment of the decorative board using the resin composition for decorative boards of this invention. FIG. 3 is a cross-sectional view showing another embodiment of a decorative board using the resin composition for a decorative board of the present invention. 3 is a view showing an embodiment of a method for manufacturing the decorative board shown in FIG. 2; FIG. FIG. 2 is a diagram showing an embodiment of a method for manufacturing a decorative board having an embossed shape on the surface of a resin-impregnated layer;

[Resin composition for decorative board]
The resin composition for a decorative board of the present invention contains at least a diallyl phthalate-based resin, a polyfunctional compound, and aluminum hydroxide.

The diallyl phthalate-based resin is a prepolymer having an allyl group in the molecule and is a thermosetting resin (thermosetting resin).

The diallyl phthalate-based resin contains at least a structural unit derived from a diallyl phthalate-based monomer. Examples of the diallyl phthalate-based monomers include diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate. Only one type of the diallyl phthalate-based monomer may be used, or two or more types may be used. Moreover, the diallyl phthalate-based resin may be used alone or in combination of two or more. The weight-average molecular weight of the diallyl phthalate-based resin as determined by the GPC method is preferably 10,000 to 50,000.

The decorative board resin composition contains a polyfunctional compound for cross-linking the diallyl phthalate resin. By using a polyfunctional compound, the hardness of the resin-impregnated layer after thermosetting can be improved, and releasability, sharpness of image, and glossiness can be improved. As the polyfunctional compound, a polyfunctional monomer having at least two polymerizable functional groups having an unsaturated carbon-carbon double bond such as a (meth)acryloyl group or a vinyl group, or a polymerization of the polyfunctional monomer. Polyfunctional compounds such as coalescence are included. Only one kind of the polyfunctional compound may be used, or two or more kinds thereof may be used.

Examples of the polyfunctional compound include hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetra Polyfunctional (meth)acrylates such as methylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di(meth)acrylate, hexyl di(meth)acrylate, etc. acrylates and the like. As the polyfunctional compound, poly(meth)acrylate of dipentaerythritol having three or more (meth)acryloyl groups in the molecule is preferable.

The content of the polyfunctional compound is preferably 5 to 100 parts by mass, more preferably 10 to 75 parts by mass, based on 100 parts by mass of the diallyl phthalate resin. When the content is within the above range, the hardness of the resin-impregnated layer after thermosetting becomes more moderate, and the releasability becomes more moderate. In addition, sharpness and gloss are further improved, and appearance is improved.

The mass ratio (the former: the latter) of the diallyl phthalate-based resin and the polyfunctional compound in the resin composition for decorative board is not particularly limited, but is preferably 90:10 to 10:90, more preferably 90:10 to When the ratio is 50:50, the glossiness, alkali resistance, and releasability of the decorative board tend to be more excellent.

The total content of the diallyl phthalate-based resin and the polyfunctional compound in the resin composition for decorative board is preferably 20 to 90% by mass with respect to the total amount (100% by mass) of the resin composition for decorative board. , more preferably 30 to 85% by mass, more preferably 40 to 80% by mass. When the content is 20% by mass or more, a resin-impregnated layer having sufficient strength can be obtained by thermocompression molding.

The resin composition for a decorative board may contain a monomer constituting a diallyl phthalate-based resin or an oligomer of the monomer (for example, a polymer of 2 to 3 units). For example, it may contain the diallyl phthalate-based monomer, which is a structural unit of the diallyl phthalate-based resin.

The resin composition for a decorative board contains aluminum hydroxide. By containing aluminum hydroxide, the decorative board has noncombustibility. The shape of aluminum hydroxide is not particularly limited, and may be columnar, acicular, spherical, and the like. Only one type of aluminum hydroxide may be used, or two or more types may be used.

The average particle size of aluminum hydroxide in the resin composition for a decorative board is 3 µm or less, preferably 2 µm or less, and more preferably 1.5 µm or less. When the average particle diameter is 3 μm or less, the flow of the resin composition during hot compression molding is suppressed, a sufficient thickness of the resin film can be secured, and the releasability from the mirror plate is excellent. In addition, it has high transparency and excellent appearance. In addition, it is presumed that when a pressure plate having an uneven shape is superimposed on the resin-impregnated layer, the movement of the color pigment is not hindered in the portion where the resin composition is thin, and the synchronism is excellent. Furthermore, it is excellent also in transparency. The average particle size is, for example, 0.2 μm or more, and may be 0.3 μm or more, or 0.5 μm or more. The average particle size can be measured by a laser diffraction/scattering particle size distribution measuring device, can be measured from an electron micrograph, or can be calculated from the electron micrograph using an image processing device. can also Generally, the average particle size is measured by a laser diffraction method.

Aluminum hydroxide may be surface-treated. By applying the surface treatment, the dispersibility in the resin composition for decorative board is improved. Compounds for surface treatment include silane coupling agents, titanium coupling agents, and the like.

Examples of the silane coupling agent include organosilicon compounds having two or three alkoxy groups in the molecule. Examples of the organosilicon compound include vinylsilanes such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane; epoxysilanes such as sidoxypropyltrimethoxysilane; aminosilanes such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; γ-mercaptopropyltrimethoxysilane; -chloropropyltrimethoxysilane and the like.

The content of aluminum hydroxide is preferably 5 to 90 parts by mass with respect to a total of 100 parts by mass of the diallyl phthalate resin and the polyfunctional compound. When the content is 5 parts by mass or more, the nonflammability is excellent, and the sharpness is excellent. From the viewpoint of improving non-combustibility and image clarity while ensuring releasability from the mirror plate, and from the viewpoint of improving synchronism when embossing is performed, the above content is 20 to 80 parts by mass. is more preferable, and more preferably 30 to 70 parts by mass.

The above-mentioned resin composition for decorative board preferably contains a polymerization initiator (curing agent). By using the above-mentioned polymerization initiator, the curing speed becomes faster than the polymerization of the diallyl phthalate-based resin alone, and a resin-impregnated layer having a sufficient degree of curing can be obtained in a short time by thermocompression molding. Examples of the polymerization initiator include organic peroxide curing agents such as benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone peroxide and dicumyl peroxide.

The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of diallyl phthalate-based resin and polyfunctional compound.

The resin composition for a decorative board may contain components other than the components described above. Other components include thermosetting resins other than diallyl phthalate-based resins (but excluding unsaturated polyester resins), flame retardants other than aluminum hydroxide, curing catalysts, curing accelerators, polymerization inhibitors, and release agents. , Fillers such as silica, plasticizers, dispersants, thickeners, viscosity modifiers, coloring agents (pigments, dyes, etc.), antifoaming agents, preservatives, ultraviolet absorbers, depleting agents, antibacterial agents, leveling agents, silane coupling agents and the like. Only one kind of each of the other components may be used, or two or more kinds thereof may be used.

When the resin composition for a decorative board is to be excellent in synchronism when embossed, the resin composition for a decorative board preferably contains a color pigment. As the color pigment, known or commonly used ones can be used, and among them, pearl pigments are preferable. The content of the color pigment is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the diallyl phthalate-based resin and the polyfunctional compound.

Other flame retardants than aluminum hydroxide include metal oxides such as magnesium hydroxide. When the resin composition for a decorative board is to be excellent in synchronism when embossed, from the viewpoint of achieving excellent synchronism and sufficient nonflammability, other ingredients are added in addition to aluminum hydroxide. It preferably contains a flame retardant. On the other hand, when the releasability from the mirror plate is to be improved or the molding stability is emphasized, magnesium hydroxide should not be included (for example, the diallyl phthalate resin and the polyfunctional compound should not contain a total of 100 parts by mass. 7 parts by mass or less) is preferable. Only one kind of the other flame retardants may be used, or two or more kinds thereof may be used.

The average particle size of the other flame retardants is such that when a pressure plate having an uneven shape is superimposed on the resin-impregnated layer, the synchronism is improved without hindering the movement of the color pigment in the portion where the thickness of the resin composition is thin. From the viewpoint of being excellent, the thickness is preferably 4 μm or less, more preferably 3 μm or less, and more preferably 2 μm or less. The average particle size is, for example, 0.2 μm or more, and may be 0.3 μm or more, or 0.5 μm or more. Incidentally, the average particle size of the other flame retardants is obtained by the same method as that for the average particle size of the aluminum hydroxide.

The content of the other flame retardants is appropriately set according to the content of all the flame retardants in the resin composition for decorative board. The content of the flame retardant in the decorative board resin composition is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, with respect to the total of 100 parts by mass of the diallyl phthalate-based resin and the polyfunctional compound. , more preferably 30 to 60 parts by mass.

When the mold release agent is contained, the releasability from the mirror plate is improved. Examples of the release agent include fluorine-based release agents, silicone-based release agents, and wax-based release agents. Only one kind of the release agent may be used, or two or more kinds thereof may be used.

The content of the releasing agent is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of diallyl phthalate-based resin and polyfunctional compound. When the content is 0.1 part by mass or more, the releasability from the mirror plate becomes better. When the content is 8 parts by mass or less, the adhesiveness between the resin-impregnated layer and the substrate in the decorative board is improved.

When the polymerization inhibitor is contained, the reaction rate of the diallyl phthalate-based resin and the polyfunctional compound can be adjusted, and molding stability can be improved. As the polymerization inhibitor, known or commonly used ones can be used, for example, hydroquinone, methylhydroquinone, p-tert-butylcatechol, mono-tert-butylhydroquinone and other hydroquinones; phenols such as tert-butyl-p-cresol; quinones such as benzoquinone, p-benzoquinone, naphthoquinone, p-toluquinone; di-tert-butylhydroxytoluene, 2,6-di-tert-butyl-4-methylphenol , copper salts such as copper naphthenate; phenothiazine and the like. Only one kind of the polymerization inhibitor may be used, or two or more kinds thereof may be used.

The content of the polymerization inhibitor is preferably 0.005 to 0.5 parts by mass, more preferably 0.05 to 0.3 parts by mass, with respect to the total 100 parts by mass of the diallyl phthalate resin and the polyfunctional compound. parts, more preferably 0.8 to 0.15 parts by mass. When the content is within the above range, the molding stability of the decorative board is more excellent.

[Decorative sheet]
A decorative sheet and a decorative board can be produced using the resin composition for a decorative board. The decorative sheet includes an impregnated base material and a resin-impregnated layer containing a thermosetting resin composition impregnated in the impregnated base material, and the thermosetting resin composition is the decorative board resin composition or its A decorative sheet that is a cured product can be mentioned.

The said decorative board resin composition is a thermosetting resin composition. The thermosetting resin composition includes a thermosetting resin composition (thermosetting resin composition) and the thermosetting resin in the thermosetting resin composition (prepolymer diallyl phthalate resin etc.) and a composition containing a resin obtained by curing (thermoset resin composition). That is, the resin-impregnated layer includes a layer in which the thermosetting resin composition is impregnated in the impregnated substrate (layer before thermosetting, prepreg), and a layer in which the thermosetting resin in the composition is cured (heat layer after curing).

The resin-impregnated layer is a layer in which an impregnated substrate is impregnated with the resin composition for a decorative board or a cured product of the resin composition. The resin-impregnated layer may be a single layer or multiple layers (laminate). In addition, the resin-impregnated layer may have a single layer of the resin composition for a decorative board, or may have a plurality of layers of different resin compositions for a decorative board (multilayer laminate). may Above all, since the resin composition for a decorative board of the present invention is excellent in releasability from a mirror plate, the resin-impregnated layer has at least the resin composition for a decorative board on the surface that faces the mirror plate during thermocompression molding. is preferred.

The base material for impregnation is not particularly limited as long as it can be impregnated with the resin composition for decorative board. Woven fabrics such as acrylic and vinylon or non-woven fabrics may be used. The impregnated paper cloth may be printed. The impregnated substrate may be a single layer or multiple layers.

The amount of the thermosetting resin composition impregnated into the impregnated substrate is preferably 10 to 500 g/m ² , more preferably 100 to 300 g/m ² per area of the impregnated substrate. When the impregnation amount is 10 g/m ² or more, the impregnation amount is sufficient and the releasability from the mirror plate is excellent. Cost can be held down as the said impregnation amount is 500 g/m< ² > or less.

Although the thickness of the resin-impregnated layer is not particularly limited, it is, for example, 10 to 200 μm, preferably 20 to 100 μm. When the thickness is 10 μm or more, it is possible to suppress the occurrence of defects such as poor flow during thermocompression molding. When the thickness is 200 μm or less, it is possible to suppress warping of the molded product due to shrinkage of the resin.

The resin-impregnated layer can be produced by a known or commonly used method, for example, it can be produced as follows. First, a resin composition for a decorative board, which is a thermosetting composition, is prepared. The decorative board resin composition is obtained by mixing a diallyl phthalate-based resin, a polyfunctional compound, aluminum hydroxide, and, if necessary, various components described above. When the resin composition for a decorative board has a low viscosity, the base material for impregnation can be immersed in a bath of the resin composition for a decorative board for impregnation. When the resin composition for a decorative board is a high-viscosity liquid or solid, the resin composition for a decorative board can be diluted or dissolved in an appropriate solvent such as acetone, toluene, or methyl ethyl ketone to obtain an appropriate viscosity. After immersing the impregnated base material in the resin liquid, it is dried to volatilize the solvent. The impregnation temperature is, for example, 10-35°C, preferably 20-30°C. In addition, although the method of immersing the impregnated base material in the bath of the resin composition for decorative board has been described, the impregnation is performed by applying the resin composition for decorative board to the surface of the impregnated base material and allowing it to permeate. you can go When the thermosetting resin composition is a cured product of the resin composition for a decorative board, the resin composition for a decorative board is obtained by thermocompression molding by a method described in detail in the method for producing a decorative board described later. can be produced by curing the

[Decorative board]
A decorative board can be produced using the decorative sheet. The decorative board includes, for example, a base material and the decorative sheet provided on one surface of the base material. More specifically, the decorative board has at least a structure in which a base material and a decorative sheet including a resin-impregnated layer in which the base material is impregnated with the resin composition for a decorative board are laminated.

In the decorative board, the surface of the resin-impregnated layer (that is, the surface opposite to the substrate) may have an embossed shape. A decorative board having a resin-impregnated layer produced using the resin composition for a decorative board of the present invention develops synchronism according to the thickness of the resin-impregnated layer when embossed.

The decorative board may include other layers in addition to the layers described above. Examples of the other layers include a primer layer for improving the adhesion between the resin-impregnated layer and the base material, a core layer for imparting shape stability to the decorative board, and the resin. A protective film for protecting the surface of the impregnation layer and the like are included. In addition, it is preferable that the surface of the resin-impregnated layer, which is the side on which the mirror plate is superimposed during thermocompression molding, does not have a release layer.

1 and 2 show an embodiment of the decorative board. A decorative board 10 shown in FIG. 1 includes a base material 1 , a resin-impregnated layer 2 and a protective film 3 . The resin-impregnated layer 2 is a layer (prepreg) before thermosetting in which an impregnated base material is impregnated with a resin composition for a decorative board, which is a thermosetting resin composition, and is formed on one surface of the base material 1. . The protective film 3 is formed on the surface of the resin-impregnated layer 2 opposite to the substrate 1 . A decorative board 10' shown in FIG. The resin-impregnated layer 2 ′ is a layer in which an impregnated substrate is impregnated with a cured resin composition for a decorative board, and is obtained by thermally curing the resin-impregnated layer 2 .

Examples of the base material include known or commonly used base materials used for decorative boards. Examples of the substrate include organic substrates and inorganic substrates. Examples of the organic base material include wooden base materials such as wood veneer, plywood, laminated wood, particle board, medium density fiberboard (MDF), high humidity fiberboard, and kenaf board; paperboard, woven fabric, and nonwoven fabric. , resin-impregnated paper, resin-impregnated cloth, etc.; acrylic resin plate, styrene resin plate, ABS resin plate, polycarbonate resin plate, nylon resin plate, polystyrene resin plate, polypropylene resin plate, polyester resin plate, glass fiber reinforced A synthetic resin base material such as a plastic plate may be used. Examples of the inorganic base material include metal plate base materials such as an aluminum plate, a stainless steel plate, a duralumin plate, a steel plate, and a brass plate; a magnesium oxide plate, an aluminum hydroxide plate, an aluminum oxide plate, a silicon oxide plate, and a titanium oxide plate. , magnesium chloride plate, calcium silicate plate, volcanic vitreous material plate, gypsum (calcium sulfate) plate, slag gypsum plate, limestone (calcium carbonate) plate, wood wool cement plate, slag cement plate, lightweight cellular concrete plate, glass fiber Inorganic substrates such as reinforced concrete plates and the like are included. The substrate may be a single layer or a laminate of the same or different layers. Further, the base material may be subjected to an easy-adhesion treatment such as a sealer treatment or a primer treatment for improving adhesion to the resin-impregnated layer.

The thickness of the substrate is not particularly limited, but is, for example, 2 to 50 mm, preferably 3 to 30 mm. If the thickness is 2 mm or more, the strength will be sufficient and it will not crack easily. When the thickness is 50 mm or less, it is lightweight and easy to handle.

As the protective film, known or commonly used films used for decorative boards can be used. For example, plastic films such as polyethylene terephthalate film (PET film), polypropylene film, polybutylene terephthalate film and the like are subjected to release treatment. and a low-adhesion film. The protective film is peeled off when the decorative board is used.

The Gd value of the surface of the resin-impregnated layer (the surface opposite to the substrate) is not particularly limited, but is preferably 0.2 or more, more preferably 0.3 or more. When the Gd value is 0.2 or more, the decorative sheet has more excellent image sharpness.

The 20° gloss value (JIS Z8741) of the surface of the resin-impregnated layer (the surface opposite to the substrate) is not particularly limited, but is preferably 50 or more, more preferably 60 or more, and still more preferably 70 or more. . When the gloss value is 50 or more, the glossiness of the decorative board is more excellent.

[Method for manufacturing decorative board]
An embodiment of the method for manufacturing the decorative board will be described with reference to FIG. First, as described above, the impregnated substrate is impregnated with the thermosetting resin composition for decorative board prepared by diluting or dissolving it with a solvent as necessary, and then drying as necessary to volatilize the solvent. to prepare a resin-impregnated layer 2 in which the impregnated base material is impregnated with the thermosetting resin composition for a decorative board. Then, if necessary, the resin-impregnated layer 2 and a releasing substrate such as a polyethylene film are pasted together to obtain a decorative sheet. The bonding can be performed by laminating using, for example, pressure rolls.

Next, the decorative sheet is placed on the base material 1 so that the resin-impregnated layer 2 faces the base material 1 side. A mirror plate 4 is superimposed on the layer 2 to obtain a laminate in which the decorative plate 10 and the mirror plate 4 are laminated. The surface of the mirror plate 4 facing the resin-impregnated layer 2 has a shape for transferring a design to the resin-impregnated layer as necessary.

Next, a pressing machine is used to perform thermocompression molding by applying pressure while heating from above and below the laminate including the decorative board 10, and curing the resin-impregnated layer 2 to cure the thermoset resin-impregnated laminate. A layer 2' is formed to obtain a laminated body in which the decorative plate 10' and the mirror plate 4 are laminated. As described above, it is preferable that the thermocompression molding method is lamination thermocompression molding, that is, the resin-impregnated layer 2 and the base material 1 are superimposed, placed in a mold, and cured under heat and pressure. The thermocompression molding can be preferably carried out under conditions of, for example, a pressure of 10 to 25 kgf/cm ² , a temperature of 120 to 190° C., and a time of 30 seconds to 15 minutes.

The laminated body obtained after hot pressing includes a decorative sheet 10' in which a substrate 1 and a thermoset resin-impregnated layer 2' provided on the substrate 1 are laminated. After that, the mirror plate 4 is removed to obtain the decorative plate 10'. In the decorative board, the resin-impregnated layer formed from the resin composition for a decorative board has excellent releasability from the mirror board, so that the mirror board 4 can be easily removed.

When producing a decorative plate 10 ′ having an embossed shape on the surface of the resin-impregnated layer 2 ′, instead of the mirror plate 4 , a pressing plate 5 having an uneven surface facing the resin-impregnated layer 2 is used. Then, as shown in FIG. 4, when the pressing plate 5 is superimposed on the resin-impregnated layer 2, an uneven shape corresponding to the uneven shape is formed on the surface of the resin-impregnated layer 2. As shown in FIG. That is, the resin-impregnated layer 2 has a thick film portion 2a and a thin film portion 2b. When the uneven shape is formed on the surface of the resin-impregnated layer 2, a higher pressure is applied to the region to be the thin film portion 2b than to the region to be the thick film portion 2a. When the resin-impregnated layer 2 contains a color pigment, the color pigment flows from the area that becomes the thin film portion 2b to the area that becomes the thick film portion 2a when pressure is applied. At this time, since the average particle size of the aluminum hydroxide is small, the flow of the color pigment is not hindered and can flow smoothly. As a result, in the resin-impregnated layer 2', the amount of color pigment per unit area in the thick film portion 2a is greater than that in the thin film portion 2b, thereby obtaining synchronism. After that, a pressing machine is used to perform hot-press molding to obtain a decorative sheet 10' having an embossed shape on the surface of the resin-impregnated layer 2'.

After that, a protective film such as a PET film may be attached to the surface of the resin-impregnated layer 2' to the decorative board 10'. As described above, the decorative board can be manufactured.

As described above, the decorative board provided with the resin-impregnated layer obtained using the resin composition for a decorative board of the present invention is made nonflammable by containing aluminum hydroxide having an average particle size within a specific range. Excellent, and yet excellent in releasability from the mirror plate after thermocompression molding. Therefore, it is not necessary to provide a separate release layer between the resin-impregnated layer and the mirror plate during thermocompression molding. When the average particle size of the aluminum hydroxide is within a specific range, the flow of the resin composition during thermocompression molding is suppressed, and a sufficient thickness of the resin film can be secured. The decorative board has excellent sharpness and gloss, high transparency, and excellent appearance. In addition, when a resin-impregnated layer is prepared by blending a coloring pigment into the resin composition for a decorative board, and the surface of the resin-impregnated layer is embossed, synchronism corresponding to the thickness of the resin-impregnated layer is exhibited. .

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited only to these examples.

<Decorative board with excellent releasability>
Example 1
Diallyl orthophthalate prepolymer (50% by mass of methyl ethyl ketone solution viscosity (30°C) 96.5 mPa s, manufactured by Osaka Soda Co., Ltd.) 70 parts by mass, dipentaerythritol hexaacrylate 30 parts by mass, aluminum hydroxide (trade name "BF013STM" , Average particle size 1 μm, with surface treatment, manufactured by Nippon Light Metal Co., Ltd.) 50 parts by mass, benzoyl peroxide 3 parts by mass, internal mold release agent (trade name “Zelec UN”, manufactured by DuPont) 1.5 parts by mass, hydroquinone (Polymerization inhibitor) 0.1 parts by mass, 0.1 parts by mass of antifoaming agent, 5 parts by mass of magnesium hydroxide (trade name "Magshees N-6", average particle size 1.3 μm) to 100 parts by mass of acetone It was dissolved to prepare a resin composition solution. After impregnating the resin composition by immersing 60 g/m ² of printed pattern paper in the resin composition solution at 25 ° C., it was heated in a hot air circulation oven at 105 ° C. for 90 seconds to volatilize the solvent. ² (impregnated amount per 100 parts by mass of printed pattern paper: 167 parts by mass).

A base material (trade name “Dailight”, manufactured by Daiken Kogyo Co., Ltd., thickness 3 mm, noncombustible material) is placed on the circulation plate, and the decorative sheet is placed on the base material, and the impregnated paper is used as the base. It was placed in contact with the material. Then, using a press, pressure was applied so that the hot plate on which the specular plate was set was on the impregnated paper side and the other hot plate was on the circulation plate side, and heat was applied to carry out thermocompression molding. The thermocompression molding was performed at a temperature of 150° C. and a pressure of 16 kgf/cm ² for 3 minutes. Thereafter, the pressure was released, and the laminate of the circulation plate, the base material, and the decorative sheet was removed from the press and cooled to room temperature to obtain a decorative sheet.

Example 2
Example 1 except that 100 parts by mass of diallyl orthophthalate prepolymer (50% by mass of methyl ethyl ketone solution viscosity (30°C) 96.5 mPa s, manufactured by Osaka Soda Co., Ltd.) and 15 parts by mass of dipentaerythritol hexaacrylate were used. A decorative sheet and a decorative board were produced in the same manner as above.

(evaluation)
Each decorative board obtained in Examples 1 and 2 was evaluated as follows. The evaluation results are shown in Table 1.

(1) Releasability When producing each decorative board obtained in the examples, the following criteria were measured based on the time required for the molded product to drop from the mirror plate when the pressure was released after the molding time had elapsed. determined by
[criterion]
◯ (Good): Detached from the mirror plate when the pressure was opened, or soon fell off the mirror plate.
x (defective): It takes a long time to fall from the mirror plate.

(2) Molding Stability The surface of the resin-impregnated layer of each decorative board obtained in Examples was visually observed and evaluated according to the following criteria.
[criterion]
◯ (Good): Flow defects such as pinholes did not occur.
x (defective): A large amount of flow defects such as pinholes occur.

(3) 20° Gloss For the surface of the resin-impregnated layer of each decorative board obtained in the Examples, a gloss meter (trade name “micro-TRI-gloss”, manufactured by Gardner) was used to measure the gloss according to JIS Z8741. It was measured according to the method in

(4) Gd value For the resin-impregnated layer surface of each decorative board obtained in the example, a portable clarity and gloss meter (trade name “PGD-4”, PGD meter, Japan Color Research Institute, Tokyo Koden Co., Ltd. (manufactured by the company) was used to measure the displayed vividness measurement value (Gd value).

As shown in Table 1, the decorative laminates obtained in Examples 1 and 2 were evaluated as having excellent releasability. Furthermore, it has non-combustibility by containing a sufficient amount of aluminum hydroxide, has excellent molding stability, has high 20° gloss and excellent gloss, has a high Gd value and excellent sharpness, and has a good appearance. was evaluated to be

<Decorative board having embossed shape>
Example 3
Diallyl orthophthalate prepolymer (50% by mass of methyl ethyl ketone solution viscosity (30°C) 96.5 mPa s, manufactured by Osaka Soda Co., Ltd.) 70 parts by mass, dipentaerythritol hexaacrylate 30 parts by mass, aluminum hydroxide (trade name "BF013STM" , average particle size 1 μm, with surface treatment, manufactured by Nippon Light Metal Co., Ltd.) 50 parts by mass, magnesium hydroxide (trade name “Magshees N-6”, average particle size 1.3 μm) 5 parts by mass, benzoyl peroxide 3 parts by mass , internal release agent (trade name “Zelec UN”, manufactured by DuPont) 1.5 parts by mass, hydroquinone (polymerization inhibitor) 0.1 part by mass, pearl pigment (trade name “Iriodin 520”, manufactured by Merck) 4 A resin composition solution was prepared by dissolving .5 parts by mass and 0.1 part by mass of an antifoaming agent in 100 parts by mass of acetone. After immersing 60 g/m ² of dark-colored printed pattern paper as an impregnating substrate in the resin composition solution at 25° C. to impregnate the resin composition, it is heated in a hot air circulation oven at 105° C. for 90 seconds to remove the solvent. was volatilized to obtain a decorative sheet made of 160 g/m ² impregnated paper (impregnated amount per 100 parts by mass of printed pattern paper: 167 parts by mass).

A base material (trade name “Dailight”, manufactured by Daiken Kogyo Co., Ltd., thickness 3 mm, noncombustible material) is placed on the circulation plate, and the decorative sheet is placed on the base material, and the impregnated paper is used as the base. It was placed in contact with the material. Then, using a press, pressure was applied so that the hot plate on which the pressing plate was set was on the impregnated paper side, and the other hot plates were on the circulation plate side, and heat was applied to carry out thermocompression molding. The surface of the pressing plate facing the impregnated paper is formed with an uneven shape for giving an embossed shape. The thermocompression molding was performed at a temperature of 150° C. and a pressure of 16 kgf/cm ² for 3 minutes. After that, the pressure was released, and the laminate of the circulation plate, the base material and the decorative sheet was removed from the press and cooled to room temperature to obtain a decorative sheet.

Example 4
Example 3 except that 100 parts by mass of diallyl orthophthalate prepolymer (50% by mass of methyl ethyl ketone solution viscosity (30°C) 96.5 mPa s, manufactured by Osaka Soda Co., Ltd.) and 15 parts by mass of dipentaerythritol hexaacrylate were used. A decorative sheet and a decorative board were produced in the same manner as above.

(evaluation)
Each decorative board obtained in Examples 3 and 4 was evaluated as follows. The evaluation results are shown in Table 2.

(5) Synchronization The surface of the resin-impregnated layer of each decorative board obtained in Examples and Comparative Examples was visually observed and evaluated according to the following criteria.
[criterion]
◯ (Good): The difference in color density between the recessed portion and the projected portion is large, and the synchronization with the embossed shape is clear.
x (defective): The difference in color density between the concave portion and the convex portion is small, and synchronization with the embossed shape is not felt.

As shown in Table 2, the decorative laminates obtained in Examples 3 and 4 were evaluated as having excellent synchronism.

(6) Combustion Test The decorative board obtained in Example 1 was subjected to a combustion test in accordance with ISO5660 "Cone calorimeter method". Each combustion test was performed three times. As a result, the average value of three combustion tests was 7.7 MJ/m ² for the total calorific value for 20 minutes after the start of heating. A total calorific value of 8 MJ/m ² or less indicates excellent nonflammability.

1 base material 2 resin-impregnated layer (before thermosetting, prepreg)
2a thick film portion 2b thin film portion 2′ resin impregnated layer (heat-cured)
3 protective film 4 mirror plate 5 pressure plate 10, 10' decorative plate

Claims (9)

Containing diallyl phthalate resin, polyfunctional compound and aluminum hydroxide,
A resin composition for a decorative board, wherein the aluminum hydroxide has an average particle size of 3 μm or less. The resin composition for a decorative board according to claim 1, which contains a color pigment. The resin composition for a decorative board according to claim 1 or 2, which contains magnesium hydroxide. The resin composition for a decorative board according to any one of claims 1 to 3, wherein the content of aluminum hydroxide is 5 to 90 parts by mass with respect to a total of 100 parts by mass of the diallyl phthalate-based resin and the polyfunctional compound. thing. An impregnated base material and a resin-impregnated layer containing a thermosetting resin composition impregnated in the impregnated base material,
A decorative sheet, wherein the thermosetting resin composition is the resin composition for a decorative board according to any one of claims 1 to 4 or a cured product thereof. 6. The decorative sheet according to claim 5, wherein the resin-impregnated layer has the resin composition for a decorative board on the surface which will be the side of the mirror plate during thermocompression molding. 7. The decorative sheet according to claim 5, wherein the surface of the resin-impregnated layer is embossed. A decorative board comprising a substrate and the decorative sheet according to any one of claims 5 to 7 provided on at least one surface of the substrate. The decorative board according to claim 8, wherein the surface of the resin-impregnated layer opposite to the substrate has an embossed shape.

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