JPH055036A - Composite material of phenol resin - Google Patents

Abstract

PURPOSE:To obtain an incombustible composite material useful as a lightweight building material having excellent mechanical strength by blending heated hollow inorganic particles with a filler and a phenol resin, kneading, molding and thermally curing. CONSTITUTION:1 liter preheated hollow inorganic particles are blended with 50-500 cubic centimeter inorganic filler having >=0.5mm average particle diameter and water of crystallization and 10-150 cubic centimeter novolak type phenol resin to give a kneaded material, which is molded into a desired shaped and thermally cured. Perlite or ceramics-based balloons are preferable as the inorganic particles. A phenol resin having <=0.15mm average particle diameter is used as the phenol resin. The hollow inorganic particles are heated to about 170-250 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol resin composite which is lightweight and has excellent mechanical strength and is useful as a building material.

[0002]

2. Description of the Related Art In recent years, the performance of building materials has advanced with the diversification of buildings, and as a result, many plastic-based building materials have been used as interior and exterior materials. However, compared to cement-based building materials, conventional plastics-based building materials are lighter, more heat-insulating, environmentally resistant to temperature and frost damage, and are more producible and workable, while they are flammable materials.
When a fire occurs, it is easy for the fire to spread, and the generation of toxic gases is also remarkable.

[0003]

Therefore, for example, a building material as disclosed in JP-A-56-62143 has been proposed. This building material is formed by hardening fly ash, pumice stone, and glass fiber as an inorganic aggregate with a resin.

However, in order to obtain a predetermined incombustibility by this method, the amount of resin used must be reduced. However, if the amount of resin is reduced, even if non-combustibility can be achieved, the strength of the obtained molded product will be remarkably low, resulting in a building material that cannot be used in actual use. In view of the above problems, the present invention eliminates the conventional drawbacks, has a nonflammability that can be suitably used for building materials and the like that can be applied as an interior / exterior material, and is a lightweight and phenolic resin having excellent mechanical strength. The purpose is to provide a complex.

[0005]

In order to achieve such an object, the present invention provides an inorganic filler having water of crystallization having an average particle size of 0.5 mm or more per 1 liter of preheated hollow inorganic particles. A kneaded product obtained by adding 50 to 500 cubic centimeters and novolac type phenolic resin 10 to 150 cubic centimeters, and mixing and kneading,
The gist is a phenol resin composite characterized by being molded into a desired shape and heat-cured.

[0006]

According to the above constitution, a kneaded material is obtained by uniformly mixing the novolak type phenol resin having excellent flame retardancy around the hollow inorganic particles and the inorganic filler by mixing and kneading, and then the kneaded material is mixed. The phenolic resin composite is formed by molding the resin into a desired shape and further heat curing the phenolic resin. The phenolic resin composite thus obtained has a hollow inorganic particle and an inorganic filler of phenolic compound. It is strongly bonded through the resin, and when heated, the crystal water in the inorganic filler is released, so that the temperature of the composite itself is cooled by the cooling action of the released crystal water. Is becoming

[0007]

The present invention will be described in detail below with reference to its examples. FIG. 1 schematically shows a cross-sectional view of a phenol resin composite according to the present invention, in which 1 is a phenol resin,
2 represents hollow inorganic particles, and 3 represents an inorganic filler having crystal water.

The hollow inorganic particles used in the present invention are particularly limited.
Not, for example perlite, vermiculite, glass
Balloon, Shirasu balloon, coal ash (fly ash)
Balloons, ceramic balloons, etc. are preferably used
It The shape, particle size, particle size distribution, etc. of these inorganic particles are special.
Not limited to. Inorganic with water of crystallization used in the present invention
Fillers are compounds that release water when heated.
And, for example, aluminum, calcium, magnet
Compounds such as sium and sodium, that is, A1 (O
H)₃, Ca (OH)₂, CaSO _Four・ 2H₂O, A1
₂(SO_Four)₃・ (NH_Four)₂SO_Four・ 24H₂O, M
g₃(PO_Four)₂・ 8H₂O, MgSO₃・ 6H₂O,
Na₂B_FourO₇・ 10H₂O and the like.

Hollow inorganic particles 1 containing inorganic filler
If it is less than 50 cubic centimeters per liter, it becomes impossible to secure incombustibility. On the other hand, when it exceeds 500 cubic centimeters, the strength of the molded product is low, and it is not possible to obtain a mechanical strength that is satisfactory as a building material. Further, when the average particle size of the inorganic filler is less than 0.5 mm, the Ministry of Construction Public Notice No. 1828 (December 28, 1945) based on the Building Standards Act.
In the base material test for evaluating nonflammability according to (Japanese), it cannot be maintained below the reference temperature, and the base material test does not pass.

That is, since the inorganic filler has crystal water, it releases water when the test piece is heated in the heating furnace in the base material test, and the temperature inside the furnace is controlled by the cooling effect of the released water. It is considered to play a role of keeping the value below the standard value. The novolak type phenol resin that can be used in the present invention is an initial condensate obtained by reacting phenols and aldehydes under an acid catalyst,
The initial condensate means one capable of further progressing polymerization while undergoing a crosslinking reaction in the presence of a curing agent (crosslinking agent).

Phenols are mainly phenols, but at least one selected from the group consisting of cresol and its isomers, alkylphenols, bisphenols and other novolak-type modified phenolic resins.
More than a seed. The aldehydes include formaldehyde, furfural, higher aldehydes and the like. Further, the acid catalyst is a strong acid such as oxalic acid, sulfuric acid, paratoluenesulfonic acid, Ca, Zn, Cd, Pb, C.
It is a metal salt catalyst such as o.

The novolac type phenol resin used in the present invention preferably has an average particle size of 0.15 mm or less. That is, if the average particle size exceeds 0.15 mm, the composite strength may not be exhibited. The amount of phenolic resin is limited to 10 to 150 cubic centimeters per liter of hollow inorganic particles. When used over 150 cubic centimeters for hollow inorganic particles, the mechanical strength is improved,
Incombustibility can no longer be secured. On the other hand, the amount of resin is 1
If it is less than 0 cubic centimeter, the strength of the molded product is low and the mechanical strength which is satisfactory as a building material cannot be obtained.

The hardener for the novolac type phenol resin is not particularly limited, but for example, hexamethylenetetramine, paraformaldehyde, resole and the like are preferably used, and the amount thereof is 6-18 per 100 parts by weight of the phenol resin. About parts by weight is preferable. In the present invention, the method of mixing and kneading the above-mentioned hollow inorganic particles with a phenol resin is carried out by adding preheated hollow inorganic particles to a stirrer, adding a predetermined amount of phenol resin while stirring and sufficiently melting and dispersing, Is a method in which a hardening agent such as an aqueous solution of hexamethylenetetramine is added to and the stirring is continued.

The temperature of the hollow inorganic particles and the inorganic filler at the time of introducing the resin is at least a temperature at which the phenol resin is sufficiently melted and fluidized, and a temperature below the temperature at which crystallization water is released from the inorganic filler, for example, 170. It is preferably about 250 ° C. Incidentally, when an aqueous solution of hexamethylenetetramine is used as the curing agent, the temperature of the hollow inorganic particles and the inorganic filler at the time of introducing the aqueous solution is preferably 100 to 140 ° C., and when it exceeds 140 ° C., hexamethylenetetramine is decomposed. The formalin is produced and the curing of the phenolic resin proceeds, and as a result, the strength of the molded product when molded is reduced.

The phenol resin composite provided by the present invention is obtained by, for example, filling the resin-coated hollow particles obtained by the above-mentioned method into a shaping mold, curing at a temperature of 140 to 220 ° C., and then demolding. However, any other thermoforming method may be used. The effects of the present invention will be described below with reference to examples and comparative examples. (Example 1) About 210 in advance in a speed mixer
Fly ash balloon heated to ℃ (true specific gravity = 0.
7. Cubic specific gravity 0.4, average particle size 110 μm) 1 liter and aluminum hydroxide (A1 (OH) ₃ ) 200 cubic centimeters with average particle size 0.75 mm heated to 210 ° C., novolac type phenol resin (trade name PR -F6
100 cubic centimeters (3, manufactured by Sumitomo Dures) were added, stirred and kneaded for 1 minute, 17 g of hexamethylenetetramine was dissolved in 170 g of water and added, and the mixture was further stirred for 1 minute. After cooling as it was, the kneaded product in which the periphery of the fly ash balloon was uniformly coated with the phenol resin was taken out from the mixer.

Next, the kneaded product was placed in a thermoforming mold heated to 180 ° C. and heated at a pressure of 30 kg / cm ² for 15 minutes to obtain a plate composite having a thickness of 10 mm. Example 2 Shirasu balloon (true specific gravity 0.21, average particle size 100 μm) was used instead of fly ash balloon, and calcium hydroxide (Ca with an average particle size of 0.6 mm was used instead of aluminum hydroxide). (OH) ₂ )
A plate-like composite was obtained in exactly the same manner as in Example 1 except that was used. (Example 3) Ceramic-based balloons (true specific gravity: 0.75, average particle size: 100 μ) instead of fly ash balloons
m) and magnesium phosphate octahydrate (Mg) having an average particle size of 0.8 mm instead of aluminum hydroxide.
_A plate-like composite was obtained in exactly the same manner as in Example 1 except that ₃ (PO ₄ ) ₂ .8H ₂ O) was used. (Example 4) Instead of aluminum hydroxide, borax (Na
_{2 B 4 O 7 · 10H 2} O) used, except that the heating temperature of the fly ash balloons and borax in 180 ° C. to obtain a composite sheet material in the same manner as in Example 1. (Comparative Example 1) A plate-like composite was obtained in exactly the same manner as in Example 1 except that aluminum hydroxide having an average particle size of 0.3 mm was used. Comparative Example 2 Example 1 except that the fly ash balloon was 1.2 liters and aluminum hydroxide was removed.
A plate-like composite was obtained in exactly the same manner as. (Comparative Example 3) Except that the amount of aluminum hydroxide was 30 cubic centimeters, the same procedure as in Example 1 was carried out.
A plate-like composite was obtained. (Comparative Example 4) A plate-like coalescence was obtained in exactly the same manner as in Example 1 except that the amount of the phenol resin was 200 cubic centimeters and the amount of hexamethylene tetramine was 34 g.

The bulk specific gravity, flexural strength, flexural modulus and nonflammability of the plate-like composites obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated, and the results are shown in Table 1. In addition,
The bending test was carried out according to JIS-K-7203 by making a test piece of 120 × 20 × 10 mm from the molded body. In addition, the non-flammability test was performed by a base material test and a surface test in accordance with the Ministry of Construction Public Notice No. 1828 (December 28, 1970) based on the Building Standards Act.

[0018]

[Table 1]

As shown in Table 1, all of the examples were lightweight, excellent in strength, and excellent in incombustibility.

[0020]

Since the phenol resin composite according to the present invention is constructed as described above, it exhibits high strength, the non-combustibility of the composite is secured by the limitation of the amount of the resin, and the composite is heated. Then, water of crystallization in the inorganic chamber filler is released, so that the inorganic chamber filler has higher incombustibility.

Moreover, since hollow inorganic particles are used as the main material, they are lightweight, can be nailed and sawed, and have excellent secondary workability, and can be suitably used as an interior / exterior material for construction. ..

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing a phenol resin composite according to the present invention.

[Explanation of symbols]

 1 Phenolic resin 2 Hollow inorganic particles 3 Inorganic filler

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Claims (1)

Claim: What is claimed is: 1. A liter of preheated hollow inorganic particles, 50 to 500 cubic centimeters of an inorganic filler having a water of crystallization having an average particle size of 0.5 mm or more, and a novolac type phenol resin 10. A phenol resin composite characterized in that a kneaded product obtained by adding ~ 150 cubic centimeters, mixing and kneading is molded into a desired shape and heat-cured.