JP2006095743A - Non-combustible decorative panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic resin type non-combustible decorative panel reduced in dimensional change, warpage and deformation. <P>SOLUTION: Decorative paper is impregnated with a resin solution comprising an oligomer having a polymerizable unsaturated group and further impregnated with a resin solution comprising an amino-formaldehide resin after drying while the resin impregnated decorative paper after dried and a prepreg, which is formed by impregnating an inorganic fiber base material with slurry composed of an inorganic filler and a thermosetting resin and dried, are laminated to be subjected to hot press molding. The content of the former is set to 3-45% in a calculation method represented by the formula 1: content=ä(weight after an A-solution is contained-weight of decorative paper)/weight of decorative paper}×100 and the content of the latter is set to 70-130% in a calculation method represented by the formula 2: content=ä(weight after B-solution is contained-weight after A-solution is contained)/weight after A-solution is contained}×100. As the oligomer having the polymerizable unsaturated group, an unsaturated polyester resin, a vinyl ester resin, an acrylic urethane oligomer or the like is used. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

Conventionally, a melamine resin decorative plate is known as a plastic decorative plate, and a non-combustible decorative plate is used in stores, offices and the like that require non-combustibility.
Non-combustible decorative boards include inorganic, metal, and organic resin types. Organic resin types that are excellent in processability and impact resistance generally consist of a decorative layer and a core layer. A resin liquid made of thermosetting resin is impregnated into a decorative paper made from the above, dried resin-impregnated decorative paper is used, and the core layer is a resin as a binder component on an inorganic fiber substrate such as a glass fiber nonwoven fabric or glass fiber fabric. It is obtained by impregnating a slurry comprising an inorganic filler and drying a prepreg of a desired thickness, and hot pressing with a resin-impregnated decorative paper.

JP-A-4-234644 JP-A-9-52315 JP-A-8-207201

  However, organic resin-based incombustible decorative boards have a large dimensional change due to moisture absorption and release due to the hydrophilicity of the decorative layer, and may be warped or deformed due to environmental changes in temperature and humidity.

The present invention has been studied for the purpose of reducing moisture permeability and greatly improving dimensional stability, and is characterized by the following.
That is, the invention according to claim 1 includes (A) an oligomer having a polymerizable unsaturated group on the inner side and (B) a resin-containing decorative paper containing an amino-formaldehyde resin on the outer side, and inorganic filling of the inorganic fiber base material. A non-combustible decorative board obtained by laminating a prepreg containing a slurry composed of an agent and a thermosetting resin and then hot pressing.
The invention according to claim 2 is the incombustible decorative board according to claim 1, wherein the oligomer (A) having a polymerizable unsaturated group is a vinyl ester resin.
The invention according to claim 3 is the nonflammable decorative board according to claim 1, characterized in that the oligomer (A) having a polymerizable unsaturated group is an unsaturated polyester resin.
Furthermore, the invention according to claim 4 is the incombustible decorative board according to claim 1, wherein the oligomer (A) having a polymerizable unsaturated group is an acrylic urethane oligomer.

Since the non-combustible decorative board of the present invention has a small dimensional change rate, it does not warp or distort even when used for a long time. Moreover, the surface appearance is beautiful.
Hereinafter, the present invention will be described in detail.

  Examples of the oligomer having a polymerizable unsaturated group used in the present invention include unsaturated polyester resins, vinyl ester resins, acrylic urethane oligomers, acrylic oligomers, etc., preferably unsaturated polyester resins, vinyl ester resins, acrylic urethane oligomers are used. It is desirable to use a resin that is insoluble in water.

The unsaturated polyester resin is made into a viscous solution by adding a polymerizable monomer or organic solvent, a curing agent, a polymerization inhibitor, an ultraviolet absorber, and a curing accelerator, a coloring pigment, if necessary, to the unsaturated polyester. It is a well-known thing. Examples of the polymerizable monomer include styrene monomers and (meth) acrylic monomers.
Unsaturated polyester comprises an acid component containing unsaturated dibasic acid and / or acid anhydride thereof and other saturated acid and / or acid anhydride used as necessary, and polyhydric alcohol with nitrogen or argon. The dehydration condensation reaction may be performed according to a conventional method at about 160 to 230 ° C., preferably 210 to 230 ° C. in an inert gas atmosphere.
Examples of the unsaturated dibasic acid and its acid anhydride include maleic acid, fumaric acid, itaconic acid, maleic anhydride and the like, and these may be used alone or in combination of two or more. The unsaturated dibasic acid and its acid anhydride are preferably used in an acid component of 50 to 100 mol%, particularly preferably 60 to 100 mol%.
Other saturated acids and / or acid anhydrides used as necessary include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic acid, tetrahydroanhydride Examples thereof include saturated dibasic acids such as phthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. These may be used alone or in combination of two or more. The blending amount of the saturated acid is 0 to 50 mol%, preferably 0 to 40 mol% in the acid component.
Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentadiol, 1,6- Examples thereof include dihydric alcohols such as hexanediol, triethylene glycol and neopentyl glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol. These may be used alone or in combination of two or more.

  The vinyl ester resin is obtained by reacting an epoxy resin with an unsaturated monobasic acid. Examples of the epoxy resin include bisphenol A-based epoxy resins, halogenated bisphenol A-based epoxy resins, bisphenol A and ethylene oxide or propylene oxide. Examples thereof include diglycidyl ethers of adducts with alkylene oxide, bisphenol F epoxy resins, novolac epoxy resins, cresol novolac epoxy resins, and the like.

  Examples of monobasic acids include acrylic acid, methacrylic acid, crotonic acid, monomethyl malate, monopropyl malate, sorbic acid or mono (2-ethylhexyl) malate, and are polybasic used in combination with unsaturated monobasic acids. Examples of the acid include succinic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, azelaic acid, 1,12-dodecanedioic acid and other dimer acids. Examples of the dibasic acid anhydride include maleic anhydride and phthalic anhydride. A modified product using trimellitic anhydride as a tribasic acid anhydride can also be used.

Acrylic urethane oligomers are obtained by oligomerizing organic isocyanate compounds and (meth) acrylic acid esters containing hydroxyl groups with urethane bonds. Polyisocyanate compounds include aliphatic, alicyclic, aromatic, and araliphatic polymers. Examples thereof include isocyanates and modified products thereof.
Aliphatic polyisocyanates include hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), and alicyclic polyisocyanates include dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (IPDI). 1,4-cyclohexane diisocyanate (CHDI), hydrogenated xylylene diisocyanate (HXDI), hydrogenated tolylene diisocyanate (HTDI) and the like.
In addition, aromatic diisocyanates include tolylene diisocyanate (TDI), 4,4 ′ (or 2,4 ′)-diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), and tolidine diisocyanate (TODI). ), P-phenylene diisocyanate (PPDI) and the like, and examples of the araliphatic polyisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like.
As a modified product of an araliphatic, aliphatic, alicyclic or aromatic polyisocyanate compound, a part or all of the isocyanate groups of the above exemplified compounds may be carbodiimide groups, uretdione groups, uretoimine groups, burette groups, isocyanates. Examples thereof include compounds modified to a nurate group, and two or more polyisocyanate compounds may be used in combination.

In order to promote the reaction with the isocyanate group of the polyisocyanate component, an organotin-based urethanization catalyst is used, but as the organotin-based urethanization catalyst, any catalyst that is generally used in a urethanization reaction may be used. For example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dialkyl malate, tin stearate, tin octylate and the like can be mentioned.
The amount of the organotin-based urethanization catalyst used is not particularly limited, but is suitably used within the range of 0.005 to 3% by weight. If the lower limit is not reached, the urethane reaction does not proceed sufficiently. If the upper limit is exceeded, the reaction control becomes difficult due to heat generation during the urethane reaction.

  Examples of the hydroxyl group-containing (meth) acrylic acid ester to be reacted with the polyisocyanate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl ( (Meth) acrylate, caprolactone-modified hydroxyethyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like. Can be used alone or in combination.

  The oligomer having a polymerizable unsaturated group is usually diluted with an organic solvent or an unsaturated monomer to adjust the viscosity. For example, acetone, toluene, ethyl acetate, butyl acetate, acrylic ester, methacrylic ester, styrene, vinyl toluene Aromatic monomers such as acrylonitrile and the like.

(A) The content of the oligomer having a polymerizable unsaturated group in the decorative paper used for the decorative board is preferably 3 to 45% by the calculation method represented by Equation 1, and the content satisfies the lower limit. Otherwise, the finished appearance tends to be inferior, and if the upper limit is exceeded, the finished appearance becomes fluttered because the amino-formaldehyde resin described below is repelled.

In the present invention, since the oligomer having a polymerizable unsaturated group is hydrophobic, it is presumed that the oligomer penetrates into the inside of the decorative paper and prevents moisture permeability of the hydrophilic amino-formaldehyde resin.

Next, the amino-formaldehyde resin is used for obtaining a normal decorative melamine resin decorative board. In addition to an initial condensate obtained by reacting an amino compound such as melamine, urea, benzoguanamine, acetoguanamine with formaldehyde, methyl alcohol A melamine-formaldehyde resin excellent in durability can be used, which can be applied by etherification with a lower alcohol such as butyl alcohol or modified with a reactive modifier that promotes plasticization such as paratoluenesulfonamide.
(B) The content of the amino-formaldehyde resin is preferably 70 to 130% by the calculation method represented by Formula 2, and if it is less than the lower limit, the surface properties such as wear resistance, hardness, and stain resistance are inferior. Easy to lose appearance. Even if the upper limit is exceeded, the appearance tends to be inferior and the impregnated paper tends to block.

  In order to include (A) an oligomer having a polymerizable unsaturated group on the inner side and (B) an amino-formaldehyde resin on the outer side, (A) an oligomer having a polymerizable unsaturated group is impregnated or coated on a decorative paper. After drying, (B) amino-formaldehyde resin may be impregnated or coated and dried.

A prepreg is an inorganic fiber base material impregnated with a slurry composed of an inorganic filler and a thermosetting resin as a binder and dried. As the inorganic fiber base material, inorganic fibers such as glass fiber, rock wool, and carbon fiber are used. The basis weight of the inorganic fiber base material is preferably in the range of 10 to ²⁰⁰ g / m ² , and in particular, glass having excellent heat resistance and flame resistance and excellent slurry impregnation properties. It is preferable to use fibers.

  Examples of the thermosetting resin include a phenol resin, the aforementioned amino-formaldehyde resin, or a combination of these. In particular, when used in combination, physical properties such as incombustibility, strength, and heat resistance are improved. When used in combination, the mixing ratio of the phenol resin and amino-formaldehyde resin is preferably a solid content ratio of 1: 0.1 to 5, and if the amino-formaldehyde resin is less than the phenol resin, the strength and adhesion are reduced. Tends to be inferior, and warping increases when there are many.

  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. Examples include phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, and bisphenol F. Examples of aldehydes include formaldehyde, paraformaldehyde, glyoxal, and trioxal.

  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.

  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.

The blending ratio of the thermosetting resin and the inorganic filler is desirably 5 to 20:95 to 80. When the inorganic filler is increased with respect to the thermosetting resin, the nonflammability is improved, but the adhesion is lowered. In addition, when the inorganic filler is decreased, the incombustibility is lowered although the adhesion is improved.
When the phenol resin and the amino-formaldehyde resin are used in combination as the thermosetting resin in the slurry, the blending ratio is preferably 1: 0.1 to 5, and the amino-formaldehyde resin with respect to the phenol resin. If the amount is small, the strength and adhesion tend to be inferior, and if the amount is large, the warp becomes large.

The slurry solid content (%) in the inorganic fiber substrate is a calculation method represented by Equation 3, and is preferably in the range of 500 to 3000%.

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.

  Resin-impregnated decorative paper is disposed on at least one side of the prepreg. The other surface may or may not be provided with a resin-impregnated decorative paper, but the arrangement causes a smaller dimensional change. Further, even if a metal foil such as an aluminum foil or a copper foil, a plastic film, or the like is disposed on the other surface instead of the resin-impregnated decorative paper, the dimensional change is small.

After the resin-impregnated decorative paper and the prepreg are laminated, the non-combustible decorative board of the present invention is obtained by hot-pressure molding at a temperature of 120 to 150 ° C. and a pressure of 50 to 100 kg / cm ² . The hot pressing may be performed using a pressing machine such as a flat plate press or a continuous press.

Hereinafter, examples and comparative examples will be described in detail.
Example 1
(A) Resin liquid comprising an oligomer having a polymerizable unsaturated group 100 parts by weight of vinyl ester resin (trade name Lipoxy RA4400, manufactured by Showa Polymer Co., Ltd.)
Acetone 50 parts by weight (B) Resin liquid composed of amino-formaldehyde resin Melamine-formaldehyde resin 100 parts by weight Curing agent 5 parts by weight The calculation method shown in Equation 1 for (A) liquid on white 120 g / m ² decorative paper 20 % Impregnation.
Next, the liquid (B) was impregnated so as to be 120% by the calculation method shown in Formula 2, and a resin-impregnated decorative paper was obtained.
A slurry in which 4 parts of amino-formaldehyde resin and 91 parts of aluminum hydroxide are blended with 5 parts of phenol resin in a glass fiber nonwoven fabric of prepreg 50 g / m ^{2 so that} the slurry content shown in Equation 3 is 1600%. To obtain a prepreg.
Non-combustible decorative board In order from the bottom, 1 sheet of resin-impregnated decorative paper, 4 sheets of prepreg, and 1 sheet of resin-impregnated decorative paper are laminated under the conditions of 130 ° C, 70 kg / cm ² and 90 minutes using a flat finish plate. The noncombustible decorative board of Example 1 was obtained by hot pressing.

Example 2 (when the oligomer having a polymerizable unsaturated group is an unsaturated polyester resin)
In Example 1, it implemented similarly except having replaced with the vinyl ester resin of (A) liquid, and using unsaturated polyester resin (brand name OT-100, Dainippon Ink).

Example 3 (when the oligomer having a polymerizable unsaturated group is an acrylic urethane oligomer)
In Example 1, it implemented similarly except having replaced the vinyl ester resin of the (A) liquid with the following acrylic urethane oligomer.
Hexamethylene diisocyanate trimer (trade name: Coronate HX, Nippon Polyurethane) 100 parts by weight, 2-ethylhexyl methacrylate 50 parts by weight, glycerin 6 parts by weight ethyl acetate 700 parts by weight, dibutyltin laurate as catalyst 0.06 part by weight was added, and the urethane reaction was advanced so that the liquid temperature did not exceed 70 ° C. The reaction solution was confirmed to have completely disappeared the absorption band based on the isocyanate group of 2266 cm −1 by infrared absorption analysis, and the reaction was completed to obtain an acrylic urethane oligomer.

Example 4
In Example 1, it implemented similarly except having made the content rate of (A) liquid into 3%.

Example 5
In Example 1, it implemented similarly except having made the content rate of (A) liquid into 45%.

Example 6
In Example 1, it implemented similarly except having made the content rate of (B) liquid into 70%.

Example 7
In Example 1, it implemented similarly except having made the content rate of (B) liquid into 130%.

Example 8
In Example 1, it implemented similarly except having made the content rate of (A) liquid into 1%.

Example 9
In Example 1, it implemented similarly except having made the content rate of (A) liquid into 50%.

Example 10
In Example 1, it implemented similarly except having made the content rate of (B) liquid into 60%.

Example 11
In Example 1, it implemented similarly except having made the content rate of (B) liquid into 130%.

Comparative Example 1
In Example 1, it implemented similarly except not having made it contain A liquid.

The evaluation results are shown in Table 1.

The evaluation results were as follows.
Dimensional change rate: A test was performed in accordance with a thermosetting resin decorative board test method defined in JIS K6902. In the evaluation, the average value in the vertical direction and the horizontal direction was evaluated as ○ when the average value was less than 0.200%, and X when 0.200% or more.
Appearance: Evaluation was performed in an environment conforming to JIS K6902. The case where surface roughness, cloudiness, gloss unevenness, and the like existed was evaluated as x.
Nonflammability: Nonflammability: Total heat generation is 8 MJ / m ² or less in a 20-minute exothermic test / evaluation method using a cone calorimeter in accordance with ISO 5660, and the maximum heat generation rate is 200 kW / m ² continuously for 10 seconds or more. The case where it did not exceed was marked as ○

Claims (4)

A slurry comprising a resin-containing decorative paper containing (A) an oligomer having a polymerizable unsaturated group on the inside and (B) an amino-formaldehyde resin on the outside, and an inorganic filler and a thermosetting resin on the inorganic fiber substrate. A non-combustible decorative board obtained by laminating a prepreg including The incombustible decorative board according to claim 1, wherein the oligomer (A) having a polymerizable unsaturated group is a vinyl ester resin. The non-combustible decorative board according to claim 1, wherein the oligomer (A) having a polymerizable unsaturated group is an unsaturated polyester resin. The incombustible decorative board according to claim 1, wherein the oligomer (A) having a polymerizable unsaturated group is an acrylic urethane oligomer.