TWI631013B - Decorative sheet - Google Patents

Abstract

The decorative board of the present invention includes: a core layer containing a fibrous substrate, a thermoplastic resin, and a heat-absorbing metal hydroxide; and an intermediate layer containing a mixed paper and a thermosetting resin, the mixed paper containing a heat-absorbing metal hydroxide And a decorative layer comprising decorative paper and a thermosetting resin; the amount of the thermoplastic resin contained in the core layer is 10 g / m ² to 100 g / m ² .

Description

Decorative plates [Reference to related applications]

The patent application of the present invention claims priority based on Japanese Patent Application No. 2014-71573 filed with the Japan Patent Office on March 31, 2014, and refers to the entire contents of Japanese Patent Application No. 2014-71573 and refers to the invention patent Application.

The present invention relates to a decorative board.

Conventionally, thermosetting resin decorative boards such as a melamine decorative board are known (see Patent Documents 1 and 2). This decorative board is widely used in residential equipment, interior materials (such as ceilings, counters, etc.) and the like.

(Prior technical literature) (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-290444

Patent Document 2: Japanese Patent Laid-Open No. 2013-99939

The conventional decorative board is prone to the problem of bending. One aspect of the present invention is to provide a decorative plate capable of suppressing bending.

A decorative board according to one aspect of the present invention includes a core layer containing a fibrous base material, a thermoplastic resin, and a heat-absorbing metal hydroxide; and an intermediate layer containing a mixed paper and a thermosetting resin, the mixed paper containing a heat-absorbing metal A hydroxide; and a decorative layer containing decorative paper and a thermosetting resin; the amount of the thermoplastic resin contained in the core layer is 10 g / m ² to 100 g / m ² . The decorative plate of the present invention can suppress bending.

1‧‧‧ decorative layer

2‧‧‧ middle layer

3‧‧‧ prepreg

4‧‧‧ core layer

5‧‧‧ balance layer

7, 8‧‧‧ decorative board

Fig. 1 is a sectional view showing the structure of a decorative plate according to the first embodiment of the present invention.

Fig. 2 is a sectional view showing the structure of a decorative plate according to a fourteenth embodiment of the present invention.

Fig. 3 is a photograph of the decorative plate of Example 1 in a state where light from a rod-shaped fluorescent lamp is projected.

4 is a photograph of a decorative plate of Comparative Example 1 in a state where light from a rod-shaped fluorescent lamp is projected.

Embodiments of the present invention will be described below.

(1) Core layer

The decorative board of the present invention has a core layer. The core layer system includes a fibrous substrate, a thermoplastic resin, and an endothermic metal hydroxide.

Examples of the fibrous substrate include an organic fibrous substrate and an inorganic fibrous substrate. Examples of the organic fibrous substrate include polyethylene, polypropylene, Vinylon, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyamide, polyester, polyurethane, and the like. Fibers composed of various copolymers such as modified products and ethylene-vinyl acetate copolymers, and mixtures thereof.

Examples of the inorganic fibrous substrate include nonwoven fabrics and woven fabrics made of inorganic fibers such as glass fibers, rock wool, and carbon fibers. The basis weight of the inorganic fiber material is preferably in the range of 10 g / m ² to 200 g / m ² . Compared with the use of organic fiber substrates, the use of inorganic fiber substrates can further enhance the non-combustibility of decorative boards. In the inorganic fiber substrate, heat resistance, fire resistance, and impregnation of the slurry can be further improved, especially when a glass fiber nonwoven fabric is used.

The thermoplastic resin can function as a binder, for example. The thermoplastic resin is preferably an acrylic resin emulsion. In particular, if an acrylic resin emulsion having a glass transition temperature (Tg) of more than 0 ° C is used, the adhesion and moldability of the core layer can be improved, so it is better.

Among acrylic resin emulsions having a Tg exceeding 0 ° C, if an acrylic resin emulsion having an average particle diameter of 150 nm to 300 nm is used, the binding force of the core layer and the bending workability and smoothness of the decorative board can be further improved, so it is even more good.

The reason why the smoothness of the decorative plate is improved is presumably because the acrylic resin emulsion is fine particles. The average particle diameter is a value calculated using a laser light diffraction / scattering particle size measuring device (ELS-8000, manufactured by Otsuka Electronics Co., Ltd.) based on scattered light detected during laser irradiation.

The amount of the thermoplastic resin contained in the core layer (the weight of the thermoplastic resin contained in the core layer per unit area) is 10 g / m ² to 100 g / m ² . By not more than 100g / m ² , the non-combustibility of the decorative board can be further improved. In addition, when a decorative plate is manufactured by hot-press molding, the thermoplastic resin may be hard to bleed out when the decorative plate is 100 g / m ² or less.

In addition, when the core layer is manufactured from a prepreg, the adhesion of the prepregs to each other can be further improved by setting the amount of the thermoplastic resin contained in the core layer to 10 g / m ² or more. In addition, when the slurry is impregnated into the fibrous substrate to manufacture the core layer, the amount of the thermoplastic resin contained in the core layer is 10 g / m ² or more, so that the impregnation amount of the slurry can be more easily controlled.

The endothermic metal hydroxide system includes crystal water, and will be separated at high temperature. Dissolve and release water. The reaction that decomposes and releases water is an endothermic reaction, so the core layer containing the endothermic metal hydroxide will suppress the temperature rise of the decorative board during the combustion process, and achieve the effect of improving the non-combustibility of the decorative board.

Examples of the endothermic metal hydroxide include aluminum hydroxide, magnesium hydroxide, and calcium hydroxide, and aluminum hydroxide and magnesium hydroxide are particularly preferred. If aluminum hydroxide or magnesium hydroxide is used, the effect of improving the non-combustibility of the decorative board will be more significant.

The amount of the endothermic metal hydroxide contained in the core layer (the weight of the endothermic metal hydroxide contained in the core layer per unit area) is preferably in the range of 100 g / m ² to 300 g / m ² . When the core layer is manufactured from the prepreg, the adhesion of the prepregs to each other can be improved within the range, and the non-combustibility of the decorative board can be improved.

The average particle diameter of the endothermic metal hydroxide can be set in a range of, for example, 1 to 50 μm. The average particle diameter is an arithmetic average diameter calculated from a particle size distribution (volume distribution) detected by a laser diffraction / scattering method (micro-track method).

When the average particle diameter of the endothermic metal hydroxide is within the above range, the dispersibility of the endothermic metal hydroxide in the slurry can be improved, and the impregnation of the slurry with the fibrous substrate can be improved. In addition, the surface of the decorative board is relatively smooth.

The core layer may contain an inorganic filler other than the endothermic metal hydroxide, a silane coupling agent, a flame retardant, and the like. Examples of the inorganic filler include carbonates such as calcium carbonate, magnesium carbonate, and zinc carbonate, silicon dioxide, talc, and fly ash. The average particle diameter of the inorganic filler can be set in a range of, for example, 0.05 μm to 20 μm. When the average particle diameter is within this range, the impregnability of the slurry to the fibrous substrate is further improved. The average particle diameter of the inorganic filler is an arithmetic average diameter calculated from a particle size distribution (volume distribution) detected by a laser diffraction / scattering method (microtrack method).

Among the inorganic fillers, carbonates (for example, calcium carbonate) are particularly preferred. When calcium carbonate is used, the workability and machinability in the manufacture of decorative boards are further improved. As the calcium carbonate, for example, heavy calcium carbonate and light calcium carbonate (precipitable calcium carbonate) can be used. The average particle diameter of calcium carbonate can be, for example, 0.05 μm to 10 μm, and more preferably 0.1 μm to 5 μm. By setting the average particle diameter of the calcium carbonate to 0.05 μm or more, it is difficult for the calcium carbonate to agglomerate in the slurry, and the impregnation adaptability of the slurry to the fibrous substrate can be improved. In addition, by setting the average particle diameter of calcium carbonate to 10 μm or less, the surface of the decorative plate becomes smoother and the appearance of the decorative plate is improved.

In addition, light calcium carbonate refers to calcium carbonate that is calcined into limestone and is chemically manufactured; and heavy calcium carbonate refers to finely divided calcium carbonate that is made by pulverizing white crystalline limestone dry or wet.

The blending ratio of the endothermic metal hydroxide to all the inorganic fillers contained in the core layer can be, for example, 30% to 100% by weight. If it is 30% by weight or more, the non-combustibility of the decorative board can be further improved. If it is 100% by weight or less, the machinability of the decorative plate can be further improved.

Regarding the boiling resistance of JIS K-6902 "Testing method for thermosetting resin high-pressure decorative board", compared with the case where the core layer does not contain a silane coupling agent, the weight increase rate becomes lower when the core layer contains a silane coupling agent. The adhesion between the core layer and the middle layer is further improved.

The amount of the silane coupling agent contained in the core layer (the weight of the silane coupling agent contained in the core layer per unit area) is preferably in the range of 1 g / m ² to 15 g / m ² . By being in this range, the efficacy of the above-mentioned silane coupling agent becomes more remarkable.

Examples of the silane coupling agent include (meth) acrylic acid such as 3- (meth) acrylfluorenyloxypropyltrimethoxysilane, and 3- (meth) acrylfluorenyloxypropyltriethoxysilane. Fluorenyloxysilane; vinyltrimethoxysilane, vinyltriethoxysilane and other vinyl-containing silanes; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Epoxy-containing silanes such as propylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styrene-based trimethoxysilanes containing styrene groups; 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxy Amine-containing silanes such as aminosilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like. In particular, when an silane containing an epoxy group or a silane containing an amine group is used, the crosslinking density in the core layer is further increased.

As the flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, and a phosphorus / nitrogen-based flame retardant are suitably used, and a phosphorus / nitrogen-based flame retardant is particularly preferred. Phosphorus / nitrogen-based flame retardants are compounds that function as both phosphorus-based and nitrogen-based flame retardants. Phosphorus / nitrogen flame retardants have both phosphorus and nitrogen atoms in one molecule. If exposed to high temperature, phosphorus will block oxygen due to strong dehydration, and nitrogen will generate ammonia gas to block oxygen. This action makes the phosphorus / nitrogen-based flame retardant highly heat-resistant and flame-retardant. Therefore, the non-combustibility of the core layer containing a phosphorus / nitrogen-based flame retardant is high.

When the total weight of the phosphorus / nitrogen-based flame retardant is 100% by weight, the total phosphorus content ratio is preferably 1% to 50% by weight, and the total nitrogen content ratio is 1% to 50% by weight; more preferably, the total The phosphorus content ratio is 1% to 30% by weight, and the total nitrogen content ratio is 5% to 35% by weight.

When the total phosphorus content ratio and the total nitrogen content ratio are within the above ranges, the non-combustibility will be further improved.

The amount of the flame retardant contained in the core layer (the weight of the flame retardant contained in the core layer per unit area) is preferably in the range of 1 g / m ² to 100 g / m ² . By being in this range, the efficacy of the flame retardant mentioned above becomes more significant.

The core layer can be made by impregnating a fibrous substrate with a slurry containing a thermoplastic resin, an endothermic metal hydroxide, or the like to produce a prepreg, and heating one or more (for example, two) prepregs thus produced with heat. Manufactured by press forming method. The slurry used may further contain a silane coupling agent, a flame retardant, and the like.

When the slurry is impregnated into the fibrous base material to produce the core layer, the value of the impregnation ratio shown in Formula 1 is preferably in the range of 500% to 1200%.

In Formula 1, "weight before impregnation" means the weight of the fibrous substrate. "Weight after impregnation" means the weight after impregnating the fibrous substrate with the slurry and drying it. When the impregnation rate is 1200% or less, the solid content of the slurry is prevented from falling off from the prepreg, and the prepreg can be easily processed. When the impregnation value is 500% or more, interlayer peeling of the prepreg is unlikely to occur.

When manufacturing the core layer by impregnating the slurry with a fibrous substrate, the thermoplastic resin, the endothermic metal hydroxide, the silane coupling agent, and the flame retardant can be adjusted in the slurry to adjust the blending ratio of the thermoplastic resin, The content of the endothermic metal hydroxide, silane coupling agent, flame retardant, etc. is set within the above-mentioned preferred range.

For example, the blending ratio of the thermoplastic resin in the slurry can be set to 3% to 17% by weight in terms of solid content. The blending ratio of the endothermic metal hydroxide in the slurry can be 20% to 95% by weight. In addition, the blending ratio of the silane coupling agent in the slurry may be 0.1% to 10% by weight in terms of solid content. In addition, the blending ratio of the flame retardant in the slurry can be 0.1 to 15% by weight in terms of solid content. The blending ratio of the slurry is a value when the entire amount of the slurry is 100% by weight.

(2) Middle layer

The intermediate layer system includes a hybrid paper and a thermosetting resin, and the hybrid paper system contains an endothermic metal hydroxide. With this intermediate layer, the bottom layer of the core layer can not easily appear on the surface of the decorative board, and the smoothness of the surface of the decorative board can be improved and the warpage of the decorative board can be suppressed.

The mixed paper containing an endothermic metal hydroxide is obtained, for example, by making paper, dehydrating, and drying a slurry containing pulp and an endothermic metal hydroxide. Examples of the pulp include natural pulp such as wood pulp, kapok pulp, and plant fiber pulp. In particular, chemical pulp that chemically treats wood pulp with short fiber length such as broadleaf bleached kraft pulp and conifer kraft pulp is preferred because it can improve the paper strength and impregnation suitability of mixed papers. It is also possible to use both broadleaf bleached kraft pulp and conifer kraft pulp. In addition, the coniferous kraft pulp may be either bleached or unbleached.

Examples of the endothermic metal hydroxide include aluminum hydroxide, magnesium hydroxide, and calcium hydroxide, and aluminum hydroxide and magnesium hydroxide are particularly preferred. When aluminum hydroxide or magnesium hydroxide is used, the effect of improving the non-combustibility of the decorative board will be more significant.

The mixing ratio of the endothermic metal hydroxide in the mixed paper containing the endothermic metal hydroxide is the ratio of the endothermic metal hydroxide when the total amount of the endothermic metal hydroxide and the pulp is 100% by weight (unit) % By weight). The mixing ratio of the endothermic metal hydroxide is preferably 40% to 95% by weight, and more preferably 55% to 85% by weight. If the mixing ratio of the endothermic metal hydroxide is 40% by weight or more, the non-combustibility of the decorative board becomes higher, and if it is 95% by weight or less, the paper strength of the mixed paper becomes higher.

In addition to the pulp and the endothermic metal hydroxide, the slurry can be added with, for example, a cohesive binder, a chemical agent, an organic fiber, an inorganic fiber, a fixing agent, and the like. In the papermaking process, a cylinder paper machine, a fourdrinier multi-cylinder paper machine, a fourdrinier-drilled paper machine, an inclined paper machine, and the like can be used. The basis weight of the mixed paper containing the endothermic metal hydroxide can be set to, for example, 60 g / m ² to 200 g / m ² . If the basis weight of the mixed paper is within this range, the smoothness of the decorative board can be further improved, and warpage of the decorative board can be further suppressed. The mixed paper containing endothermic metal hydroxide has a self-extinguishing property and can suppress flame diffusion.

Examples of the thermosetting resin include an amino-formaldehyde resin, a diallyl phthalate resin, an unsaturated polyester resin, or a mixed resin thereof. Amine-formaldehyde tree with excellent properties such as heat resistance and strength among thermosetting resins Fat is preferred. Amine-formaldehyde resin can be obtained by condensing an amine compound such as melamine, urea, acetoguanamine, benzoguanamine, and formaldehyde.

The intermediate layer can be produced, for example, by impregnating a resin liquid whose main component is a thermosetting resin into a mixed paper containing an endothermic metal hydroxide and drying it. The impregnation rate when impregnating and drying a resin liquid whose main component is a thermosetting resin is preferably in the range of 5% to 150%. This impregnation rate is a value defined by the above formula 1. At this time, "weight before impregnation" in Formula 1 means the weight of the mixed paper containing the endothermic metal hydroxide; "weight after impregnation" means the resin paper is impregnated with the mixed paper containing the endothermic metal hydroxide And the weight after drying.

(3) Decorative layer

The decorative layer contains decorative paper and a thermosetting resin. The decorative paper can be, for example, a decorative paper of 30 g / m ² to 140 g / m ² for a thermosetting resin decorative board.

As the thermosetting resin, for example, an amino-formaldehyde resin, a diallyl phthalate resin, an unsaturated polyester resin, or a mixed resin of these can be used. Among the resins, amine-formaldehyde resins having excellent heat resistance and abrasion resistance are preferred; melamine-formaldehyde resins having excellent water resistance, heat resistance, abrasion resistance, chemical resistance, and pollution resistance are particularly preferable.

The decorative layer can be produced, for example, by impregnating a decorative paper with a resin liquid whose main component is a thermosetting resin and drying it. The resin solution is impregnated with decorative paper and The impregnation rate during drying is preferably in the range of 30% to 300%. At this time, the "weight before impregnation" in Formula 1 means the weight of the decorative paper; the "weight after impregnation" means the value after impregnating the resin solution and drying it.

(4) Other

The decorative sheet of the present invention can be produced, for example, by hot-press forming each layer including the core layer, the intermediate layer, and the decorative layer with a press such as a flat plate press or a continuous press.

The stacking order of the decorative boards can be set to the order of the core layer, the intermediate layer, and the decorative layer, for example. The core layer and the intermediate layer may be in direct contact, or there may be other layers between the core layer and the intermediate layer. In addition, the intermediate layer and the decoration layer may be in direct contact, or there may be other layers between the intermediate layer and the decoration layer.

The decorative panel can have a decorative layer on one side or a decorative layer on both sides. When a decorative layer is provided on one side of the decorative plate, the decorative plate preferably includes a balance layer. In this case, the decorative board may include an intermediate layer and a decorative layer on one side of the core layer, and a balance layer on the opposite side of the core layer. When the balance layer is provided, it is possible to further suppress the warpage or damage of the decorative plate.

The balance layer system can be produced, for example, by impregnating a resin solution with paper and drying it. At this time, the balance layer system includes paper and a resin contained therein. Examples of the resin contained in the resin solution include melamine resin, urea resin, guanamine resin, diallyl phthalate resin, unsaturated polyester resin, acrylic resin, and mixed resins thereof.

Examples of the paper for the balance layer include surface paper for decorative boards having a basis weight of 18 g / m ² to 40 g / m ² .

The impregnation rate when the resin liquid is impregnated into the paper for the equilibrium layer and dried is preferably in the range of 260% to 320%. This impregnation rate is a value defined by the above formula 1. At this time, "weight before impregnation" in Formula 1 means the weight of the paper for the balance layer; "weight after impregnation" means the weight after impregnating the resin solution and drying.

[Example 1]

(1) Manufacturing of slurry

The following ingredients were mixed to make a slurry. In addition, the numerical value of a weight part is a solid content conversion value.

Acrylic resin emulsion (model RAX-208, AICA Industrial Co., Ltd.): 32 parts by weight

Aluminum hydroxide: 300 parts by weight

3-glycidoxypropyltrimethoxysilane: 3.5 parts by weight

Phosphorus / nitrogen flame retardant: 18 weight points

Water: 170 weight points

An example of the acrylic resin emulsion-based thermoplastic resin. The glass transition temperature (Tg) of the acrylic resin emulsion was 60 ° C. The acrylic resin emulsion uses 2-ethylhexyl acrylate and methyl methacrylate as the main monomers. The average particle diameter of the acrylic resin emulsion was 200 nm. Acrylic resin emulsion It functions as an adhesive.

An example of an aluminum hydroxide-based endothermic metal hydroxide. The average particle diameter of aluminum hydroxide was 8 μm. An example of a 3-glycidoxypropyltrimethoxysilane-based silane coupling agent. The phosphorus / nitrogen-based flame retardant has a phosphorus content of 16% and a nitrogen content of 22%.

Table 1 shows the composition of the slurry in Example 1 and other examples and comparative examples described later.

(2) Manufacturing of prepreg

A glass fiber nonwoven fabric of 40 g / m ² was prepared as a fibrous substrate. The fibrous substrate is impregnated with the slurry produced in the above (1) so that the impregnation rate defined in the above formula 1 becomes 750%, and dried to produce a prepreg. The prepreg includes a fibrous substrate, an acrylic resin emulsion, and aluminum hydroxide.

The amount (weight per unit area) of the acrylic resin emulsion, aluminum hydroxide, silane coupling agent, and flame retardant contained in one piece of prepreg was 27.16 g / m ² , 254.60 g / m ² , and 2.97 g / m ² , 15.28g / m ² .

Table 2 shows the composition of the prepreg in Example 1 and other examples and comparative examples described later.

The numerical values in Table 2 are the weights of the components contained in the 1 m ² prepreg.

(3) Manufacturing of intermediate layers

An aluminum hydroxide mixed paper having a basis weight of 110 g / m ^{2 was} prepared as a mixed paper (trade name: SUN WALL, manufactured by Sanzen Paper Co., Ltd., and the aluminum hydroxide mixed ratio was 69% by weight). This mixed paper is an example of a mixed paper containing an endothermic metal hydroxide.

A resin liquid whose main component is a melamine-formaldehyde resin is impregnated into the mixed paper so that the impregnation rate defined in the aforementioned Formula 1 becomes 30%, and dried to produce an intermediate layer. The intermediate layer comprises a mixed paper containing aluminum hydroxide, and a melamine-formaldehyde resin contained in the mixed paper. An example of the melamine-formaldehyde resin-based thermosetting resin. The amount of the melamine-formaldehyde resin contained in the intermediate layer was 33 g / m ² .

The contents of the intermediate layer in Example 1 and other examples and comparative examples described later are shown in Table 3.

In Table 3, "Al mixed paper" means aluminum hydroxide mixed paper, and "KP paper" means kraft pulp paper. The "weight per unit area" in Table 3 means the weight per unit area of the aluminum hydroxide mixed paper. The "impregnation rate" in Table 3 means the impregnation rate when the resin liquid is impregnated with the mixed paper. The “impregnation amount” in Table 3 means the resin adhesion amount (solid content conversion) per 1 m ² of aluminum hydroxide mixed paper or kraft pulp paper.

(4) Manufacturing of decorative layer

A resin liquid whose main component is melamine-formaldehyde resin is impregnated with a decorative paper for a white thermosetting resin decorative board having a basis weight of 100 g / m ² so that the impregnation rate defined in the foregoing formula 1 becomes 130%, and dried to Manufacture of decorative layers. The decorative layer includes decorative paper and a melamine-formaldehyde resin contained in the decorative paper. An example of the melamine-formaldehyde resin-based thermosetting resin. The amount of the melamine-formaldehyde resin contained in the decoration layer was 130 g / m ² .

(5) Manufacturing of decorative boards

Starting from the bottom, two prepregs, one intermediate layer, and one decorative layer were sequentially laminated, and a flat processing board was used, which was hot-pressed and integrated at 132 ° C, 70 kgf / cm ² for 64 minutes, and integrated. Get decorative boards. At this time, the two prepregs form a core layer.

As shown in FIG. 1, the decorative plate 7 manufactured as described above is a laminated body in which a core layer 4, an intermediate layer 2, and a decorative layer 1 composed of two prepregs 3 are laminated.

The structure of the decorative plate in Example 1 and other examples and comparative examples described later is shown in Table 4.

In addition, since the core layer in each of Examples and Comparative Examples is composed of two prepregs, the content of each component is twice the content shown in Table 2.

[Example 2]

Except that the basis weight of aluminum hydroxide mixed paper 180g / m ² (trade name: SUN WALL, three good Paper Co., Ltd., aluminum hydroxide, the mixing ratio of 69 wt%) in the manufacturing process of the intermediate layer is used as the mixed paper, with the The decorative plate was manufactured in the same manner as in the aforementioned embodiment 1.

[Example 3]

Except that 80g / m of the intermediate layer in the manufacturing process of aluminum hydroxide in the mixed paper ² (manufactured by Awa Paper Co., Ltd., mixing ratio of aluminum hydroxide 69 wt%) was used as mixed paper, in the same manner as the foregoing embodiment 1 is manufactured decorative board.

[Example 4]

A decorative board was manufactured in the same manner as in Example 1 except that the impregnation rate when the resin solution was impregnated with the aluminum hydroxide mixed paper was set to 100% during the manufacturing process of the intermediate layer.

[Example 5]

A decorative plate was produced in the same manner as in Example 1 except that the impregnation rate when the resin solution was impregnated with the aluminum hydroxide mixed paper was set to 10% during the manufacturing process of the intermediate layer.

[Example 6]

In addition to the amount of acrylic resin emulsion formulated in the slurry manufacturing process The decorative plate was manufactured in the same manner as in the above-mentioned Example 1 except that it was set to 58 parts by weight.

[Example 7]

A decorative plate was produced in the same manner as in Example 1 except that the blending amount of the acrylic resin emulsion was set to 17 parts by weight during the production of the slurry.

[Example 8]

A decorative plate was produced in the same manner as in Example 1 except that the compounded amount of 3-glycidoxypropyltrimethoxysilane was set to 18 parts by weight during the production of the slurry.

[Example 9]

A decorative plate was produced in the same manner as in Example 1 except that the compounded amount of 3-glycidoxypropyltrimethoxysilane was set to 1.8 parts by weight in the manufacturing process of the slurry.

[Example 10]

A decorative plate was manufactured in the same manner as in Example 1 except that the blending amount of aluminum hydroxide was set to 600 parts by weight in the manufacturing process of the slurry.

[Example 11]

In the manufacturing process of a slurry, the compounding quantity of aluminum hydroxide was 100 weight%. In addition, 100% by weight of heavy calcium carbonate having an average particle diameter of 1 μm was added to the slurry. Other than that, a decorative plate was manufactured in the same manner as in the aforementioned first embodiment.

[Example 12]

A decorative plate was manufactured in the same manner as in Example 1 except that the blending amount of the phosphorus / nitrogen-based flame retardant was set to 35 parts by weight in the manufacturing process of the slurry.

[Example 13]

A decorative plate was manufactured in the same manner as in Example 1 except that the blending amount of the phosphorus / nitrogen-based flame retardant was set to 3.5 parts by weight in the manufacturing process of the slurry.

[Example 14]

(1) Manufacturing of balance layer

A resin liquid whose main component is melamine-formaldehyde resin is impregnated into a surface paper for a decorative board having a basis weight of 24 g / m ² so that the impregnation rate defined by the above formula 1 becomes 280%, and the equilibrium layer is produced by drying. . The balancing layer comprises a surface paper and a melamine resin contained in the surface paper. The amount of the melamine-formaldehyde resin contained in the balance layer was 67.2 g / m ² .

(2) Manufacturing of decorative boards

From the bottom, one piece of the balance layer made in the above (1), two pieces of prepreg, one piece of intermediate layer, and one piece of decorative layer were laminated in this order, and a flat processing board was used at 132 ° C, 70 kgf / cm ² , 64 Under the condition of one minute, hot press molding and integration were performed to obtain a decorative board. In addition, the prepreg, the intermediate layer, and the decoration layer used in this embodiment are the same as those in the first embodiment.

As shown in FIG. 2, the decorative plate 8 manufactured in the above manner is a laminated body including a core layer 4, an intermediate layer 2, and a decorative layer 1 composed of a balance layer 5 and two prepregs 3. The decorative plate 8 is provided with the intermediate layer 2 and the decorative layer 1 on one side (upper side in FIG. 2) of the core layer 4, and includes a balance layer 5 on the opposite side (lower side in FIG. 2) of the core layer 4.

[Example 15]

A decorative plate was manufactured in the same manner as in the aforementioned embodiment 14, except that the intermediate layer was the same as the aforementioned embodiment 2.

[Example 16]

A decorative plate was manufactured in the same manner as in the aforementioned embodiment 14, except that the intermediate layer was the same as the aforementioned embodiment 3.

[Example 17]

A decorative plate was manufactured in the same manner as in the foregoing Example 14 except that the intermediate layer was the same as in the foregoing Example 4.

[Example 18]

A decorative plate was manufactured in the same manner as in the aforementioned embodiment 14, except that the intermediate layer was the same as the aforementioned embodiment 5.

[Example 19]

A decorative plate was manufactured in the same manner as in the aforementioned Example 14, except that the prepreg was the same as the aforementioned Example 6.

[Example 20]

A decorative plate was manufactured in the same manner as in the foregoing Example 14 except that the prepreg was the same as in the foregoing Example 7.

[Example 21]

A decorative plate was manufactured in the same manner as in the aforementioned Example 14, except that the prepreg was the same as the aforementioned Example 8.

[Example 22]

A decorative plate was manufactured in the same manner as in the aforementioned Example 14, except that the prepreg was the same as the aforementioned Example 9.

[Example 23]

A decorative plate was manufactured in the same manner as in the foregoing Example 14 except that the prepreg was the same as in the foregoing Example 10.

[Example 24]

A decorative plate was manufactured in the same manner as in the foregoing Example 14 except that the prepreg was the same as in the foregoing Example 11.

[Example 25]

A decorative plate was manufactured in the same manner as in the aforementioned Example 14, except that the prepreg was the same as the aforementioned Example 12.

[Example 26]

A decorative plate was manufactured in the same manner as in the foregoing Example 14, except that the prepreg was the same as in the foregoing Example 13.

[Example 27]

Except that in the manufacturing process of the slurry, the same amount of 3- (2-aminoethyl) aminopropyltrimethoxysilane was blended to replace 3-glycidoxypropyltrimethoxysilane, and The decorative plate was produced in the same manner as in Example 1.

[Example 28]

Except that in the manufacturing process of the slurry, the same amount of 3- (2-aminoethyl) aminopropyltrimethoxysilane was blended to replace 3-glycidoxypropyltrimethoxysilane, and Example 14 produced a decorative plate in the same manner.

[Example 29]

Except in the manufacturing process of the slurry, the same amount of nitrogen-based flame retardant (trade name APINON-901, the main component is melamine sulfate, the total nitrogen is 48%, and the total sulfur is 9%. ) A decorative plate was produced in the same manner as in Example 1 except that the phosphorus / nitrogen-based flame retardant was replaced.

[Example 30]

Except in the manufacturing process of the slurry, the same amount of nitrogen-based flame retardant (trade name APINON-901, the main component is melamine sulfate, the total nitrogen is 48%, and the total sulfur is 9%. ) A decorative plate was produced in the same manner as in Example 14 except that the phosphorus / nitrogen-based flame retardant was replaced.

[Example 31]

A decorative plate was manufactured in the same manner as in the foregoing Example 1 except that RAX-208E was replaced with the same amount in the manufacturing process of the slurry. RAX-208E is an acrylic resin emulsion made by AICA Industrial Co., Ltd. The glass transition temperature (Tg) of RAX-208E was 0 ° C. The main single system of RAX-208E is 2-ethylhexyl acrylate and methyl methacrylate.

[Example 32]

Except that the same amount of RAX-208E was substituted in the manufacturing process of the slurry to replace RAX-208, it was manufactured in the same manner as in Example 14 Decorative plates.

[Example 33]

A decorative plate was manufactured in the same manner as in the foregoing Example 1 except that RAX-208D was replaced with the same amount in the manufacturing process of the slurry. RAX-208D is an acrylic resin emulsion made by AICA Industrial Co., Ltd. RAX-208D has a glass transition temperature (Tg) of 30 ° C. The main single system of RAX-208D is 2-ethylhexyl acrylate and methyl methacrylate.

[Example 34]

A decorative panel was manufactured in the same manner as in the aforementioned Example 14 except that RAX-208D was replaced with the same amount in the manufacturing process of the slurry.

[Example 35]

A decorative plate was manufactured in the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was not blended in the manufacturing process of the slurry.

[Example 36]

A decorative plate was manufactured in the same manner as in Example 14 except that 3-glycidoxypropyltrimethoxysilane was not blended in the manufacturing process of the slurry.

[Example 37]

A decorative plate was manufactured in the same manner as in Example 1 except that the phosphorus / nitrogen-based flame retardant was not blended in the manufacturing process of the slurry.

[Example 38]

A decorative plate was manufactured in the same manner as in Example 14 except that a phosphorus / nitrogen-based flame retardant was not blended in the manufacturing process of the slurry.

[Example 39]

A decorative plate was manufactured in the same manner as in the foregoing Example 1 except that the same amount of magnesium hydroxide was used in place of aluminum hydroxide in the manufacturing process of the slurry.

[Example 40]

A decorative plate was manufactured in the same manner as in Example 1 except that an aluminum hydroxide mixed paper having a mixing ratio of aluminum hydroxide of 60% by weight was used in the manufacturing process of the intermediate layer.

[Example 41]

A decorative board was manufactured in the same manner as in Example 1 except that an aluminum hydroxide mixed paper having a mixing ratio of aluminum hydroxide of 80% by weight was used in the manufacturing process of the intermediate layer.

(Comparative example 1)

A decorative plate was manufactured in the same manner as in the aforementioned embodiment 1 except that the intermediate layer was not provided.

(Comparative example 2)

A decorative plate was manufactured in the same manner as in Example 1 except that the blending amount of the acrylic resin emulsion was set to 7 weight percent and the blending amount of aluminum hydroxide was set to 250 weight percent during the manufacturing process of the slurry.

(Comparative example 3)

A decorative plate was produced in the same manner as in Example 1 except that the blending amount of the acrylic resin emulsion was set to 76 parts by weight during the production of the slurry.

(Comparative Example 4)

A decorative board was manufactured in the same manner as in Example 1 except that the kraft paper was impregnated with a phenol resin impregnated with 50%. The phenolic resin-impregnated kraft paper having an impregnation ratio of 50% is impregnated with a phenolic resin in 190 g / m ² of kraft paper so that the impregnation ratio defined in the above formula 1 becomes 50% and dried.

(Comparative example 5)

A decorative board was manufactured in the same manner as in Example 1 except that the kraft paper was impregnated with a phenol resin impregnated with 30%. The phenolic resin-impregnated kraft paper having an impregnation rate of 30% is impregnated with 110 g / m ² of phenolic resin in kraft paper so that the impregnation rate defined in the above formula 1 becomes 30%, and dried.

<Decoration board evaluation>

Smoothness and non-combustibility for the decorative plates in each Example and Comparative Example Evaluation test of properties, bending workability, weight increase rate, and warpage. The evaluation test method is as follows.

(1) Smoothness

Visually observe the decorative board. The smoothness of the decorative layer is "○" if there are no cracks or wrinkles, and the smoothness is "△" if there are slight wrinkles.

In addition, the light of a rod-shaped fluorescent lamp was projected on the decorative plate of Example 1 and Comparative Example 1, and the decorative plate was imaged in this state. A photograph of the decorative plate of Example 1 is shown in FIG. 3, and a photograph of the decorative plate of Comparative Example 1 is shown in FIG. 4. Since the smoothness of the surface of the decorative plate of Example 1 is high, the shape of the fluorescent lamp can be faithfully reflected. On the other hand, since the smoothness of the surface of the decorative plate of Comparative Example 1 was low, the shape of the fluorescent lamp was blurred.

(2) Non-combustibility

A 20-minute exothermic test was performed by a cone calorimeter according to ISO5660. When all the following conditions of α to γ are satisfied, it is evaluated as ○, and the other systems are evaluated as ×.

α: The total calorific value is 8 MJ / m ² or less.

β: The maximum heating speed is more than 10 seconds and does not exceed 200KW / m ² .

γ: No cracks or holes penetrated to the back surface occurred within 20 minutes after the start of the test.

(3) Bendability

A 150 mm wide sample was cut from the decorative board. Then, the rod heater is arranged at a predetermined distance from the surface of the sample. At this time, the axial direction of the rod-shaped heater is parallel to the fiber direction of the decorative plate. In this state, the temperature of the heater was set to 700 ° C, and the surface temperature of the sample was set to 170 ° C.

Next, the sample whose surface is kept horizontal is placed on the upper end of the plate fixture which is standing upright and pressed from above. At this time, the fiber direction of the decorative plate is parallel to the longitudinal direction of the plate-shaped jig. The cross-sectional shape of the upper end of the jig is an arc shape with a specific curvature radius.

Next, in a state in which the sample is pressed on the jig in the manner described above, both ends of the sample are further pressed down to make the sample bend, and it is confirmed whether the sample has cracks.

The test for bending the sample as described above was repeated while gradually reducing the radius of curvature of the upper end of the jig. The minimum curvature radius of the sample without cracks is an evaluation value of bending workability.

(4) Weight increase rate

The weight increase rate of the decorative plate was measured in accordance with the boiling resistance of JIS K 6902 "Testing method for thermosetting resin high-pressure decorative plate". The specification value is 17% or less.

(5) Evaluation of warpage

A 50 mm x 300 mm sample was cut from the decorative board. The fiber direction of the decorative plate was parallel to the width direction of the sample. The sample was cured for 24 hours in an environment of a room temperature of 40 ° C and a humidity of 30%. Then place the sample on a horizontal plane and measure the warpage height from the horizontal plane at this time (the distance between the opposite end of the sample and the horizontal plane when one end of the sample in the longitudinal direction is pressed to the horizontal plane).

The evaluation results are shown in Tables 5 and 6. The "thickness" in Table 5 means the thickness of the decorative plate.

The decorative boards of the examples obtained good results in each evaluation item. That is, although the decorative plate of the embodiment is a thin object, it is not easily warped and has a smooth appearance, and has excellent bending workability and non-combustibility. The decorative plate of the comparative example was inferior in any of the evaluation items of smoothness, bending workability, non-combustibility, and warpage.

Claims (8)

A decorative board comprising: a core layer comprising a fibrous substrate, a thermoplastic resin and an endothermic metal hydroxide; and an intermediate layer comprising a mixed paper and a thermosetting resin, the mixed paper containing 55% to 85% An endothermic metal hydroxide; and a decorative layer comprising decorative paper and a thermosetting resin; the decorative plate is a laminated body laminated in the order of the core layer, the intermediate layer, and the decorative layer; amount of the thermoplastic resin is ^{29.38g / m 2 ~ 100g / m} 2. The decorative board according to claim 1, wherein the endothermic metal hydroxide in the core layer is aluminum hydroxide or magnesium hydroxide; the endothermic metal hydroxide in the intermediate layer is aluminum hydroxide or hydrogen Magnesium oxide. The decorative board according to claim 1 or 2, wherein the thermoplastic resin in the core layer is an acrylic resin emulsion. The decorative board according to claim 1 or 2, wherein the core layer contains a silane coupling agent. The decorative board according to claim 1, wherein the core layer contains a flame retardant. The decorative board according to claim 5, wherein the core layer contains the flame retardant in the range of 1 g / m ² to 100 g / m ² . The decorative board according to claim 5 or 6, wherein the flame retardant is a nitrogen-based flame retardant or a phosphorus / nitrogen-based flame retardant. The decorative board according to claim 7, wherein the phosphorus content in the phosphorus / nitrogen flame retardant is 1% to 30% by weight, and the nitrogen content in the phosphorus / nitrogen flame retardant is 5% to 35% by weight. .