JP5685451B2 - Flame-retardant composition and decorative board - Google Patents

Description

  The present invention relates to a flame retardant composition and a decorative board.

  Conventionally, a decorative board provided with functions such as fire prevention and non-flammability is known, and a resin-impregnated decorative paper in which a decorative liquid for a decorative board is impregnated with a resin liquid mainly composed of a thermosetting resin, and an inorganic fiber A prepreg impregnated with a nonwoven fabric containing phenol-formaldehyde resin or melamine-formaldehyde resin as a binder component and impregnated with a slurry containing an inorganic filler is used as a core layer, and both are laminated and hot-press molded.

JP 2008-74943 A JP 2008-290444 A

  However, the prepreg used in the core layer for the nonflammable decorative board has a limit in the amount of the organic resin component as the binder component for the purpose of ensuring nonflammability, and the nonflammability is poor when the organic resin content is large. When the organic resin content is small, adhesion between prepregs is poor, water resistance tends to be poor, and delamination may occur in a boiling test.

  In addition, metal hydroxides such as aluminum hydroxide and magnesium hydroxide impart incombustibility due to the endothermic action when releasing crystal water, but since the incombustibility is small with a small amount of compounding, it is not suitable for organic resin components. Compared to this, a large amount must be blended, resulting in inferior machinability and workability, such as a decrease in the adhesion of the core layer and damage to the blade.

The present invention has been studied in view of such a situation, and reacts a thermosetting resin, an inorganic filler such as calcium carbonate, talc, fly ash, silica, kaolin , colloidal silica and a silane coupling agent. flame retarded composition der to organic-inorganic composite binder as essential components consisting Te Ru.

By using the flame retardant composition of the present invention, a decorative board having nonflammability and excellent water resistance can be obtained, and delamination between prepregs does not occur.
Further, in order to impart nonflammability , endothermic metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used, but in the present invention, these metal hydroxides do not need to be used, and resources are depleted. Can be prevented. Hereinafter, the present invention will be described in detail.

  The organic / inorganic composite binder of the present invention is a composite of an organic substance and an inorganic substance, and exhibits a binder force in the organic part and nonflammability in the inorganic part. Specifically, colloidal silica and silane A reaction product of a coupling agent may be mentioned. When the colloidal silica and the silane coupling agent are used individually, nonflammability is hardly exhibited. By blending this reactant, the water resistance of the decorative board is improved, and the interlayer strength after the boiling test is also excellent. Furthermore, this reaction product (organic / inorganic composite binder) does not reduce the nonflammability unlike ordinary resins, and the colloidal silica vitrifies when the decorative board is heated strongly. An effect of inhibiting combustion of a thermosetting resin such as a certain phenol-formaldehyde resin or amino-formaldehyde resin was also confirmed.

  The colloidal silica is a colloidal solution in which colloidal silica is stably dispersed in water or an organic solvent, and the silica concentration is preferably 1 to 50% by weight, and more preferably 40% by weight or less for preventing gelation. When colloidal silica having a larger particle diameter is used, the storage stability tends to be inferior, and an average particle diameter of 5 to 50 nm is more preferable. Commercially available products include “Snowtex”, “IPA-ST”, “IPA-ST-ZL”, “methanol silica sol”, “NPC-ST-30”, “MIBK-ST”, “manufactured by Nissan Chemical Industries, Ltd.” “MEK-ST”, “PMA-ST”, “NBAC-ST”, etc., “OSCAL” (registered trademark) manufactured by Nikka Catalysts & Chemicals Co., Ltd., “Quartron” (registered trademark) manufactured by Fuso Chemical Industries, Ltd., Clariant “Highlink OG silica organosol” manufactured by Japan Corporation may be mentioned. These colloidal silicas are mixed with various solvents, and hydrophobic (nonpolar) solvent species such as paraffinic hydrocarbons, fluorocarbon solvents, silicone oils, such as ethyl acetate, butyl acetate, diethyl ether, methyl ether, methyl isobutyl ketone, Hexane, chloroform, and the like have few hydroxyl groups on the particle surface, so the binder power tends to be inferior. In hydrophilic (polar) solvent type colloidal silica, the hydroxyl group on the silica surface binds strongly to the binder component (thermosetting resin). To do.

  Here, the hydrophilic (polar) solvent is a solvent having an affinity for water, for example, a hydrophilic organic solvent having a hydrophilic group such as a hydroxyl group, a carboxyl group, or a carbonyl group in the molecule. Examples include aprotic polar solvents. Specific examples of the protic polar solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene dialcohol, and propanol, and cellosolv solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and n-propyl cellosolve. . Examples of the aprotic polar solvent include acetone, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), pyridine and the like.

  As the silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and an acrylic silane coupling agent are preferable from the viewpoint of adhesion. As the epoxy silane coupling agent, for example, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, glycidoxypropyltrimethoxysilane and the like. In particular, when an epoxy-based silane coupling agent is used, the interlayer strength is improved due to high reactivity with amino-formaldehyde resin and phenol-formaldehyde resin.

  As amino-based silane coupling agents, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Examples include -3-aminopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, 3-ureidopropyltriethoxysilane, and isopropyltri (N-amidoethyl / aminoethyl) titanate. In particular, when an amino silane coupling agent is used, the interlayer strength is improved due to high reactivity with amino-formaldehyde resin and phenol-formaldehyde resin.

  The acrylic silane coupling agent is a silane coupling agent having a methacryl group in the skeleton, and examples thereof include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane.

コロイド状シリカとシランカップリング剤の反応割合は固形分で１：０．１〜５、より好ましくは１：０．３〜３．５とするのが良く、下限に満たないと、煮沸試験後に乾燥させるとヒビが入りやすく、上限を超えると不燃性が劣りやすくなる。 In the reaction between the colloidal silica and the silane coupling agent, the OH group of the hydrolysis product of the silane coupling agent and the OH group on the surface of the colloidal silica are dehydrated to form an organic / inorganic composite. Here, Me is a methyl group. The reaction may be mixed and stirred at room temperature.

The reaction ratio of the colloidal silica and the silane coupling agent should be 1: 0.1 to 5, more preferably 1: 0.3 to 3.5 in terms of solid content. When dried, cracks tend to occur, and when the upper limit is exceeded, nonflammability tends to be poor.

  In general, when a metal oxide is used as an inorganic filler, it is possible to modify the surface with a silane coupling agent because OH groups exist on the surface of the metal oxide, but in the case of calcium carbonate, there are no OH groups, Modification is not possible and water resistance is not improved, but by using the above organic / inorganic composite as an organic / inorganic composite binder as in the present invention, water resistance is improved and there is no delamination. Become.

  The flame retardant composition of the present invention uses a thermosetting resin such as a phenol-formaldehyde resin or an amino-formaldehyde resin that is excellent in dimensional change and impact resistance as an organic resin component. Phenol-formaldehyde resin is composed of 1 to 3 moles of formaldehyde with respect to 1 mole of phenolic hydroxyl groups of phenols such as phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F, water, Any generally known one obtained by reacting under a basic catalyst such as sodium oxide or triethylamine may be used. Examples of formaldehyde include formalin, paraformaldehyde, formit B, formit 1B, formit M (formit is a product name manufactured by Guangei Chemical Co., Ltd.), and the like.

  Among the thermosetting resins, amino-formaldehyde resin is particularly preferable because nonflammability is improved as compared with the case of using phenol-formaldehyde resin. The amino-formaldehyde resin is a polycondensate of ordinary melamine and formaldehyde, and as an amino compound, melamine and guanamine, specifically benzoguanamine, melamine / guanamine-formaldehyde resin co-condensed with acetoguanamine and formaldehyde, or this The warpage is reduced by using a mixture of melamine and formaldehyde resin. This is because guanamine has higher hydrophobicity than melamine and is less likely to absorb moisture, so warpage is considered to be small. The molar ratio at the time of reaction shall be 0.5-1.5 mol of guanamine with respect to 1 mol of melamine, and formaldehyde shall be 3.5-5.0 mol. If the amount of guanamine is small, the warpage tends to be large, and if it is large, the weather resistance tends to be poor. Examples of formaldehyde include formalin, paraformaldehyde, formit B, formit 1B, formit M (formit is a product name manufactured by Guangei Chemical Co., Ltd.), and the like.

Examples of the inorganic filler blended in the flame retardant composition include calcium carbonate, talc, fly ash, silica, kaolin and the like, and two or more kinds may be used in combination. It is preferable to use inexpensive calcium carbonate as an essential component. There is no restriction | limiting in particular as calcium carbonate, Heavy calcium carbonate, light calcium carbonate (precipitation calcium carbonate), etc. can be used. Heavy calcium carbonate having an average particle size of 0.05 to 20 μm, more preferably 1 to 10 μm is preferable. If the lower limit is not reached, secondary agglomeration tends to occur and agglomeration tends to occur and impregnation is likely to deteriorate. The surface of the decorative resin decorative board is not smooth, resulting in poor appearance. Light calcium carbonate refers to calcium carbonate that is chemically produced by firing limestone, and heavy calcium carbonate refers to finely powdered calcium carbonate prepared by dry or wet pulverization of white crystalline limestone.

The blending ratio of the thermosetting resin such as phenol-formaldehyde resin and amino-formaldehyde resin and the inorganic filler is preferably from 1:22 to 30, more preferably from 1:24 to 26 in terms of solid content. If it does not satisfy the lower limit, the nonflammability is not satisfied and the warping of the decorative board is further increased. If the upper limit is exceeded, the water resistance and strength of the decorative board will decrease.

  The blending ratio of the thermosetting resin such as phenol-formaldehyde resin or amino-formaldehyde resin and the organic / inorganic composite binder is 1: 0.1 to 1, more preferably 1: 0.17 to 0.00 in terms of solid content. If it is preferably less than the lower limit and dried after the boiling test, the core layer tends to crack, and if the upper limit is exceeded, nonflammability tends to be poor.

The base material of the prepreg impregnated with the flame retardant composition is a woven or non-woven fabric of inorganic fiber, and examples of the inorganic fiber include glass fiber, rock wool, carbon fiber, alumina fiber, ceramic fiber, The basis weight of the substrate is preferably in the range of 10 to ²⁰⁰ g / m ² , and in particular, it is preferable to use a glass fiber nonwoven fabric excellent in impregnation property of the flame retardant composition.

The impregnation rate of the flame retardant composition to the base material is preferably 500 to 3000% by the calculation method represented by Equation 1, and if the impregnation rate exceeds the upper limit, the solid content drops off and is difficult to handle. If the lower limit is not reached, delamination is likely to occur.

The content of the thermosetting resin component in the prepreg should be 3 to 4% by the calculation method shown in Equation 2, and if the lower limit is not reached, the strength and adhesion tend to be inferior. Does not meet.

The decorative board of the present invention comprises a plurality of prepregs obtained by impregnating a substrate with a flame retardant composition and drying, a resin-impregnated decorative paper as a decorative layer, and, if necessary, a resin-impregnated surface paper It is obtained by laminating and hot pressing with a flat plate press or continuous press. The hot pressure conditions may be a temperature of 120 to 140 ° C. and a pressure of 40 to 70 kgf / cm ² .

The resin-impregnated decorative paper is obtained by impregnating a decorative liquid for decorative board of 80 to 160 g / m ^{2 with} a resin liquid composed of a thermosetting resin and drying it. As the thermosetting resin, the amino-formaldehyde described above is used. Resins are preferably used because they are excellent in heat resistance, wear resistance and the like.

The resin-impregnated surface paper is used for the purpose of improving the abrasion resistance when printing paper is used as decorative paper, and is made of a thermosetting resin on the surface paper that becomes transparent after impregnation of 20 to 40 g / m ^2. As the thermosetting resin, an amino-formaldehyde resin is preferably used as in the case of decorative paper.

  EXAMPLES Hereinafter, although an Example is given and demonstrated in detail, this invention is shown more concretely and is not specifically limited. In addition, the part in an Example and a comparative example shows solid content.

Manufacture of organic / inorganic composite binder As colloidal silica, 10 parts of Snowtex S (water-dispersed silica sol, average particle size 18-11 nm, SiO ₂ 30%, manufactured by Nissan Chemical Industries, Ltd.), as a silane coupling agent, 15 parts of glycidoxypropyltrimethoxysilane (SH-6040: manufactured by Toray Dow Corning Co., Ltd.) was mixed and stirred at room temperature to obtain an organic / inorganic composite binder.
Production of core layer Flame retardant in which 80 g / m ² of glass fiber nonwoven fabric is blended with 50 parts of phenol-formaldehyde resin, 1300 parts of calcium carbonate having an average particle diameter of 8 μm as an inorganic filler , and the above organic / inorganic composite binder. A prepreg was obtained by impregnating the chemical composition so that the impregnation ratio shown in Formula 1 was 1200%.
In this case, the weight of the solid content after impregnation with the slurry is 1040 g / m ² from Equation ¹ , and the slurry content is 960 g / m ² by subtracting the weight of the glass fiber nonwoven fabric from 1040 g / m ² .
Further, 960 g / m ² includes 50 parts of phenol-formaldehyde resin, 1300 parts of calcium carbonate, and 25 parts of organic / inorganic composite binder, so that the organic resin component is 35 g / m ² and calcium carbonate is 908 g / m ^2. It is.
Therefore, the content (%) of the organic resin component in the prepreg calculated from Equation 2 is 3.5% by (35/1040) × 100.
A plain pattern decorative paper having a decorative layer basis weight of 80 g / m ² was impregnated with a melamine-formaldehyde resin so that the impregnation ratio represented by Formula 1 was 130% to obtain a melamine resin-impregnated decorative paper.
From the bottom of the production of the decorative board, one sheet of melamine resin-impregnated decorative paper, four sheets of prepreg, and one sheet of melamine-formaldehyde resin-impregnated decorative paper are laminated at 140 ° C. and 70 kg / cm ² using a flat finish plate. The decorative board of Example 1 was obtained by hot pressing under the condition of 90 minutes.

  In Example 1, it implemented similarly except having made the silane coupling agent 7.5 parts.

  In Example 1, it carried out similarly except having made colloidal silica into 20 parts.

  In Example 1, it carried out similarly except having made 20 parts of colloidal silica and 7.5 parts of silane coupling agents.

  In Example 1, it carried out similarly except having made colloidal silica into 4.5 parts.

  In Example 1, it carried out similarly except having silane coupling agent 7.5 parts, calcium carbonate 1200 parts, and mixing 100 parts of kaolin.

Manufacture of organic / inorganic composite binder As colloidal silica, 10 parts of Snowtex S (water-dispersed silica sol, average particle size 18-11 nm, SiO ₂ 30%, manufactured by Nissan Chemical Industries, Ltd.), as a silane coupling agent, 7.5 parts of glycidoxypropyltrimethoxysilane (SH-6040: manufactured by Toray Dow Corning Co., Ltd.) was mixed and stirred at room temperature to obtain an organic / inorganic composite binder.
Manufacture of core layer To 50 g / m ² glass fiber nonwoven fabric, with respect to 50 parts of melamine-formaldehyde resin, 1200 parts of calcium carbonate having an average particle diameter of 8 μm as an inorganic filler, 100 parts of kaolin, and the above organic / inorganic composite binder A prepreg was obtained by impregnating the blended flame retardant composition so that the impregnation ratio shown in Formula 1 was 1200%.
In this case, the weight of the solid content after impregnation with the slurry is 1040 g / m ² from Equation ¹ , and the slurry content is 960 g / m ² by subtracting the weight of the glass fiber nonwoven fabric from 1040 g / m ² .
Further, 960 g / m ² contains 50 parts of melamine-formaldehyde resin, 1200 parts of calcium carbonate, 100 parts of kaolin, and 17.5 parts of organic / inorganic composite binder, so the organic resin component is 35 g / m ² . .
Therefore, the content (%) of the organic resin component in the prepreg calculated from Equation 2 is 3.4% by (35/1040) × 100.
A plain pattern decorative paper having a decorative layer basis weight of 80 g / m ² was impregnated with a melamine-formaldehyde resin so that the impregnation ratio represented by Formula 1 was 130% to obtain a melamine resin-impregnated decorative paper.
From the bottom of the production of the decorative board, one sheet of melamine resin-impregnated decorative paper, four sheets of prepreg, and one sheet of melamine-formaldehyde resin-impregnated decorative paper are laminated at 140 ° C. and 70 kg / cm ² using a flat finish plate. The decorative board of Example 1 was obtained by hot pressing under the condition of 90 minutes.

  In Example 7, it implemented similarly except having made 7.5 parts of silane coupling agents 4.2 parts.

  In Example 7, it carried out similarly except not using kaolin and using 1100 parts of calcium carbonate.

Comparative Example 1
In Example 1, it implemented similarly except not using an organic and inorganic composite binder.

Comparative Example 2
In Example 1, it implemented similarly except having used 20 parts of colloidal silica instead of the organic-inorganic composite binder.

Comparative Example 3
In Example 1, it carried out similarly except not using colloidal silica instead of the organic-inorganic composite binder.

Comparative Example 4
In Example 1, colloidal silica and a silane coupling agent were not reacted, and the same procedure was performed except that the following core layer was used.
Manufacture of core layer On 80 g / m ² glass fiber nonwoven fabric, with respect to 50 parts of melamine-formaldehyde resin, 1200 parts of calcium carbonate with an average particle diameter of 8 μm as inorganic filler, 100 parts of kaolin, and SNOWTEX S as colloidal silica 10 parts of (water-dispersed silica sol, average particle size 18 to 11 nm, SiO ₂ 30%, manufactured by Nissan Chemical Industries, Ltd.) and glycidoxypropyltrimethoxysilane (SH-6040: Toray A prepreg was obtained by impregnating a flame retardant composition containing 7.5 parts of Dow Corning Co., Ltd. so that the impregnation ratio shown in Equation 1 was 1200%.
However, colloidal silica appeared on the prepreg surface, and the interlayer adhesion was extremely inferior.

The evaluation method was as follows.
Nonflammability: Exothermic test of 20-minute test using a corn calorimeter conforming to ISO 5660 ◎: The total calorific value is 6 MJ / m ² or less in the evaluation method, and the maximum heat generation rate continues for more than 10 seconds and exceeds 200 kW / m ² When there is no ◎.
○: In the evaluation method, the total heat generation amount is 6 to 8 MJ / m ² or less, and the case where the maximum heat generation rate continues for 10 seconds or more and does not exceed 200 kW / m ² is evaluated as ○.
X: In the evaluation method, the case where the total heat generation amount exceeds 8 MJ / m ² and the maximum heat generation rate continues for 10 seconds or more and exceeds 200 kW / m ² is determined as x.

  Cracking of the core layer by boiling and drying: after immersion in boiling water for 2 hours, forced drying with a thermostat for 15 hours, visually confirming the appearance, ◯ without cracks, x with cracks .

  Interlayer adhesion: After immersion in boiling water for 2 hours, the case where there was no peeling of the decorative layer and no significant crack between the core layer and the decorative layer was accepted, and the case where there was peeling and cracking was rejected. The above tests were performed, and those that passed both were marked with ◯, and those that were not, with x.

FIG. 2 is a structural cross-sectional view of the incombustible decorative board of the present invention.

2 Resin-impregnated decorative paper layer 3 Prepreg 6 Non-combustible decorative board

Claims (6)

Organic / inorganic composite made by reacting thermosetting resin, one or more inorganic fillers selected from the group consisting of calcium carbonate, talc, fly ash, silica and kaolin , colloidal silica and silane coupling agent A flame retardant composition comprising a binder as an essential component. 2. The flame retardant composition according to claim 1, wherein a blending ratio of the thermosetting resin and the organic / inorganic composite binder is 1: 0.1 to 1 in a solid content ratio. The flame retardant composition according to claim 1, wherein a reaction ratio of the colloidal silica and the silane coupling agent is 1: 0.3 to 3.5 in solid content. The flame retardant composition according to claim 1, wherein calcium carbonate is used as an essential component as the inorganic filler. The flame retardant composition according to claim 1 or 2, wherein the thermosetting resin is a phenol-formaldehyde resin or an amino-formaldehyde resin. A decorative board comprising a prepreg impregnated with a flame retardant composition according to any one of claims 1 to 5 and dried on an inorganic fiber base material, and a resin-impregnated decorative paper.

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