JPH0834656A - Refractory material and its production - Google Patents

Abstract

PURPOSE:To produce a lightweight refractory material having superior fire and heat resistances, superior heat insulating property and satisfactory workability at a low cost. CONSTITUTION:A soln. of silanol having a siloxane skeleton is mixed with at least a volcanic ash-based admixture, montmorillonite and mineral fibers and the resultant mixture is cured and molded by heating to obtain the objective refractory material. The silanol soln. is prepd. by mixing metal silicon with sodium fluoride or hydrogen fluoride, sodium hydroxide and water and bringing the resultant mixture into an exothermic reaction or a reaction by heating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fireproof material excellent in fireproofing / fireproofing, heat resistance, heat insulation, and sound insulation, which can be used as a fireproof coating material, a fireproof partition material, a smokeproof material and the like. is there.

[0002]

BACKGROUND OF THE INVENTION Fireproof coatings for buildings are widely used for fireproofing using a plate-like member that can be easily installed on site. For such a fire resistant member, there is a demand for a fire resistant material that is thinner and has sufficient fire resistance, fire resistance, and heat resistance, is lightweight, and has good workability. However, the gypsum board, which has been widely used as a conventional inexpensive fireproof plate-like member, is as thick as 6 cm after 2 hours of fireproofing and needs to have a thickness of 20 cm for use as a fireproof partitioning material. Therefore, there is a drawback that it becomes a heavy member and is inconvenient to handle.

Japanese Patent Application Laid-Open No. 4-239079 proposes a fire-resistant composite material using a sheet-like fire-resistant adhesive material containing an inorganic compound as a main component in order to reduce the thickness.
This sheet-shaped fire-resistant adhesive is a pressure-sensitive adhesive sheet obtained by adding Poval's aqueous solution and cement for eluting polyvalent metal in order to cure silanol having a siloxane skeleton described in JP-A-1-313303, and gelating the mixture by alcohol treatment. It is what This sheet-like adhesive has excellent fire resistance and heat resistance, but since this adhesive itself does not have self-sustainability, it must be used by laminating it on other non-combustible materials such as conventional gypsum board and fire resistant materials. However, there is a limit to reduce the thickness of the laminated composite material. Further, in the production of the sheet-shaped fire-resistant adhesive, a solution A in which cement is mixed with an aqueous solution of Poval and a solution B in which a water-retaining and solidifying material such as zeolite is added to the silanol solution are separately prepared, and these are separately alcoholized. It was necessary to mix after treatment, or to mix both solutions and then treat with alcohol to gel and mold into a sheet, which was troublesome to manufacture. Furthermore, there is also a disadvantage that it is necessary to stack it on another noncombustible material or a refractory material to form a composite material, or to perform a lamination work on site.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has excellent fire resistance, heat resistance, and heat insulation.
A first object of the present invention is to provide a refractory material that is lightweight, has good workability, and can be manufactured at low cost. The present invention also provides a method of manufacturing the refractory material together.
The purpose of.

[0006]

The first object of the present invention is a refractory material obtained by curing and molding a mixture of a silanol solution having a siloxane skeleton with at least a volcanic ash mixture material, montmorillonite and mineral fibers by heating. Achieved by

A second object of the present invention is to manufacture a refractory material by mixing at least a volcanic ash mixture material, montmorillonite and mineral fiber with a silanol solution having a siloxane skeleton and heating and mixing the mixture. This is achieved by a method for manufacturing a characteristic refractory material.

That is, in the present invention, a silanol solution having a siloxane skeleton is used as a main agent, and a volcanic ash mixture material and montmorillonite which is a clay mineral are added as a water retention solidifying material, and mineral fibers are added as a heat insulating fibrous material This is a refractory material having excellent fire resistance, light weight, and easy handling, which is obtained by mixing and molding and curing it by heating. Further, it is a more preferable embodiment that diatomaceous earth or fine silica sand and layered silica such as mica are also mixed and heated to be molded and cured.

A silanol solution is disclosed in JP-A-1-31330.
3 and the silanol having a siloxane skeleton described in JP-A-4-239079 can be used. In particular, a fluoric silanol salt solution containing silicon, fluorine, and sodium as a basic skeletal element is preferable, and metallic silicon, sodium fluoride (or hydrogen fluoride), sodium hydroxide, and water are mixed to heat or generate heat. It is possible to obtain by reacting. The mixing ratio is not particularly limited. If the silanol solution produced becomes excessively alkaline, post-treatment is required, so it is better not to use more sodium fluoride (or hydrogen fluoride) or sodium hydroxide than necessary. In addition, it is advantageous from the viewpoint of production that excess water is not used in order to carry out the heating reaction only by the heat generated by the mixed reaction of water and sodium hydroxide. If the silanol liquid produced becomes excessively alkaline, waste liquid treatment becomes necessary. Therefore, it is better not to use more sodium fluoride (or hydrogen fluoride) or sodium hydroxide than necessary. In addition, it is advantageous from the viewpoint of production that excess water is not used in order to carry out the heating reaction only by the heat generated by the mixed reaction of water and sodium hydroxide. If the exothermic reaction is insufficient, heat to bring the reaction solution to a boil.
The less water used in producing this silanol solution, the more viscous silanol solution, and the more water used, the less viscous silanol solution. It is preferable that the silanol liquid used as the main ingredient of the refractory material is viscous to some extent, but if the amount of water used is reduced to make it highly viscous, the water will evaporate due to an exothermic reaction. I can't get it.

From this viewpoint, 3 to 40 parts by weight of sodium fluoride and 3 to 40 parts by weight of metallic silicon are used.
Preference is given to using 30 parts by weight of sodium hydroxide and 50 to 2000 parts by weight of water. A particularly preferred ratio is
For 50 parts by weight of metallic silicon, 3 to 20 parts by weight of sodium fluoride, 3 to 20 parts by weight of sodium hydroxide and 100 to 1000 parts by weight of water. The most preferred silanol solution is 50 parts by weight of metallic silicon,
10 to 20 parts by weight of sodium fluoride, 10 to 20 parts by weight of sodium hydroxide and 100 to 200 parts by weight of water are mixed to cause an exothermic reaction, and after cooling to room temperature, the generated floating slag and precipitation residue are removed. Viscous supernatant (fluoric silanol salt solution) can be used.

The volcanic ash mixture is used as a lightweight siliceous filler. By using such a lightweight and low-density filler, a lightweight refractory material can be obtained. Further, since it contains silicic acid (silica) as a main component, the refractory material of the present invention containing this may crack and crack due to vitrification of the surface when exposed to high heat. Is prevented. As such a volcanic ash mixture, lightweight natural volcanic ash such as Shirasu (Asoyama volcanic ash) and other volcanic ash produced in Kagoshima prefecture can be used. With respect to 500 parts by weight of the silanol solution, preferably 100 to 300 parts by weight, particularly preferably 120 to 20 parts by weight.
Mix 0 parts by weight of volcanic ash mixture.

Montmorillonite is a clay mineral that is the main component of acid clay and bentonite, and swells when it contains water. In the present invention, this is used as a swelling agent. Bentonite, which is Na- or Ca-montmorillonite, is preferable as the montmorillonite. With respect to 500 parts by weight of silanol solution, preferably 50 to 200 parts by weight, particularly preferably 60 to 180 parts by weight of montmorillonite is used.

The mineral fiber, that is, the inorganic fibrous material is a heat insulating filler and has a function as a binder due to the fiber structure. As the mineral fiber, one or more selected from Chinese cotton, carbon fiber, alumina fiber, alumina silica fiber and the like can be used, and Chinese cotton (China fiber) is particularly preferable. The mixing ratio is preferably 5 to 20 parts by weight of mineral fiber to 500 parts by weight of silanol solution. When using Chinese fiber (China fiber) and carbon fiber together, 2 to 10 parts by weight of Chinese cotton, 2 parts by weight to 500 parts by weight of silanol solution, 2
It is preferable to use 10 to 10 parts by weight of carbon fiber.

When diatomaceous earth or fine silica sand is used in combination, the mixing ratio is preferably 10 to 200 parts by weight, and particularly preferably 20 to 1 part with respect to 500 parts by weight of the silanol solution.
00 parts by weight of diatomaceous earth or fine silica sand. Further, when layered silica such as mica (muscovite, biotite, etc.) is used in combination, the mixing ratio thereof is preferably 1 to 50 parts by weight, particularly preferably 2 to 500 parts by weight of the silanol solution.
20 parts by weight.

By mixing these volcanic ash mixture materials, montmorillonite, mineral fibers, and, if necessary, layered silica such as diatomaceous earth or fine silica sand and mica, with the above silanol solution, an extremely viscous mixed solution is obtained. After uniformly stirring and mixing this, it can be cured by placing it in a molding frame and heating it from both front and back sides under pressure. The heating temperature required for curing is 130 ° C. or higher, preferably 160 ° C. or higher, and more preferably 260 ° C. or higher. The target refractory material can be obtained by releasing from the mold after heating and curing.

[0016]

Example 5 kg of metallic silicon mass, 1.8 kg of sodium fluoride and 1.6 kg of sodium hydroxide were put into a reaction vessel, and finally put into 16 L (Kg) of water. The reaction solution was heated by an exothermic reaction, started boiling at about 80 ° C, and reached a maximum temperature of about 120 ° C. This was left to stand, and when the temperature dropped to room temperature, the slag floating on the upper surface of the reaction solution was removed. At the bottom of the reaction vessel, undissolved metallic silicon and sodium fluoride were precipitated as residues. This precipitate was also discarded and the low-viscosity supernatant was taken to obtain the desired silanol solution.

For 5 kg of the obtained silanol solution, 1.4 kg of shirasu, 800 g of bentonite, and 300 diatomaceous earth.
g, carbon fiber 30g, China fiber 60g, muscovite 40g, and stirred for about 30 minutes with an omni mixer,
Mix and knead well until uniform. This kneaded mixture was placed on a release plate and had a length of 30 cm, a width of 30 cm, and a depth of 30 cm.
The mold was placed in a 6 cm mold, and a mold release plate that fits inside the mold was placed on the upper surface. The upper and lower mold release plates were sandwiched and pressed, and heated at 260 ° C. for 30 minutes to cure. This was unmolded to obtain a plate-shaped refractory material.

A fire resistance test was carried out using this plate-like refractory material (thickness: about 15 mm). As a comparative example, a commercially available gypsum board (thickness: about 15 mm) was used. This commercial gypsum board is
It is manufactured from lime, water, fine silica sand and white cement. When the flame of the LPG gas burner for construction was sprayed from a distance of about 7 cm, the conventional gypsum board started to emit smoke after about 5 minutes, and cracked due to heating after 20 to 30 minutes due to heating. A flame came to reach from the crack to the back of the board. On the other hand, in the plate-like refractory material of this example, no smoke was generated even after 20 minutes of flame spraying, and even if flame spraying was performed for 1 hour, the flame sprayed surface only vitrified, and smoke was emitted. There was no cracking or cracking, and there was no flame on the back of the board. The refractory material (board) of this example was lighter than the conventional gypsum board. According to the Fire Service Act, in order to satisfy the fire resistance required for the fireproof partition, the conventional gypsum board required a thickness of 20 cm, but the fire resistant board of the present invention can satisfy this with a thickness of 1.5 cm. It was The fireproof material (board) of this example was also excellent in heat insulation and sound insulation.

[0019]

As described above, the refractory material of the present invention is obtained by mixing the silanol solution having a siloxane skeleton with at least a volcanic ash mixture material, montmorillonite and mineral fibers.
This is molded and cured by heating, and has excellent fire resistance, heat resistance, and heat insulation. Further, it is possible to make a lightweight refractory material having a low specific gravity. Further, since it has excellent fire resistance, even if the thickness of the refractory material is thinner than that of the conventional one, it is possible to secure the fire prevention / fireproof performance superior to that of the conventional one.
For this reason, there is an effect that it is lightweight and has good workability. Further, the refractory material of the present invention is easy to manufacture and can be manufactured at low cost.

Claims (8)

[Claims] 1. A refractory material obtained by curing and molding a mixture of a silanol solution having a siloxane skeleton and at least a volcanic ash mixture material, montmorillonite and mineral fibers by heating. 2. A refractory material formed by mixing at least the following and heat-curing: (a) 500 parts by weight of a silanol solution having a siloxane skeleton; (b) 100-300 parts by weight of volcanic ash mixture. Material,
(c) 50 to 200 parts by weight of montmorillonite, (d) 5 to
20 parts by weight of heat insulating mineral fiber. 3. The silanol solution is metallic silicon,
The refractory material according to claim 1 or 2, which is a fluoric silanol salt solution obtained after an exothermic or heating reaction by mixing sodium fluoride (or hydrogen fluoride), sodium hydroxide and water. 4. The silanol solution comprises 50 parts by weight of metallic silicon, 3 to 40 parts by weight of sodium fluoride, 3 to 40 parts by weight.
The refractory material according to claim 3, which is a fluoric silanol salt solution obtained by mixing 30 parts by weight of sodium hydroxide and 50 to 2000 parts by weight of water and reacting with heat or heat. 5. The refractory material according to any one of claims 1 to 4, wherein diatomaceous earth or fine silica sand and layered silica are mixed together with the silanol solution, and the mixture is heat-molded and cured. . 6. The refractory material according to claim 1, wherein the mineral fiber is any one of Chinese cotton, carbon fiber, alumina fiber and alumina silica. 7. The refractory material according to claim 1, wherein the montmorillonite is bentonite. 8. A refractory material produced by mixing a silanol solution having a siloxane skeleton with at least a volcanic ash mixture material, montmorillonite and mineral fibers, and heating the mixture to cure the mixture to produce a refractory material. Method.