JPH11207877A - Decorative plate and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily manufacture a decorative plate of a low cost having a heat resistance and stain resistance by sequentially laminting an adhesive layer made of a thermosetting resin, a design print sheet layer and a surface protective layer on one side surface of a base plate. SOLUTION: The decorative plate 1 is obtained by seqentially laminating from its bottom a base plate 2, a sealer layer 3, an adhesive layer 4, a design print sheet layer 5 and a surface protective layer 7. The plate 1 has a feature of a constitution obtained by laminating a thermosetting resin on a lower surface of the plate 1 by utilizing a papery sheet or a heat resistant film executed with a design print layer. The protective layer is formed of a curable resin to provide the plate having excellent heat resistance, stain resistance and wear resistance. Particularly, if the layer 6 is made of the papery sheet, the papery sheet is uniformly impregnated with a thermosetting resin for forming the layer 7 of an upper surface side and a thermosetting resin for forming the layer 4 of a lower surface side and cured, and hence it has a stable adhesive force and a heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative board having heat resistance, stain resistance and the like, which is used for various furniture surface materials and building interior materials, and a method for producing the same.

[0002]

2. Description of the Prior Art Conventionally, decorative boards having good printed patterns, heat resistance and stain resistance on surfaces used for various furniture surface materials and building interior materials include, for example, wood plywood, medium density fiberboard, particle board and the like. For example, (1) a sheet on which a pattern and a surface protective layer are formed is adhered to an inorganic substrate such as a wood substrate, a calcium silicate plate, an asbestos slate plate, and a cement slate plate using an emulsion adhesive. (2) After a picture pattern is provided by a method of transferring a picture pattern to an inorganic base material surface using a transfer paper or the like, a transparent paint is applied over the picture pattern layer to form a surface protective layer. Was known.

[0003] However, the decorative board adhered with the emulsion adhesive (1) is weak in heat resistance, and the decorative board (2) is satisfactory in heat resistance, but the process becomes complicated. However, there is a problem that the yield is low and the cost is high because transfer paper is used.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide heat resistance and stain resistance which are used for various furniture surface materials and building interior materials. It is an object of the present invention to provide a low-cost decorative board having the above and a manufacturing method capable of easily manufacturing the decorative board.

[0005]

Means for Solving the Problems A solution of the present invention for achieving the above object is to provide a laminate in which an adhesive layer, a pattern printing sheet layer, and a surface protective layer are sequentially laminated on one surface of a substrate, A decorative plate is characterized in that the adhesive layer is made of a thermosetting resin. With this configuration, since the adhesive layer is made of a thermosetting resin, a decorative board having excellent heat resistance of the adhesive layer can be obtained.

[0006] By forming the surface protective layer from a decorative board made of a curable resin, the surface of the decorative board can have fire resistance and stain resistance.
It also has excellent abrasion resistance.

The pattern printing sheet layer is a paper-based sheet, a pattern printing is performed on the opposite surface of the substrate, and the same surface as the substrate is impregnated with a thermosetting resin for forming the adhesive layer. Or a decorative board impregnated with a thermosetting resin and a curable resin forming the adhesive layer and the surface protective layer on both surfaces thereof, and in particular, the curable resin is impregnated over all layers of the paper-based sheet. By doing so, the interlayer adhesion strength of the entire decorative board is increased, and heat resistance, stain resistance and abrasion resistance are also excellent.

When the curable resin forming the surface protective layer is made of an ionizing radiation curable resin, the abrasion resistance and the abrasion resistance of the surface of the decorative board are further improved, and the stain can be easily wiped off.

When the substrate is made of an inorganic base material, it becomes a nonflammable decorative board, and its use is expanded.

[0010] A curable resin is applied to one side of the pattern printing sheet on which the pattern printing layer is formed, and after curing, a thermosetting resin is applied to the other side of the pattern printing sheet, followed by drying to the touch. The other side of the pattern printing sheet is overlapped and pressurized and heated so as to face one side of the substrate,
By the method of manufacturing a decorative board obtained by curing the thermosetting resin, heat resistance, excellent stain resistance, excellent wear resistance, and because the production process is simplified, production efficiency, An inexpensive decorative board with good yield can be easily and reliably manufactured.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an embodiment of a decorative board according to the present invention, FIG. 2 is a cross-sectional view for explaining a manufacturing process of the decorative board of the present invention, 1 is a decorative board, 2 is a substrate, 3 is a sealer layer, Reference numeral 4 denotes an adhesive layer, 5 denotes a pattern printing sheet layer, 6 denotes a paper-based sheet, 6 ′ denotes a pattern printing layer, 7 denotes a surface protective layer, and 10 denotes a hot plate.

As shown in FIG. 1, the decorative plate 1 of the present invention has a structure in which a substrate 2, a sealer layer 3, an adhesive layer 4, a pattern printing sheet layer 5, and a surface protective layer 7 are laminated in this order from the bottom. The decorative plate 1 is characterized in that a thermosetting resin is laminated on the lower surface of a paper-based sheet or a heat-resistant film provided with a picture printing layer, and an adhesive layer having excellent heat resistance. It becomes a decorative board having. Further, by using a curable resin for the surface protective layer, a decorative plate having excellent heat resistance, stain resistance, and abrasion resistance can be obtained. In particular, when the pattern printing sheet layer 5 is a paper-based sheet, the curable resin forming the upper surface side surface protection layer 7 and the thermosetting resin forming the lower surface side adhesive layer 4 uniformly penetrate the paper-based sheet. It has stable adhesive strength and heat resistance because it is hardened. Further, since the curable resin and the thermosetting resin penetrate all the layers of the paper-based sheet and are cured in a state of being in contact with each other, the interlayer bonding strength of the entire decorative board can be increased.

Next, a method for manufacturing the decorative board 1 of the present invention will be described with reference to the drawings, using a curable resin as a paper-based sheet and a surface protective layer. First, as shown in FIG. 2A, a decorative board substrate provided with the sealer layer 3 on the upper surface of the substrate 2 is prepared. Next, as shown in FIG. 2B, a picture print sheet 5 having a picture print layer 6 'provided on the surface of the paper-based sheet 6 is produced. Subsequently, as shown in FIG. 2A, a curable resin is applied from the upper surface, impregnated and cured to form a surface protective layer 7, and then, as shown in FIG. 2D, a thermosetting resin is formed on the lower surface of the pattern printing sheet 5 as an adhesive layer 4. Resin is applied and impregnated to dry to the touch. Subsequently, as shown in FIG. 2 (e), the surface of the thermosetting resin (adhesive layer 4) on the lower surface of the pattern printing sheet 5 is superimposed on the surface of the sealer layer 3 of the substrate 2, and the heated platen is heated. 10 and pressurize and heat. The thermosetting resin applied and impregnated on the paper-based sheet 6 is cured and integrated to obtain the decorative board 1 of the present invention as shown in FIG.

As the substrate 2 used for the decorative board 1 of the present invention, wood base materials such as wood, plywood, particle board, MDF, calcium silicate board, asbestos slate board, cement slate board, lightweight foam concrete board, hollow An inorganic base material such as an extruded cement plate, a metal base material such as a polished steel plate, a galvanized steel plate, or an aluminum plate can be used.

Here, when the substrate 2 is an inorganic base material, the sealer layer 3 prevents the elution of alkali components from the substrate 2.
In the case of a wood-based substrate, it is preferably provided for the purpose of preventing suction of an adhesive to the substrate 2 and, in the case of a metal-based substrate, for the purpose of preventing rust of the substrate 2 and the like. It is desirable to use a curable resin such as an isocyanate-based resin, a moisture-curable urethane-based resin, or an epoxy-based resin, but this is not necessarily required depending on the substrate.

In the case of a paper-based sheet 6 as a printing sheet used for the decorative board 1 of the present invention, the weight is 30 to 100 g /
building materials for printing paper m ^2, pure blank, bleached or unbleached kraft paper, one or ordinary titanium sheet or the like, mixed paper was混抄a so-called synthetic resin or the like, impregnated paper or the like impregnated with a latex or the like is used, Density, so that the curable resin as the surface protection layer 7 and the thermosetting resin as the adhesive layer 4 can penetrate,
It is preferable that the paper is subjected to papermaking with sufficient thickness control and calender roll processing for smoothing the surface. In addition, if the paper is impregnated, the paper-to-paper strength increases, which is more preferable.
In the case of a synthetic resin film, it is preferably made of a resin having excellent heat resistance, such as polyethylene terephthalate, polybutylene terephthalate, and polyamide, and has good adhesion to a thermosetting resin and a curable resin. If the material is porous so that the thermosetting resin as the adhesive layer 4 can penetrate, improvement of the adhesive strength is expected, which is still preferable.

The pattern printing layer 6 'is composed of a pattern ink layer formed by printing an arbitrary pattern such as a wood pattern, an abstract pattern, and a stone pattern, or a solid ink layer entirely printed thereon. Is a colorant that is a pigment or dye in the vehicle,
A mixture obtained by kneading a plasticizer, a stabilizer, other additives, a solvent or a diluent is used. Suitable materials for the vehicle include cellulose derivatives such as ethyl cellulose, cellulose nitrate, ethyl hydroxycellulose, cellulose acetate propionate and cellulose acetate, and butyral.

In the present invention, as the surface protective layer 7,
A film made of a resin having excellent heat resistance such as polyethylene terephthalate, polybutylene terephthalate, and polyamide, and a curable resin such as an ionizing radiation curable resin or a thermosetting resin (including a room temperature curable resin and a two-component reaction curable resin). Resin can be used. Here, when a curable resin is used as the surface protective layer 7, the ionizing radiation curable resin has a high curing speed and good workability, and can easily adjust the physical properties of the resin such as flexibility and hardness. Stain, abrasion resistance,
It is preferable because it has excellent properties such as abrasion resistance and solvent resistance. In the case of a film having excellent heat resistance, the film can be laminated as a surface protective layer by bonding with an adhesive having excellent heat resistance such as an epoxy resin-based or polyurethane-based adhesive.

The ionizing radiation-curable resin forming the surface protective layer 7 includes a (meth) acryloyl group,
It is composed of a monomer, prepolymer or polymer having a radically polymerizable unsaturated group such as a (meth) acryloyloxy group or a cationically polymerizable functional group such as an epoxy group (hereinafter, these are collectively referred to as compounds). . These monomers,
The prepolymer and the polymer may be used alone or as a mixture of two or more. In this specification, (meth) acrylate is used to mean acrylate or methacrylate.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, silicon (meth) acrylate, epoxy (meth) acrylate, and melamine (meth) acrylate. A) acrylate, triazine (meth) acrylate, polyvinylpyrrolidone and the like. This prepolymer usually has a molecular weight of about 10,000 or less. If the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. Although the above acrylate and methacrylate can be shared,
Acrylates are faster than acrylates in terms of the rate of crosslinking and curing by ionizing radiation. Therefore, acrylates are more advantageous for the purpose of curing efficiently at high speed and in a short time.

Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol epoxy resin, novolak epoxy resin and alicyclic epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, urethane vinyl ether, and the like. Vinyl ether resins such as ester vinyl ethers, cyclic ether compounds,
Prepolymers such as spiro compounds are exemplified.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers of a (meth) acrylate compound such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-
Dimethylaminomethyl (meth) acrylate, N, N-
Dimethylaminoethyl (meth) acrylate, N, N-
Diethylaminoethyl (meth) acrylate, N, N-
Diethylaminopropyl (meth) acrylate, N, N
-Dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobonyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (meth) acryloyloxypropyl hydrogen terephthalate and the like.

Further, as a polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, dipropylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acryl Over DOO, glycerin polyethylene oxide tri (meth) acrylate, tris (meth)
Acryloyloxyethyl phosphate and the like.

The monomer having a cationically polymerizable functional group is
Prepolymer monomers having a cationically polymerizable functional group can be used.

When the ionizing radiation-curable resin forming the surface protective layer 7 is cured by ultraviolet light or visible light, a photopolymerization initiator is added. Photopolymerization initiator in the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl Oxite, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoinsulfonic acid ester, a freeloxysulfoxonium diallyliodosyl salt, or the like is used alone or as a mixture. be able to. The amount of the photoinitiator added generally depends on the amount of the ionizing radiation curable resin 10.
It is about 0.1 to 10 parts by weight with respect to 0 parts by weight.

The ionizing radiation used in the present invention means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and cross-linking a molecule, such as visible light, ultraviolet (near ultraviolet, vacuum ultraviolet) X-ray, electron Line, ion beam and the like. Usually, ultraviolet rays or electron beams are used. Ultraviolet light sources, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamp lamps can be used as the ultraviolet light source. As the wavelength of the ultraviolet light, a wavelength range of 1900 to 3800 ° is mainly used. Also, as the electron beam source, various electron beam accelerators such as Cockloft-Walton type, Van degraft type, Resonant transformer type, Insulating core transformer type, or linear type, Dynamitron type, high frequency type lamp, Irradiation with electrons having an energy of 1000 KeV, preferably 100 to 300 KeV can be used. Upon irradiation with ionizing radiation, the ionizing radiation-curable resin undergoes a cross-linking polymerization reaction and changes to a three-dimensional polymer structure.

The coating method of the ionizing radiation-curable resin includes known methods such as gravure coat, gravure reverse coat, gravure offset coat, natural roll coat, reverse roll coat, bar coat, knife coat, screen coat, flow coat and spray coat. Coating means can be used, and the coating amount is 5 to 3 when dry.
0 g / m ² is appropriate. In addition, coloring may be performed by adding a pigment, a dye, or the like, if necessary.

The thermosetting resin used for the adhesive layer 4 which is applied to the lower surface side of the pattern printing sheet layer 5 and is used for curing by pressing and heating is, for example, a melamine resin.
Phenol resin, urea resin, guanamine resin, melamine-urea co-condensation resin, diallyl phthalate resin, unsaturated polyester resin and the like. Among the thermosetting resins, diallyl phthalate resin can be processed while hot when performing hot pressing, so that belt press molding, continuous processing by roll press molding is also possible, and the processing capacity is high, It is preferred. Further, an unsaturated polyester resin may be added to the diallyl phthalate resin in order to impart alkali resistance or adjust the reaction curing rate, thereby improving the performance.

The hot-press forming step in the manufacturing method of the decorative board 1 of the present invention is mainly a press forming step by a flat plate press or a roll press.
It is manufactured by hot pressing under the conditions of 0 ° C., a pressure of 10 to ²⁰ kg / cm ² , and a time of about 10 to 30 minutes.

[0030]

EXAMPLE 1 A solid printing layer and a stone-pattern printing layer were applied to the surface of an impregnated paper weighing 60 g / m ^{2 with} a normal gravure printing machine using a nitrifying cotton-based ink, and then two liquids were applied from above. A curable urethane-based ink was applied at 8 g / m ² (dry) and dried with hot air at 80 ° C. to form a surface protective layer. Then, a thermosetting unsaturated polyester-based resin is applied on the back surface of the urethane-coated paper for 3 hours.
It was coated with 0 g / m ² (dry), penetrated into the interior of the impregnated paper, and dried by touch. Subsequently, the thermosetting unsaturated polyester-based resin layer surface of the urethane coated paper has a thickness of 15 mm.
And placed in a hot press, at a temperature of 140 ° C. and a pressure of 5 kg / cm.
^The mixture was cured and integrated by heating and pressing at ^{2 for} 10 minutes to obtain a decorative board.

Example 2 A moisture-curable urethane paint was applied to a calcium silicate plate having a thickness of 5 mm by a 40 g / m ² (dry) sponge roll coater, dried at 150 ° C. for 1 minute, and treated with a sealer-treated inorganic substrate. Got ready. Separately, a solid printing layer and a stone pattern printing layer were applied to the surface of impregnated paper weighing 60 g / m ² using a cellulose nitrate-based ink using a usual gravure printing machine, and then an electron beam-curable resin coating was applied thereon. 15g
/ M ² (dry), and apply 3Mrad (175
kv) Irradiation to obtain EB coated paper. Next, 30 g / m ² (dry) of a thermosetting unsaturated polyester resin was applied to the back surface of the EB-coated paper, and was penetrated to the inside of the impregnated paper and dried by touch. Subsequently, the thermosetting unsaturated polyester-based resin layer surface of the EB coated paper was overlapped so as to be in contact with the sealer-treated surface of the calcium silicate plate, and set in a hot press, at a temperature of 135 ° C. and a pressure of 10 kg / c.
The mixture was cured by heating and pressing at m ^{2 for} 10 minutes to obtain an inorganic decorative board.

[0032]

As described above, the decorative sheet of the present invention has excellent heat resistance because the pattern printing sheet layer is laminated on the substrate surface via the adhesive layer made of thermosetting resin. In addition, since molding can be performed with a normal hot-press molding apparatus and the production process is simplified, production efficiency and yield can be improved, and an inexpensive decorative plate can be obtained.

Further, the pattern printing sheet layer is a paper-based sheet, and the surface protection layer is made of a thermosetting resin.
Adhesion with the surface protective layer and the adhesive layer located on both sides of the pattern printing sheet layer is also good, and particularly, a thermosetting resin and a curable resin that form the adhesive layer and the surface protective layer on all the layers of the pattern printing sheet layer By impregnation, the interlayer bonding strength of the entire decorative board is increased, and the decorative board is also excellent in heat resistance, stain resistance, and abrasion resistance.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a decorative board of the present invention.

FIG. 2 is a cross-sectional view illustrating a manufacturing process of the decorative board of the present invention.

[Explanation of symbols]

1 decorative board 2
Substrate 3 Sealer layer 4
Adhesive layer 5 Picture printing sheet layer 6
Paper-based sheet 6 'Picture print layer 7
Surface protective layer 10 hot plate

Claims (8)

[Claims] 1. A laminate in which an adhesive layer, a pattern printing sheet layer, and a surface protective layer are sequentially laminated on one surface of a substrate,
The decorative board, wherein the adhesive layer is made of a thermosetting resin. 2. The decorative board according to claim 1, wherein the surface protective layer is made of a curable resin. 3. The pattern printing sheet layer is a paper type sheet, a pattern printing is performed on an opposite surface of the substrate, and a thermosetting resin forming the adhesive layer on the same surface as the substrate is impregnated. The decorative board according to claim 1, wherein the decorative board is formed. 4. A thermosetting resin in which the pattern printing sheet layer is a paper-based sheet, a pattern printing is performed on the opposite surface of the substrate, and the adhesive layer and the surface protection layer are formed on both surfaces thereof. The decorative board according to claim 2, wherein the decorative board is impregnated with a curable resin. 5. The makeup according to claim 4, wherein the thermosetting resin and the curable resin forming the adhesive layer and the surface protective layer are impregnated in all of the paper-based sheet layers. Board. 6. The decorative board according to claim 2, wherein the curable resin forming the surface protective layer comprises an ionizing radiation curable resin. 7. The decorative board according to claim 1, wherein the substrate is made of an inorganic base material. 8. A curable resin is applied to one surface of a pattern printing sheet having a pattern printing layer formed thereon, and after curing, a thermosetting resin is applied to the other surface of the pattern printing sheet, and touch drying is performed. A decorative plate obtained by overlapping and applying pressure and heat so that the other surface of the pattern printing sheet faces one surface of the substrate to cure the thermosetting resin. Manufacturing method.