JP2005103769A - Non-combustible decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-combustible decorative sheet keeping a non-combustibility, eliminating in brittleness and obtaining excellent processability. <P>SOLUTION: A core layer, which comprises a prepreg impregnated with a slurry composed of a thermosetting resin, an inorganic filler, a synthetic resin emulsion resin and/or a rubber latex, and resin impregnated decorative paper, which is obtained by impregnating raw paper for the decorative sheet with a resin solution mainly based on a thermosetting resin and drying the impregnated one, are laminated on an inorganic fiber base material and the whole is thermoformed under pressure. The compounding ratios of the thermosetting resin, the inorganic filler, the synthetic resin emulsion resin and/or a rubber latex are 1:10-20:0.3-1 as a solid ratio and the content of the slurry in the prepreg is 500-2,000% in a calculation method shown by a numerical formula of Fig.b. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a non-combustible decorative board.

  Conventionally, a decorative board imparted with fireproofing and nonflammability is known, and a prepreg obtained by impregnating an inorganic fiber nonwoven fabric with a slurry containing a phenol resin or a melamine resin as a binder component has been used for the core layer.

JP-A-3-253342 JP-A-11-268196 JP 2000-291175 A

  However, those using a prepreg impregnated with a slurry containing these resins as a binder component as a core layer have a limit in the amount of binder component added to ensure nonflammable performance, and the resulting nonflammable decorative board is There was a problem that the workability was poor because it was slightly inferior in strength, hard and brittle.

The present invention has been studied in view of such circumstances, and aims to obtain a decorative board having nonflammability, excellent strength, eliminating brittleness, and free from warping. It is characterized by.
That is, in the invention described in claim 1, the inorganic fiber base material is impregnated with a slurry containing an amino-formaldehyde resin as an essential component as a thermosetting resin and an inorganic filler and a synthetic resin emulsion and / or rubber latex. A non-combustible decorative board comprising a core layer made of a prepared prepreg and a decorative layer.
In the invention according to claim 2, the mixing ratio of the thermosetting resin, the inorganic filler, the synthetic resin emulsion and / or the rubber latex in the slurry is a solid content ratio of 1:10 to 20: 0.3 to 2. The incombustible decorative board according to claim 1, wherein a blending ratio of the thermosetting resin component and the inorganic filler is 5 to 20:95 to 80 in terms of solid content.
Furthermore, the invention described in claim 3 is the incombustible decorative board according to claim 1 or 2, wherein an amino-formaldehyde resin and a phenol resin are used in combination as the thermosetting resin.
Furthermore, the invention according to claim 4 is characterized in that the solid content of the slurry in the prepreg is 500 to 2000% by the calculation method represented by equation (1). It is a non-combustible decorative board.

The non-combustible decorative board according to claim 1 or 2, wherein the synthetic resin emulsion and / or rubber latex has a glass transition temperature (Tg) of -20 ° C or lower.

The present invention comprises a prepreg in which a core layer is impregnated with a slurry composed of an organic resin component, an inorganic filler, and an emulsion on an inorganic fiber substrate, thereby maintaining nonflammability performance, eliminating brittleness, and more High adhesion to the surface decorative layer and strength of the molded product can be realized.
Moreover, there are no chipping at the time of cutting, peeling of the decorative layer, cornering at the time of construction work, dents and cracks.

Hereinafter, the present invention will be described in detail.
The core layer of the incombustible decorative board of the present invention is made of a prepreg obtained by impregnating an inorganic fiber base material with a slurry comprising a thermosetting resin component, an inorganic filler, and an emulsion.

Examples of the inorganic fiber substrate include nonwoven fabrics and woven fabrics made of inorganic fibers such as glass fiber, rock wool, and carbon fiber. The basis weight of the inorganic fiber substrate is preferably in the range of 10 to ²⁰⁰ g / m ^2. In particular, it is preferable to use glass fibers that are excellent in heat resistance and flame resistance and excellent in impregnation of slurry.

  As a thermosetting resin component, amino-formaldehyde resin is an essential component, and when used alone or in combination with a phenol resin, physical properties such as nonflammability, strength, and heat resistance are more excellent than phenol resin alone.

Phenol resins are obtained by reacting phenols and aldehydes at a ratio of 1 to 3 moles of aldehydes with 1 mole of phenolic hydroxyl group under a basic catalyst or an acidic catalyst. Phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, glyoxal, trioxal and the like.
In addition, those modified with a modifying agent that promotes plasticization such as paratoluene sulfonamide, tung oil, phosphoric esters, glycols, etc. can be applied as necessary, and basic catalysts include alkali metals such as sodium and potassium, And oxides and hydroxides of alkaline earth metals such as magnesium and calcium, amines such as triethylamine and triethanolamine, and ammonia. Examples of acidic catalysts include paratoluenesulfonic acid and hydrochloric acid.

  Amino-formaldehyde resins include initial condensates obtained by reacting amino compounds such as melamine, urea, benzoguanamine, and acetoguanamine with formaldehyde, etherification with lower alcohols such as methyl alcohol and butyl alcohol, and paratoluene. Those modified with a reactive modifier that promotes plasticization such as sulfonamide can be applied, and among them, a melamine-formaldehyde resin excellent in durability is preferable.

  Examples of the inorganic filler contained in the slurry include aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica and the like, and those having an average particle diameter in the range of 0.5 to 200 μm impregnate the inorganic fiber nonwoven fabric. Among them, those containing crystal water such as aluminum hydroxide and magnesium hydroxide are optimal in terms of nonflammability because they decompose at high temperatures and release endothermic and bound water.

Synthetic resin emulsion and / or rubber latex is for imparting plasticity to the core layer and eliminating brittleness. As synthetic resin emulsion, polyacrylate emulsion, polyvinyl acetate emulsion, polyvinyl chloride emulsion, ethylene Examples thereof include vinyl acetate emulsion, ethylene acrylic emulsion, ethylene vinyl chloride emulsion, acrylic vinyl chloride emulsion, and ethylene emergence.
Examples of the rubber latex include natural rubber latex, styrene / butadiene copolymer latex, methyl methacrylate / butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, and the like.

In particular, when rubber latex is used, moderate flexibility and elasticity are imparted and brittleness is eliminated. Among them, those having a glass transition point (Tg) of −20 ° C. or lower and a viscosity of 100 cps or lower can be suitably used. .
When the glass transition point exceeds -20 ° C, the core layer becomes too hard, which is not preferable.

The blending ratio of the thermosetting resin content, the inorganic filler, the synthetic resin emulsion and / or the rubber latex is preferably a solid content ratio of 1:10 to 20: 0.3 to 1, with respect to the organic resin content. When the inorganic filler is increased, the incombustibility is improved, but the adhesiveness is lowered. When the inorganic filler is decreased, the adhesiveness is improved, but the incombustible performance is lowered.
If the emulsion resin and / or rubber latex is less than the lower limit, the finished product is fragile and difficult to process. If the upper limit is exceeded, flexibility is increased and processing becomes easier, but incombustibility is inferior.
As the solvent for diluting the compounded resin to a predetermined impregnating solution concentration, water or a lower alcohol such as methanol is suitable.

  The blending ratio when the amino-formaldehyde resin and the phenol resin are used in combination as the thermosetting resin in the slurry is preferably a solid content ratio of 1: 0.2 to 10, and the amino- If the formaldehyde resin is small, the strength and adhesion tend to be inferior, and if it is large, the warp is large.

The slurry solid content (%) in the inorganic fiber substrate is a calculation method represented by Equation 1, and is preferably in the range of 500 to 2000%.

If the upper limit is exceeded, the solid content will drop off, making it difficult to handle, and if the lower limit is not reached, delamination will easily occur.

  A decorative layer is formed on at least one side of a core layer made of a prepreg in which an inorganic fiber base material is impregnated with slurry. As a forming method, a coating method, a resin-impregnated decorative paper method, or a transfer foil is used. Examples of the method include transferring a decorative layer, and the use of resin-impregnated decorative paper is particularly preferable from the viewpoints of productivity, adhesion to the core layer, and wear resistance.

  As a means for coating, a resin liquid containing an unsaturated polyester resin colored with a pigment, a curing agent such as methyl ethyl ketone peroxide, and a curing accelerator such as cobalt naphthenate is applied on the core molding. After coating, the coated surface is covered with a vinylon film, spread with a roller, and after the resin is cured, the vinylon film is peeled off.

  The unsaturated polyester resin contains an acid component containing an unsaturated dibasic acid and / or an acid anhydride thereof and other saturated acid and / or acid anhydride used as necessary, and a polyhydric alcohol. A dehydration-condensation reaction is carried out according to a conventional method at about 160 to 230 ° C., preferably 210 to 230 ° C. in an inert gas atmosphere such as argon, and a polymerizable monomer such as a styrene monomer is added.

The method using resin-impregnated decorative paper is a method in which a base resin for decorative board is impregnated with a resin liquid containing a thermosetting resin as a main component, dried resin-impregnated decorative paper is laminated, and hot pressing is performed. As a decorative paper, a resin liquid composed of a thermosetting resin such as an amino-formaldehyde resin, a diallyl phthalate resin, and an unsaturated polyester resin is impregnated with a decorative paper of 30 to 140 g / m ² for a decorative board expressed by the following equation ( ² ). Those impregnated with a rate of 80 to 300% can be applied. Hot pressing may be performed with a press such as a flat plate press or a continuous press.

EXAMPLES Hereinafter, although an Example is given and demonstrated in detail, this invention is shown more concretely and is not specifically limited.
Example 1 (Combination of amino-formaldehyde resin and phenol resin)
Core layer A prepreg (a) was obtained by impregnating a glass fiber nonwoven fabric having a basis weight of 70 g / m ² with a slurry having the following composition so that the slurry solid content shown in Formula 1 was 1500%.
Melamine-formaldehyde resin (solid content 60%) 3 parts Phenol resin (solid content 50%) 7 parts Aluminum hydroxide 67 parts Rubber latex (SBR system, solid content 50%, Tg-20 ° C)
Product name Asahi Kasei Latex L-7850 Asahi Kasei Co., Ltd. 6 parts Water 6 parts Methanol 11 parts Makeup layer Solid color decorative paper with a basis weight of 80 g / m ² has an impregnation ratio of melamine-formaldehyde resin expressed by the number 2 of 100% A melamine resin-impregnated decorative paper (b) was obtained.
Non-combustible decorative board Two prepregs (a) and one melamine resin-impregnated decorative paper (b) are laminated and hot-press molded using a flat finish plate at 130 ° C and 100 kg / cm ² for 90 minutes. Thus, the incombustible decorative board of Example 1 was obtained.

Example 2 (example using acrylic emulsion)
In Example 1, it replaced with rubber latex and implemented similarly except having used the acrylic emulsion (Brand name Ultrasol B750 Gantz Kasei Co., Ltd. solid content 50%), and obtained the incombustible decorative board of Example 2. .

Example 3 (in the case of melamine resin alone)
In Example 1, it carried out similarly except not using a phenol resin and mix | blending 10 parts of melamine-formaldehyde resins, and the noncombustible decorative board of Example 3 was obtained.

Comparative example 1 (when there are few inorganic fillers with respect to a resin component)
The makeup of Comparative Example 1 was carried out in the same manner as in Example 1 except that a slurry containing 6 parts of melamine-formaldehyde resin, 35 parts of aluminum hydroxide and 12 parts of rubber latex was used for 14 parts of phenol resin. I got a plate.

Comparative example 2 (when there are many inorganic fillers with respect to the resin component)
The makeup of Comparative Example 2 was carried out in the same manner as in Example 1 except that a slurry containing 1 part of melamine-formaldehyde resin, 76 parts of aluminum hydroxide and 3 parts of rubber latex was used for 3 parts of phenol resin. I got a plate.

Comparative example 3 (when there is little rubber latex)
In Example 1, Comparative Example 3 was carried out in the same manner except that a slurry containing 5 parts of melamine-formaldehyde resin, 67 parts of aluminum hydroxide and 2 parts of rubber latex was used for 9 parts of phenol resin. A decorative board was obtained.

Comparative Example 4 (when there is a lot of rubber latex)
The cosmetic of Comparative Example 4 was carried out in the same manner as in Example 1, except that a slurry containing 1 part of melamine-formaldehyde resin, 67 parts of aluminum hydroxide and 10 parts of rubber latex was used for 5 parts of phenol resin. I got a plate.

Comparative Example 5 (when the fixing rate of the slurry is less than the lower limit)
The decorative plate of Comparative Example 5 was obtained in the same manner as in Example 1 except that the slurry solid content fixing rate was 500%.

Comparative Example 6 (when the slurry fixing rate exceeds the upper limit)
The decorative plate of Comparative Example 6 was obtained in the same manner as in Example 1 except that the slurry solid content fixing rate was 3000%.

Comparative Example 7 (when the glass transition temperature exceeds the upper limit)
A decorative board of Comparative Example 7 was obtained in the same manner as in Example 1 except that rubber latex having a glass transition temperature of 30 ° C. was used.

Comparative Example 8 (in the case of phenol resin alone)
A decorative board of Comparative Example 8 was obtained in the same manner as in Example 1 except that melamine-formaldehyde resin was not used and 10 parts of phenol resin was added.

The evaluation results are shown in Table 1.

The test method was as follows.
Nonflammability: According to Article 4, Item 9 of the Building Standards Law, “4.9.2 Exothermic test and evaluation method”. (20-minute test with a corn calorimeter based on ISO 5660)
Strength: A 500 g iron ball was dropped from 20 cm above the sample.
Brittleness: Bending at room temperature with a bending rod, bending at 30R was marked with ◯, and not bending was marked with x.
Warpage: The product was placed flat in a room at 40 ° C.-30% for 7 days. A warpage of less than 1 mm was evaluated as “◯”, a thickness of 1-2 mm as “Δ”, and a warpage of more than 2 mm as “X”.
Water resistance: A JAS 2 class immersion peeling test was conducted.

1 is a configuration cross-sectional view of a non-combustible decorative board of Example 1.

Explanation of symbols

2 Prepreg 3 Melamine resin impregnated paper 6 Non-combustible decorative board

Claims (5)

A core layer composed of a prepreg impregnated with an inorganic fiber base material, an amino-formaldehyde resin as an essential component as a thermosetting resin, and impregnated with a slurry containing an inorganic filler and a synthetic resin emulsion and / or rubber latex, and a decorative layer A non-combustible decorative board characterized by comprising: The mixing ratio of the thermosetting resin, the inorganic filler, the synthetic resin emulsion and / or the rubber latex in the slurry is 1:10 to 20: 0.3 to 1 in terms of solid content, and the thermosetting resin content is The non-combustible decorative board according to claim 1, wherein the blending ratio of the inorganic filler and the inorganic filler is 5 to 20:95 to 80 in terms of solid content. The incombustible decorative board according to claim 1 or 2, wherein an amino-formaldehyde resin and a phenol resin are used in combination as the thermosetting resin. 3. The incombustible decorative board according to claim 1, wherein the solid content of the slurry in the prepreg is 500 to 2000% by the calculation method represented by Equation 1. 4.
The incombustible decorative board according to claim 1 or 2, wherein the synthetic resin emulsion and / or rubber latex has a glass transition temperature (Tg) of -20 ° C or lower.