JP2022045973A - Resin composition for decorative plate, decorative sheet, and decorative plate - Google Patents

Abstract

To provide a resin composition for a decorative plate capable of providing an incombustible decorative plate that achieves at least one of excellent releasability from a mirror plane after hot press molding and excellent tunability in emboss processing.SOLUTION: A resin composition for a decorative plate contains a diallyl phthalate resin, an unsaturated polyester resin, and aluminum hydroxide. The unsaturated polyester resin has a number average molecular weight of 500-2,800. The aluminum hydroxide has an average particle diameter of 3 μm or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition for a decorative board, a decorative sheet, and a decorative board. More specifically, the present invention relates to a resin composition for a decorative board, a decorative sheet using the resin composition for a decorative board, and a decorative board provided with the decorative sheet.

Conventionally, the surface of a table, counter, wall, floor, etc. is covered with a resin-impregnated layer such as impregnated paper obtained by impregnating a paper-quality base material such as titanium paper with a thermosetting resin such as a diallyl phthalate resin. A decorative plate obtained by curing the thermosetting resin by laminating the mirror surface plate on the resin impregnated layer and hot-press molding is used. The surface of the decorative board may be subjected to high-gloss treatment, low-gloss treatment (matte treatment), embossing, or the like for the purpose of imparting a high-class feeling or a desired pattern. Among them, a decorative board using a diallyl phthalate resin is known as a decorative board having weather resistance, natural texture, heat resistance, chemical resistance, and dimensional stability.

By superimposing the base material having the uneven shape on the surface of the decorative board, the uneven shape is formed on the surface of the resin impregnated layer, and embossing can be performed. When the resin impregnated layer contains a coloring pigment, when embossed, the convex portion of the resin impregnated layer becomes a dark color and the concave portion becomes a light color, and the color depth (synchronism) according to the thickness of the resin impregnated layer. ) Is expressed (see, for example, Patent Document 1).

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

Japanese Unexamined Patent Publication No. 5-147050. Japanese Unexamined Patent Publication No. 2011-79870 Japanese Unexamined Patent Publication No. 2009-234200 Japanese Unexamined Patent Publication No. 2006-35839

However, when aluminum hydroxide is added to the resin impregnated layer in an amount sufficient to be nonflammable, the mirror plate to be overlapped with the resin impregnated layer and the resin impregnated layer adhere to each other during thermal pressure molding for molding the decorative plate. There was a problem that it was difficult to release the mirror plate.

Further, when aluminum hydroxide is added to the resin-impregnated layer containing the coloring pigment and embossing is performed, the color depth (synchronization) corresponding to the thickness of the resin-impregnated layer may not be exhibited.

Therefore, an object of the present invention is a decorative plate having nonflammability, which is excellent in mold releasability with respect to a mirror surface plate after thermal pressure molding and excellent in synchronization when embossed. It is an object of the present invention to provide a resin composition for a decorative board, which can obtain a decorative board to be satisfied.

As a result of diligent studies to achieve the above object, the present inventors have made an unsaturated polyester having a number average molecular weight within a specific range in a resin composition for a decorative board containing a diallyl phthalate resin and an unsaturated polyester resin. By using a based resin and blending aluminum hydroxide whose average particle size is within a specific range, it is a nonflammable decorative board, which is excellent in releasability from a mirror plate after thermal pressure molding. , It has been found that a veneer that satisfies at least one of excellent synchronization when embossed can be obtained. The present invention has been completed based on these findings.

That is, the present invention contains a diallyl phthalate resin, an unsaturated polyester resin, and aluminum hydroxide. The unsaturated polyester resin has a number average molecular weight of 500 to 2800, and the average particle size of the aluminum hydroxide is A resin composition for a decorative board having a size of 3 μm or less is provided.

The mass ratio of the diallyl phthalate resin to the unsaturated polyester resin (the former: the latter) is preferably 20:80 to 90:10.

The viscosity (rotation speed: 6 rpm) of the solid content 50% by mass acetone solution of the resin composition for a decorative board at 20 ° C. is preferably 100 to 800 mPa · s.

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 100 parts by mass in total of the diallyl phthalate resin and the unsaturated polyester resin.

Further, the present invention comprises a resin impregnated layer containing the impregnated base material and the thermosetting resin composition impregnated in the impregnated base material, and the thermosetting resin composition is any one of claims 1 to 6. A decorative sheet, which is the resin composition for a decorative board or a cured product thereof according to the above item, is provided.

It is preferable that the resin impregnated layer has the resin composition for a decorative plate on the surface that becomes the mirror plate side at the time of thermal pressure molding.

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

The present invention provides a decorative board provided with 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 base material may have an embossed shape.

According to the resin composition for a decorative plate of the present invention, it is a nonflammable decorative plate, which is excellent in mold releasability with respect to a mirror surface plate after thermal pressure molding, and is excellent in synchronization when embossed. You can get a veneer that meets at least one of the things.

It is sectional drawing which shows one Embodiment of the decorative board using the resin composition for a decorative board of this invention. It is sectional drawing which shows the other embodiment of the decorative board which used the resin composition for a decorative board of this invention. It is a figure which shows one Embodiment of the manufacturing method of the decorative board shown in FIG. It is a figure which shows one Embodiment of the manufacturing method of the decorative board which has 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, an unsaturated polyester-based resin, and aluminum hydroxide.

The diallyl phthalate 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 the diallyl phthalate-based monomer. Examples of the diallyl phthalate-based monomer include diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate. As the diallyl phthalate-based monomer, only one kind may be used, or two or more kinds may be used. Further, as the diallyl phthalate resin, only one kind may be used, or two or more kinds may be used. The weight average molecular weight of the diallyl phthalate resin by the GPC method is preferably 10,000 to 50,000.

The unsaturated polyester resin may be in a liquid state or a solid state at room temperature. As the unsaturated polyester resin, only one kind may be used, or two or more kinds may be used.

Examples of the unsaturated polyester-based resin include compounds containing a structural unit derived from a polybasic unsaturated acid and a structural unit derived from a polyhydric alcohol. Further, the unsaturated polyester-based resin may further contain a structural unit derived from a polybasic saturated acid. The unsaturated acid, the saturated acid, and the polyhydric alcohol may be used alone or in combination of two or more.

Examples of the polybasic unsaturated acid include maleic acid, fumaric acid, itaconic acid, and phthalic acid-based monomers (orthophthalic acid, isophthalic acid, and terephthalic acid). The unsaturated acid preferably contains a phthalic acid-based monomer. It also preferably contains maleic acid.

Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, hydrogenated bisphenol A and the like. The polyhydric alcohol component preferably contains propylene glycol. Further, from the viewpoint of being more excellent in mold releasability with respect to the mirror surface plate, it is preferable to contain ethylene glycol and / or hydrogenated bisphenol A.

Further, an air-curable unsaturated polyester resin may be used as the unsaturated polyester resin. For example, the constituent units derived from an aliphatic cyclic unsaturated acid such as tetrahydrophthalic acid as the unsaturated acid, 3,6-endomethylenetetrahydrophthalic acid, and methyl-3,6-endomethylenetetrahydrophthalic acid, and the above-mentioned many. Examples thereof include a polyester resin containing a structural unit derived from allyl glycidyl ether as a phthalic alcohol.

The number average molecular weight (Mn) of the unsaturated polyester resin is 500 to 2800, preferably 800 to 2200. When the number average molecular weight is 500 or more, the fluidity of the resin composition can be maintained, and the impregnation property into the impregnated substrate is excellent. When the number average molecular weight is 2800 or less, it is presumed that the bond with the diallyl phthalate resin is increased after the thermosetting, and the mold releasability, the vividness, and the glossiness with respect to the mirror surface plate are good. Become. Further, when the pressing plate having an uneven shape is superposed on the resin impregnated layer, the fluidity of the resin composition is high, and the curing speed is relatively slow, so that the movement of the coloring pigment is promoted and the synchronization is excellent. The number average molecular weight is more preferably 800 to 1500 from the viewpoint of being more excellent in releasability, glazing property and glossiness with respect to the mirror surface plate. Further, the number average molecular weight is more preferably 1600 to 2200 from the viewpoint of further promoting the flow of the coloring pigment when embossed and being more excellent in synchronization. The number average molecular weight is a value obtained by GPC measurement.

The weight average molecular weight (Mw) of the unsaturated polyester resin is not particularly limited, but is preferably 2500 to 7000, and more preferably 3500 to 5500. When the weight average molecular weight is 2500 or more, the fluidity of the resin composition can be maintained, and the impregnation property into the impregnated substrate is more excellent. When the weight average molecular weight is 7,000 or less, it is presumed that the bond with the diallyl phthalate resin is increased after the thermosetting, and the releasability, glazing property, and glossiness with respect to the mirror surface plate are better. Become. Further, the fluidity of the resin composition when the pressing plate having an uneven shape is superposed on the resin impregnated layer is high, and the curing speed is relatively slow, so that the movement of the coloring pigment is promoted and the synchronization is more excellent. It becomes a tendency. The weight average molecular weight is a value obtained by GPC measurement.

The molecular weight dispersion (Mw / Mn) of the unsaturated polyester resin is not particularly limited, but is preferably 1.5 to 4.5, more preferably 2.0 to 4.0.

The acid value of the unsaturated polyester resin is not particularly limited, but is preferably 5 to 30 KOHmg / g, more preferably 10 to 25 KOH mg / g.

The mass ratio of the diallyl phthalate resin to the unsaturated polyester resin (the former: the latter) in the resin composition for a decorative board is preferably 20:80 to 90:10, more preferably 30:70 to 70:30. be. When the mass ratio is 30:70 or more, the glossiness, alkali resistance, and mold releasability of the decorative board tend to be more excellent. The mass ratio is more preferably 51:49 to 70:30, and particularly preferably 52:48 to 60:40, from the viewpoint of being more excellent in releasability, sharpness, and gloss with respect to the mirror surface plate. Further, the mass ratio is more preferably 30:70 to 40:60 from the viewpoint of being more excellent in nonflammability.

The total content ratio of the diallyl phthalate resin and the unsaturated polyester resin in the resin composition for a decorative board is 20 to 90% by mass with respect to the total amount (100% by mass) of the resin composition for a decorative board. It is preferable, more preferably 30 to 85% by mass, still more preferably 40 to 80% by mass. When the content ratio is 20% by mass or more, a resin impregnated layer having sufficient strength can be obtained by thermal pressure molding.

The resin composition for a decorative board may contain a monomer constituting a diallyl phthalate resin or an unsaturated polyester resin, or an oligomer of the monomer (for example, 2 to 3 polymers). For example, the diallyl phthalate-based monomer, which is a constituent unit of the diallyl phthalate-based resin, may be contained.

The resin composition for a decorative board contains aluminum hydroxide. By containing aluminum hydroxide, the veneer is nonflammable. The shape of aluminum hydroxide is not particularly limited, and examples thereof include a columnar shape, a needle shape, and a spherical shape. As the aluminum hydroxide, only one kind may be used, or two or more kinds may be used.

The average particle size of aluminum hydroxide in the resin composition for decorative boards is 3 μm or less, preferably 2 μm or less, and more preferably 1.5 μm or less. When the average particle size is 3 μm or less, the flow of the resin composition during thermal pressure molding is suppressed, the resin film thickness can be secured to a sufficient thickness, and the mold releasability to the mirror surface plate is excellent. It is also highly transparent and has an excellent appearance. Further, it is presumed that when the pressing plate having an uneven shape is superposed on the resin impregnated layer, the movement of the coloring pigment is not hindered in the portion where the thickness of the resin composition is thin, and the synchronization is excellent. Furthermore, it is also excellent in transparency. The average particle size is, for example, 0.2 μm or more, and may be 0.3 μm or more and 0.5 μm or more. The average particle size can be measured by a laser diffraction / scattering particle size distribution measuring device, or can be actually measured from an electron micrograph, and further calculated from the electron micrograph using an image processing device. You can also. Usually, it is common to measure the average particle size by a laser diffraction method.

The aluminum hydroxide may be surface-treated. By applying the surface treatment, the dispersibility in the resin composition for a decorative board becomes good. Examples of the compound for surface treatment include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include organosilicon compounds having two or three alkoxy groups in the molecule. Examples of the organic silicon compound include vinyl silanes such as vinyl triethoxysilane, vinyl trimethoxysilane, and vinyl tris (β-methoxyethoxy) silane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-gly. Epoxysilanes such as Sidoxypropyltrimethoxysilane; Aminosilanes such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane; γ-mercaptopropyltrimethoxysilane; γ -Cloropropyltrimethoxysilane and the like.

The content of aluminum hydroxide is preferably 5 to 90 parts by mass with respect to 100 parts by mass in total of the diallyl phthalate resin and the unsaturated polyester resin. When the content is 5 parts by mass or more, it is more excellent in nonflammability and more excellent in vividness. From the viewpoint of ensuring good releasability with respect to the mirror plate and improving nonflammability and vividness, the content is more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass. From the viewpoint of improving the synchronism when embossed, 7 to 50 parts by mass is more preferable, and 10 to 40 parts by mass is more preferable.

The resin composition for a decorative board may contain a cross-linking agent for cross-linking a diallyl phthalate resin or an unsaturated polyester resin. When a cross-linking agent is used, the hardness of the resin-impregnated layer after thermosetting can be improved, and the releasability, image quality, and glossiness are further improved. Examples of the cross-linking agent include 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, and a polymer of the polyfunctional monomer. Polyfunctional compounds of. As the cross-linking agent, only one kind may be used, or two or more kinds may be used.

Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, dodecanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, and (poly) propylene glycol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropanthry (meth) acrylate, tetra Polyfunctional (meth) such as methylol methanetri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyldi (meth) acrylate, and hexyldi (meth) acrylate. Examples include acrylate. As the polyfunctional compound, a poly (meth) acrylate of dipentaerythritol having three or more (meth) acryloyl groups in the molecule is preferable.

The content of the cross-linking agent is preferably 0.6 to 20 parts by mass, more preferably 1 to 16 parts by mass, based on 100 parts by mass of the total of the diallyl phthalate resin and the unsaturated polyester resin. When the content is within the above range, the hardness of the resin-impregnated layer after heat curing becomes more appropriate, and the releasability becomes more appropriate. In addition, the vividness and glossiness are further improved, and the appearance is improved.

The fat composition for a decorative board preferably contains a polymerization initiator (curing agent). By using the above polymerization initiator, the curing rate becomes faster than the polymerization of the diallyl phthalate resin or the unsaturated polyester resin alone, and the resin impregnated layer having a sufficient degree of curing can be obtained in a short time by thermal pressure molding. Can be done. Examples of the polymerization initiator include organic peroxide-based curing agents such as benzoyl peroxide, tertiary butyl peroxide, 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 the total of the diallyl phthalate resin and the unsaturated polyester resin. ..

The resin composition for a decorative board may contain other components other than the above components. Examples of the above other components include thermosetting resins other than diallyl phthalate resins and unsaturated polyester resins, flame retardants other than aluminum hydroxide, curing catalysts, curing accelerators, polymerization inhibitors, mold release agents, silica and the like. Fillers, plasticizers, dispersants, thickeners, viscosity modifiers, colorants (pigments, dyes, etc.), defoaming agents, preservatives, UV absorbers, depleting agents, antibacterial agents, leveling agents, silane coupling agents And so on. As for each of the above other components, only one kind may be used, or two or more kinds may be used.

When the resin composition for a decorative board is excellent in synchronization when embossed, it is preferable that the resin composition for a decorative board contains a coloring pigment. As the coloring pigment, known or commonly used pigments can be used, and among them, pearl pigments are preferable. The content of the coloring 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 total of the diallyl phthalate resin and the unsaturated polyester resin.

Examples of the flame retardant other than the aluminum hydroxide include metal oxides such as magnesium hydroxide. When the resin composition for a decorative board is excellent in synchronism when embossed, in addition to aluminum hydroxide, from the viewpoint of sufficient nonflammability while being excellent in synchronism, other materials are used. It is preferable to contain a flame retardant. On the other hand, when the releasability to the mirror plate is improved or when the molding stability is emphasized, magnesium hydroxide should not be contained (for example, a total of 100 parts by mass of the diallyl phthalate resin and the unsaturated polyester resin). On the other hand, 5 parts by mass or less) is preferable. As the above other flame retardants, only one kind may be used, or two or more kinds may be used.

The average particle size of the other flame retardants is such that when the pressing plate having an uneven shape is superposed on the resin impregnated layer, the synchronization is improved without further hindering the movement of the coloring pigment in the portion where the thickness of the resin composition is thin. From the viewpoint of making it excellent, it 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 and 0.5 μm or more. The average particle size of the other flame retardant is obtained by the same method as the average particle size of the aluminum hydroxide.

The contents of the other flame retardants are appropriately set according to the contents of all the flame retardants in the resin composition for decorative boards. The content of the flame retardant in the resin composition for a decorative board is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, based on 100 parts by mass of the total of the diallyl phthalate resin and the unsaturated polyester resin. Parts, more preferably 30 to 60 parts by mass.

When the above-mentioned mold release agent is contained, the mold release property with respect to the mirror surface plate becomes better. Examples of the mold release agent include a fluorine-based mold release agent, a silicone-based mold release agent, and a wax-based mold release agent. As the release agent, only one kind may be used, or two or more kinds may be used.

The content of the release 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 the total of the diallyl phthalate resin and the unsaturated polyester resin. .. When the content is 0.1 part by mass or more, the releasability to the mirror surface plate becomes better. When the content is 8 parts by mass or less, the adhesion between the resin impregnated layer and the base material is good in the decorative board.

When the above-mentioned polymerization inhibitor is contained, the reaction rates of the diallyl phthalate-based resin and the unsaturated polyester-based resin can be adjusted, and the molding stability can be improved. As the polymerization inhibitor, known or commonly used agents can be used, for example, hydroquinones such as hydroquinone, methylhydroquinone, p-tert-butylcatechol, mono-tert-butylhydroquinone; hydroquinone monomethyl ether, di-. Phenols such as tert-butyl-p-cresol; quinones such as benzoquinone, p-benzoquinone, naphthoquinone, p-tolucinone; di-tert-butylhydroxytoluene, 2,6-di-tert-butyl-4-methylphenol , Copper salts such as copper naphthenate; phenothiazine and the like. As the polymerization inhibitor, only one kind may be used, or two or more kinds 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 100 parts by mass of the total of the diallyl phthalate resin and the unsaturated polyester resin. It is by mass, 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.

The viscosity (rotation speed: 6 rpm) of the solid content 50% by mass acetone solution of the resin composition for a decorative board at 20 ° C. is preferably 110 to 800 mPa · s, and more preferably 150 to 700 mPa · s. The viscosity (rotation speed: 60 rpm) of the solid content 50% by mass acetone solution of the resin composition for a decorative board at 20 ° C. is preferably 30 to 200 mPa · s, more preferably 40 to 120 mPa · s. The viscosity is a value measured using a B-type viscometer for a solution obtained by adding acetone to the resin composition for a decorative board until the solid content concentration reaches 50% by mass.

The thixotropic index (TI) of the resin composition for a decorative board in a 50% by mass acetone solution having a solid content at 20 ° C. is preferably 3 to 8, and more preferably 4 to 7. When the TI is 3 or more, the thixotropic property is high and the impregnation property into the impregnated substrate is more excellent. When the TI is 8 or less, the resin composition has appropriate fluidity when impregnated into the impregnated substrate, and is more excellent in impregnating the impregnated substrate. The TI is a value obtained by [viscosity (6 rpm) / viscosity (60 rpm)] based on the viscosity of the solid content 50% by mass acetone solution at 20 ° C.

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

The decorative board resin composition is a thermosetting resin composition. The thermosetting resin composition is a thermosetting resin composition (thermosetting resin composition) and a thermosetting resin (dialyl phthalate resin which is a prepolymer) in the thermosetting resin composition. , An unsaturated polyester resin, etc.) and a composition containing a resin (thermosetting resin composition) obtained by curing the resin. 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). The layer after curing).

The resin impregnated layer is a layer in which the impregnated base material 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 a plurality of layers (laminated body). Further, the resin impregnated layer may have a single layer of a resin composition for a decorative board, or may have a layer of a plurality of different resin compositions for a decorative board (multi-layered body). You may. Above all, since the resin composition for a decorative plate of the present invention is excellent in mold releasability with respect to the mirror surface plate, the resin impregnated layer has at least the resin composition for a decorative plate on the surface on the mirror surface plate side at the time of thermal pressure molding. Is preferable.

The impregnated base material is not particularly limited as long as it can be impregnated with the resin composition for decorative boards, and is, for example, impregnated paper cloth such as titanium paper, thin leaf paper, reinforced paper, kraft paper, and cellulose paper; polyester, rayon, and the like. Examples thereof include woven fabrics such as acrylic and rayon or non-woven fabrics. The impregnated paper cloth may be printed. The impregnated substrate may be a single layer or a plurality of layers.

The amount of the thermosetting resin composition impregnated into the impregnated base material is preferably 10 to 500 g / m ² and more preferably 100 to 300 g / m ² per area of the impregnated base material. When the impregnation amount is 10 g / m ² or more, the impregnation amount is sufficient and the mold releasability to the mirror surface plate is excellent. When the impregnation amount is 500 g / m ² or less, the cost can be suppressed.

The thickness of the resin impregnated layer is not particularly limited, but 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 flow defects during thermal pressure molding. When the thickness is 200 μm or less, warpage of the molded product can be suppressed due to shrinkage of the resin.

The resin impregnated layer can be produced by a known or conventional method, and can be produced, for example, as follows. First, a resin composition for a decorative board, which is a thermosetting composition, is prepared. The resin composition for a decorative board is obtained by mixing a diallyl phthalate resin, an unsaturated polyester resin, and aluminum hydroxide, and if necessary, various components described above. When the resin composition for a decorative board has a low viscosity, the impregnated base material can be impregnated by immersing the impregnated base material in the resin composition bath for a decorative board. When the decorative plate resin composition is a high-viscosity liquid or a solid, the decorative plate resin composition is diluted or dissolved in an appropriate solvent such as an organic solvent such as acetone, toluene, or methyl ethyl ketone to have an appropriate viscosity. A resin solution is prepared, and the impregnated substrate is dipped in the resin solution, and then dried to volatilize the solvent. The impregnation temperature is, for example, 10 to 35 ° C, preferably 20 to 30 ° C. Although the method of immersing the impregnated base material in the resin composition bath for the decorative board has been described, the impregnation is performed by applying the resin composition for the decorative board to the surface of the impregnated base material and leaving it to soak. You may go there. 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 formed by hot pressure molding by the method described in detail in the method for manufacturing a decorative board described later. Can be produced by curing.

[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 containing a resin-impregnated layer impregnated with the resin composition for the decorative board are laminated.

In the decorative board, the surface of the resin-impregnated layer (that is, the surface opposite to the base material) may have an embossed shape. The decorative board provided with the resin-impregnated layer produced by using the resin composition for a decorative board of the present invention exhibits synchronization according to the thickness of the resin-impregnated layer when embossed.

The decorative board may include other layers in addition to the above-mentioned layers. Examples of the other layers include a primer layer for improving the adhesion between the resin impregnated layer and the base material, a core material layer for the purpose of imparting shape stability of a decorative plate, and the resin. Examples thereof include a protective film for protecting the surface of the impregnated layer. It is preferable that the surface of the resin-impregnated layer, which is the side on which the mirror plates are overlapped during thermal pressure molding, does not have a release layer.

1 and 2 show an embodiment of the decorative board. The 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 heat curing in which the resin composition for a decorative plate, which is a thermosetting resin composition, is impregnated into the impregnated base material, 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 on the opposite side of the base material 1. The decorative board 10'shown in FIG. 2 includes a base material 1, a resin impregnated layer 2', and a protective film 3. The resin impregnated layer 2'is a layer in which a cured product of the resin composition for a decorative board is impregnated into the impregnated base material, 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 base material include an organic base material and an inorganic base material. Examples of the organic base material include wood base materials such as wood single plate, plywood, laminated material, particle board, medium density fiber board (MDF), high humidity fiber board, and Kenaf board; board paper, woven cloth, and non-woven fabric. , Resin-impregnated paper, fibrous base material such as resin-impregnated cloth; 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 Examples thereof include a synthetic resin base material such as a plastic plate. 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 bubble concrete plate, glass fiber Examples thereof include an inorganic base material such as a reinforced concrete plate. The base material may be a single layer, or may be 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 the adhesion to the resin impregnated layer.

The thickness of the base material 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 is sufficient and it is difficult to crack. When the thickness is 50 mm or less, it is lightweight and easy to handle.

As the protective film, a known or conventional film used for a decorative board can be used. For example, a plastic film such as a polyethylene terephthalate film (PET film), a polypropylene film, or a polybutylene terephthalate film is subjected to a mold release treatment. Examples thereof include a film made of plastic and a low-adhesion film. The protective film is peeled off when the decorative board is used.

The Gd value (the surface opposite to the substrate) of the surface of the resin impregnated layer is not particularly limited, but is preferably 0.2 or more, and more preferably 0.3 or more. When the Gd value is 0.2 or more, the vividness of the decorative board is more excellent.

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, still more preferably 70 or more. .. When the gloss value is 50 or more, the glossiness of the decorative board is more excellent.

[Manufacturing method of decorative board]
An embodiment of the method for manufacturing a decorative board will be described with reference to FIG. First, as described above, the impregnated substrate is impregnated with a thermosetting resin composition for a decorative board prepared by diluting or dissolving with a solvent as necessary, and then dried as necessary to volatilize the solvent. The resin impregnated layer 2 is prepared by impregnating the impregnated base material with the thermosetting resin composition for a decorative board. Then, if necessary, the resin impregnated layer 2 and a releasable base material such as a polyethylene film are bonded to obtain a decorative sheet. The bonding can be performed by laminating using, for example, a crimping roll.

Next, the decorative sheet is placed on the base material 1 so that the resin impregnated layer 2 is on the base material 1 side, and if it has a releasable base material, the releasable base material is peeled off and impregnated with the resin. The mirror surface plate 4 is superposed on the layer 2 to obtain a laminated body in which the decorative plate 10 and the mirror surface plate 4 are laminated. The surface of the mirror plate 4 facing the resin impregnated layer 2 has a shape for transferring the design to the resin impregnated layer, if necessary.

Next, using a press machine, thermosetting is performed by applying pressure while heating from above and below the laminate including the decorative plate 10, and the resin impregnated layer 2 is cured to impregnate the heat-cured resin. A layer 2'is formed, and a laminated body in which the decorative plate 10'and the mirror plate 4 are laminated is obtained. As described above, as the method of thermal pressure molding, it is preferable to use a laminated thermal pressure molding method, that is, the resin impregnated layer 2 and the base material 1 are overlapped with each other, placed in a mold, and heat-pressurized and cured. The thermal pressure molding can be preferably performed under the 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 laminate obtained after thermal pressure molding includes a decorative plate 10'in which a base material 1 and a thermosetting resin impregnated layer 2'provided on the base material 1 are laminated. After that, the mirror plate 4 is removed to obtain a decorative plate 10'. In the decorative board, the resin impregnated layer formed from the resin composition for the decorative board has excellent mold releasability with respect to the mirror surface plate, so that the mirror surface plate 4 can be easily removed.

When the decorative plate 10'having an embossed shape on the surface of the resin impregnated layer 2'is manufactured, a pressing plate 5 having an uneven shape on the surface facing the resin impregnated layer 2 is used instead of the mirror surface plate 4. Then, as shown in FIG. 4, when the pressing plate 5 is superposed 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. 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 high pressure is applied to the region to be the thin film portion 2b with respect to the region to be the thick film portion 2a. When the resin impregnated layer 2 contains a coloring pigment, the coloring pigment flows from the region that becomes the thin film portion 2b to the region that becomes the thick film portion 2a when pressure is applied. At this time, since the average particle size of aluminum hydroxide is small, the flow of the coloring pigment is not hindered and can flow smoothly. As a result, in the resin impregnated layer 2', the amount of the coloring pigment per unit area in the thick film portion 2a is larger than the amount in the thin film portion 2b, and synchronization is obtained. Then, it is subjected to thermal pressure molding using a press machine to obtain a decorative plate 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'on the decorative plate 10'. As described above, the decorative board can be manufactured.

As described above, the decorative plate provided with the resin-impregnated layer obtained by using the resin composition for decorative plates of the present invention is made nonflammable by containing aluminum hydroxide having an average particle size within a specific range. Excellent, yet excellent in releasability to the mirror plate after thermal pressure molding. Therefore, it is not necessary to separately provide a mold release layer between the resin impregnated layer and the mirror surface plate at the time of thermal pressure molding. When the average particle size of aluminum hydroxide is within a specific range, the flow of the resin composition during thermal pressure molding is suppressed, and the resin film thickness can be secured to a sufficient thickness. The decorative board has excellent vividness and gloss, is highly transparent, and has an excellent appearance. Further, when a resin-impregnated layer is produced by blending a coloring pigment with the resin composition for a decorative board and the surface of the resin-impregnated layer is embossed, synchronization is exhibited according to the thickness of the resin-impregnated layer. ..

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

<Decorative board with excellent releasability>
Example 1
Dialyl orthophthalate prepolymer (methyl ethyl ketone 50% by mass solution viscosity (30 ° C.) 96.5 mPa · s, manufactured by Osaka Soda Co., Ltd.) 56 parts by mass, unsaturated polyester (trade name "TH-2510", number average molecular weight 1291, weight) Average molecular weight 4404, molecular weight dispersion 3.41, acid value 12.8 KOHmg / g, manufactured by DIC Material Co., Ltd.) 43 parts by mass, dipentaerythritol hexaacrylate 14 parts by mass, aluminum hydroxide (trade name "BF013STM", average particles) Diameter 1 μm, with surface treatment, manufactured by Nippon Light Metal Co., Ltd.) 50 parts by mass, benzoyl peroxide 4 parts by mass, internal release agent (trade name "Zelec UN", manufactured by DuPont) 3 parts by mass, hydroquinone (polymerization prohibiting agent) A resin composition solution was prepared by dissolving 0.2 parts by mass of 0.2 parts by mass and 0.1 parts by mass of the defoaming agent in 100 parts by mass of acetone. A 60 g / m ² printing pattern paper is dipped in the resin composition solution at 25 ° C. to impregnate the resin composition, and then heated in a hot air circulation oven at 105 ° C. for 90 seconds to volatilize the solvent to 160 g / m. A decorative sheet composed of ² impregnated papers (impregnated amount with respect to 100 parts by mass of printing pattern paper: 167 parts by mass) was obtained.

A base material (trade name "Dylite", manufactured by Daiken Corporation, thickness 3 mm, non-combustible material) is placed on the migratory board, and the decorative sheet is placed on the base material, and the impregnated paper is used as the base. It was placed so that it was in contact with the material. Then, using a press machine, pressure was applied so that the hot plate on which the mirror surface plate was set was on the impregnated paper side and the other hot plate was on the migratory plate side, and the hot plate was heated to perform thermal pressure molding. The thermal pressure molding was carried out at a temperature of 160 ° C. and a pressure of 16 kgf / cm ² for 1 minute. Then, the pressure was released, and the laminated body of the migratory board, the base material, and the decorative sheet was taken out from the press machine and cooled to room temperature to obtain a decorative board.

Example 2
A decorative sheet and a decorative board were produced in the same manner as in Example 1 except that the blending amount of hydroquinone was changed to 0.1 parts by mass.

Comparative Example 1
A decorative sheet and a decorative plate were produced in the same manner as in Example 1 except that 60 parts by mass of aluminum hydroxide having a trade name "BE043STM", an average particle diameter of 4 μm, and surface treatment was used (manufactured by Nippon Light Metal Co., Ltd.). did.

(evaluation)
Each of the decorative boards obtained in Examples 1 and 2 and Comparative Example 1 was evaluated as follows. The evaluation results are shown in Table 1.

(1) Releasability In producing each of the decorative plates obtained in Examples and Comparative Examples, based on the time until the molded product falls from the mirror surface plate when the pressure is opened after the molding time has elapsed. Judgment was made according to the following criteria.
[criterion]
○ (Good): It peeled off from the mirror plate at the time of opening pressure, or soon fell from the mirror plate.
× (defective): It takes time to fall from the mirror plate.

(2) Molding stability The surface of the resin-impregnated layer of each decorative board obtained in Examples and Comparative Examples was visually observed and judged according to the following criteria.
[criterion]
○ (Good): No poor flow such as pinholes has occurred.
△ (Available): Slight flow defects such as pinholes have occurred.
× (Defective): A large amount of poor flow such as pinholes has occurred.

(3) 20 ° gloss For the surface of the resin-impregnated layer of each decorative board obtained in Examples and Comparative Examples, use a gloss meter (trade name "micro-TRI-gloss", manufactured by Gardener) to JIS Z8741. Measured according to the specified method.

(4) Gd value For the surface of the resin-impregnated layer of each decorative board obtained in Examples and Comparative Examples, a portable sharpness gloss meter (trade name "PGD-4", PGD meter, Japan Color Research Institute, Japan, Inc. The vividness measurement value (Gd value) to be displayed was measured using (manufactured by Tokyo Photoelectric Co., Ltd.).

As shown in Table 1, the decorative boards obtained in Examples 1 and 2 were evaluated to be excellent in mold releasability. Furthermore, it has nonflammability by containing a sufficient amount of aluminum hydroxide, has excellent molding stability, has high 20 ° gloss and excellent gloss, has a high Gd value, has excellent vividness, and has a good appearance. It was evaluated as. On the other hand, when the average particle size of aluminum hydroxide was 4 μm (Comparative Example 1), it was evaluated that the releasability was inferior.

<Decorative board with embossed shape>
Example 3
Dialyl orthophthalate prepolymer (methyl ethyl ketone 50% by mass solution viscosity (30 ° C.) 96.5 mPa · s, manufactured by Osaka Soda Co., Ltd.) 38 parts by mass, unsaturated polyester (trade name "DH-2000B", number average molecular weight 1869, weight) Average molecular weight 4846, molecular weight dispersion 2.59, acid value 21.1KOHmg / g, manufactured by DIC Material Co., Ltd. 81 parts by mass, dipentaerythritol hexaacrylate 5 parts by mass, aluminum hydroxide (trade name "BF013STM", average particles) Diameter 1 μm, with surface treatment, manufactured by Nippon Light Metal Co., Ltd.) 37.5 parts by mass, magnesium hydroxide (trade name “Magnice N-6”, average particle diameter 1.3 μm) 12.5 parts by mass, benzoyl peroxide 3 mass Part, internal release agent (trade name "Zerek UN", manufactured by DuPont) 1 part by mass, hydroquinone (polymerization prohibiting agent) 0.05 part by mass, fine powder silica (trade name "Carplex", Shionogi Pharmaceutical Co., Ltd.) A resin composition solution was prepared by dissolving 3 parts by mass of a pearl pigment (trade name "Iriodin 520", manufactured by Merck) and 0.15 parts by mass of an antifoaming agent in 100 parts by mass of acetone. A 60 g / m ² dark-colored printing pattern paper as an impregnating base material is dipped in the resin composition solution at 25 ° C. to impregnate the resin composition, and then heated in a hot air circulation oven at 105 ° C. for 90 seconds to form a solvent. Was volatilized to obtain a decorative sheet made of 160 g / m ² of impregnated paper (impregnation amount per 100 parts by mass of printing pattern paper: 167 parts by mass).

A base material (trade name "Dylite", manufactured by Daiken Corporation, thickness 3 mm, non-combustible material) is placed on the migratory board, and the decorative sheet is placed on the base material, and the impregnated paper is used as the base. It was placed so that it was in contact with the material. Then, using a press machine, 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 plate was on the migratory plate side, and the hot plate was heated to perform thermal pressure molding. The surface of the pressing plate facing the impregnated paper is formed with an uneven shape for imparting an embossed shape. The thermal pressure molding was carried out at a temperature of 150 ° C. and a pressure of 16 kgf / cm ² for 3 minutes. Then, the pressure was released, and the laminated body of the migratory board, the base material, and the decorative sheet was taken out from the press machine and cooled to room temperature to obtain a decorative board.

Example 4
A decorative sheet and a decorative board were produced in the same manner as in Example 3 except that 80 g / m ² of white paper was used as the impregnated base material.

Example 5
A decorative sheet and a decorative plate were produced in the same manner as in Example 3 except that the trade name "BF013" (average particle diameter 1 μm, no surface treatment, manufactured by Nippon Light Metal Co., Ltd.) was used as the aluminum hydroxide.

Example 6
A decorative sheet and a decorative board were produced in the same manner as in Example 5 except that 80 g / m ² of white paper was used as the impregnated base material.

Comparative Example 2
A decorative sheet and a decorative board were produced in the same manner as in Example 3 except that the trade name "BE043STM" (average particle diameter 4 μm, surface treatment, manufactured by Nippon Light Metal Co., Ltd.) was used as the aluminum hydroxide.

Comparative Example 3
A decorative sheet and a decorative board were produced in the same manner as in Comparative Example 2 except that 80 g / m ² of white paper was used as the impregnated base material.

(evaluation)
The decorative boards obtained in Examples 3 to 6 and Comparative Examples 2 to 3 were evaluated as follows. The evaluation results are shown in Table 2.

(5) Synchronism The surface of the resin-impregnated layer of each decorative board obtained in Examples and Comparative Examples was visually observed and judged according to the following criteria.
[criterion]
○ (Good): There is a large difference in the shade of coloring between the concave and convex parts, and the synchronization with the embossed shape is clear.
× (Defective): The difference in the shade of coloring between the concave portion and the convex portion is small, and the synchronization with the embossed shape cannot be felt.

As shown in Table 2, the decorative plates obtained in Examples 3 to 6 were evaluated to be excellent in synchronization. On the other hand, when the average particle size of aluminum hydroxide was 4 μm (Comparative Examples 2 to 3), it was evaluated that the synchronism was inferior.

Example 7
A decorative sheet and a decorative board were produced in the same manner as in Example 3 except that the impregnation amount with respect to 100 parts by mass of the print pattern paper was 183 parts by mass.

(6) Combustion test Each of the decorative boards obtained in Examples 3 and 7 was subjected to a combustion test in accordance with ISO5660 “Corn calorimeter method”. The combustion test was performed twice for each veneer. As a result, regarding the total calorific value for 20 minutes after the start of heating, the average value of the two combustion tests was 6.5 MJ / m ² in Example 3 and 7.5 MJ / m ² in Example 7. It should be noted that when the total calorific value is 8 MJ / m ² or less, it is shown that the nonflammability is excellent. From this result, it is recognized that the decorative boards of Examples 4 to 6 having the same impregnation amount also have nonflammability.

The physical characteristics of the unsaturated polyester resin used in Examples and Comparative Examples and the viscosity of the obtained solid content 50% by mass acetone solution of each resin composition were evaluated as follows.

(7) Average molecular weight of unsaturated polyester resin The weight average molecular weight and the number average molecular weight were measured by the GPC method using a standard polystyrene calibration curve under the following conditions.
Equipment: Shimadzu Prominence-i, LC-2030
Column: ShodexLF-804 x 2, guard column S
Transmutation phase: THF
Flow velocity: 1.0 ml / min
Injection volume: 50 μl
Column temperature: 40 ° C

(8) Viscosity Acetone was added to the resin composition so that the solid content concentration was 50% by mass, and the obtained solution was subjected to a B-type viscometer (trade name "BM type viscometer", Co., Ltd.) at 20 ° C. (Made by Tokimec) is used, and No. 1 is used as the rotor. 1 was used to measure at 6 rpm and 60 rpm, respectively. The rotor was rotated for at least 30 seconds, and then the value when the value became stable was read and used as the viscosity.

1 Base material 2 Resin impregnated layer (before thermosetting, prepreg)
2a Thick film part 2b Thin film part 2'Resin impregnated layer (thermoset)
3 Protective film 4 Mirror plate 5 Pressing plate 10,10'Decorative plate

Claims (11)

Contains diallyl phthalate resin, unsaturated polyester resin, and aluminum hydroxide,
The unsaturated polyester resin has a number average molecular weight of 500 to 2800 and has a number average molecular weight of 500 to 2800.
A resin composition for a decorative board, wherein the average particle size of the aluminum hydroxide is 3 μm or less. The resin composition for a decorative board according to claim 1, wherein the mass ratio of the diallyl phthalate resin to the unsaturated polyester resin (the former: the latter) is 20:80 to 90:10. The resin composition for a decorative board according to claim 1 or 2, wherein the viscosity (rotation number: 6 rpm) of the solid content 50% by mass acetone solution of the resin composition for a decorative board at 20 ° C. is 100 to 800 mPa · s. .. The resin composition for a decorative board according to any one of claims 1 to 3, which contains a coloring pigment. The resin composition for a decorative board according to any one of claims 1 to 4, which contains magnesium hydroxide. The decorative board according to any one of claims 1 to 5, wherein the content of aluminum hydroxide is 5 to 90 parts by mass with respect to 100 parts by mass in total of the diallyl phthalate resin and the unsaturated polyester resin. Resin composition. A resin impregnated layer containing the impregnated base material and the thermosetting resin composition impregnated in the impregnated base material is provided.
A decorative sheet, wherein the thermosetting resin composition is the resin composition for a decorative board according to any one of claims 1 to 6 or a cured product thereof. The decorative sheet according to claim 7, wherein the resin impregnated layer has the resin composition for a decorative plate on a surface that becomes a mirror plate side at the time of thermal pressure molding. The decorative sheet according to claim 7 or 8, which has an embossed shape on the surface of the resin impregnated layer. A decorative board comprising the base material and the decorative sheet according to any one of claims 7 to 9 provided on at least one surface of the base material. The decorative board according to claim 10, which has an embossed shape on the surface of the resin impregnated layer opposite to the base material.

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