JP2966430B2 - Refractory material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]

The present invention relates to a refractory material used for forming a refractory layer on a surface of a building material or the like to protect the building material or the like from a flame.

[Prior art]

As a refractory material to protect building materials from flames,
The use of carbon powder such as graphite powder has been proposed by the present applicant. This refractory material contains carbon powder as a refractory filler and a resin as a binder. The refractory material is molded and formed as a refractory layer on the surface of a building material or the like. Thereby, the action of the flame on the building materials and the like is blocked by the refractory layer, thereby preventing the building materials and the like from being burned by the action of the flame and increasing the scale of the fire or burning the fire. This refractory material is easy to form a refractory layer by molding because the resin is used as a binder, and has an excellent effect of blocking a flame due to excellent fire resistance of carbon powder used as a refractory filler. have.

In this case, the flame acts on the refractory layer, so that the binder resin in the refractory layer is carbonized. This is desirable from the viewpoint of improving the heat insulation of the refractory layer. However, since the resin shrinks when carbonized, there is a problem that cracks are generated in the refractory layer due to the shrinkage, and there is a possibility that the flame may penetrate and invade from gaps created by the cracks. The present invention has been made in view of the above points, and provides a refractory material that can reduce the occurrence of cracks in a refractory layer and can prevent the invasion of flame even if cracks occur. It is intended to do so.

[Means for Solving the Problems]

The present invention is a refractory material containing carbon powder and sand as a refractory filler, and a resin as a binder, respectively, a carbon-resin composite material prepared by reacting a resin raw material while mixing carbon powder, As the sand, a resin-coated sand in which a resin is coated on the surface of the sand is blended. Hereinafter, the present invention will be described in detail. Carbon powder used as a refractory filler in the present invention can be generally used as long as it is a carbonaceous powder, and examples thereof include natural graphite, artificial graphite, carbon black, coke powder, charcoal powder, chaff charcoal, and the like. These can be used alone or in combination of two or more. The particle size of the carbon powder is not particularly limited, but is preferably about 1 to 200 μm. The resin used as the binder is not particularly limited, but is preferably cured by heating or the like, that is, it is preferable to use a thermosetting resin having a self-curing property, among which a phenol resin, a melamine resin, and a furan resin are used. Resins and the like are preferred. This binder resin is generally used as a self-curing composite material attached to the surface of carbon powder. In preparing the self-curable composite material, the thermosetting resin can be attached to the surface of the carbon powder at the same time when the initial condensate of the thermosetting resin is prepared. This is a method provided by the present applicant as Japanese Patent Application No. 61-191083.For example, in preparing an initial condensate of a phenolic resin, a phenol and an aldehyde are placed in a reaction vessel in the presence of a catalyst in the presence of a catalyst. By mixing and reacting with the powder, a phenolic resin is uniformly attached to the surface of the carbon powder, and this is filtered and dried to obtain a self-curing composite material as a spherical powder. It is. A self-curing composite material can be obtained from melamine resin and furan resin in the same manner as in this method. In the case of melamine resin, it is possible to obtain a self-curing composite material as spherical particles as in the case of phenol resin, but in the case of furan resin, it is generally not possible to prepare spherical particles, so It will be used after freeze-drying. In general, carbon powder is poorly coated with a resin.When preparing a self-curing composite material by kneading the carbon powder and the resin in a kneader, it is difficult to uniformly disperse the carbon powder and a large amount of carbon powder is used. It is difficult to mix, but when synthesizing a thermosetting resin at the same time as in the above method and simultaneously preparing a self-curable composite material by mixing carbon powder, there is no such problem, And a self-curable composite material containing a large amount of carbon powder can be easily prepared. In order to obtain sufficient fire resistance, the content of the carbon powder in the self-curing composite material is preferably 30% by weight or more. In addition to the carbon powder, a powdery material such as alumina or magnesia can be blended as needed, and a fibrous material or a lightweight aggregate can also be added as a reinforcing material or an expanding material. The refractory material according to the present invention can be obtained by mixing the self-hardening composite material and sand. It is preferable to use silica sand as the sand, and it is not particularly limited, but the particle size is preferably about 1 to 500 μm. It is prepared and used in the form of resin-coated sand. Resin-coated sand is obtained by coating a sand surface with a self-hardening thermosetting resin, and it is preferable to use the same resin as the resin of the self-hardening composite material as the resin to be coated. It constitutes a part of the binder resin. In preparing resin-coated sand by coating sand with a resin, dry hot coating, cold coating, semi-hot coating,
It can be performed by a powdered solvent method or the like. In the dry hot coating method, a solid resin is added to heated sand and mixed,
This is a method in which a solid resin is melted by heating with sand, the surface of the sand is wetted and coated with the molten resin, and then cooled while maintaining the mixture to obtain a granular, resin-coated sand. The cold coat method is a method in which a resin is dissolved in a solvent such as methanol to form a liquid, which is added to sand, mixed, and then the solvent is volatilized to obtain a resin-coated sand. The semi-hot coating method is a method in which a resin dissolved in the above solvent is added to sand heated to about 50 to 90 ° C. and mixed to obtain a resin coated sand. The powder solvent method crushes solid resin,
This is a method in which the ground resin is added to sand, a solvent such as methanol is further added, and this is mixed to obtain a resin-coated sand. In any of the above methods, a granular and coated resin-coated sand can be obtained, but a dry hot coating method is preferred in terms of workability and the like. In addition, when mixing to prepare resin-coated sand, if necessary, a curing agent, other coupling agents such as a silane coupling agent for making the sand and resin compatible, and a lubricant such as calcium stearate are compounded. can do. The refractory material obtained as described above is heated and press-molded to cure the binder resin, whereby a refractory layer having an arbitrary form such as a sheet (thin plate) can be formed. The formation of a refractory layer on the surface of a base material such as a building material using this refractory material can be performed, for example, as follows. First, a first method is a method in which a refractory material is sprayed on the surface of a base material at a uniform thickness and then heated and pressed to thereby integrally form a refractory layer on the surface of the base material. The method is to spread a refractory material uniformly, press it with a roll or the like heated to about 50 to 100 ° C. to partially adhere a binder resin to form a sheet material, and then based on the sheet material. This is a method in which a refractory layer is integrally laminated on the surface of the base material by heating and press-molding the material on the surface of the material. If necessary, an adhesive may be used to improve the adhesiveness. Furthermore, a refractory layer can be formed simultaneously with the production of a wood chip cement board or a particle board.
That is, a refractory material or a sheet thereof is arranged on the surface of a forming mat in which a piece of wood and an adhesive or cement are kneaded, and this is heated and pressed to form a board such as a wood chip cement board or a particle board. At the same time, a refractory layer can be integrally laminated on the surface. As described above, in the refractory layer formed of the refractory material of the present invention, even if a flame acts at the time of a fire, the base material such as a building material is exposed to the flame by blocking the flame with carbon powder and sand. Can be prevented. Further, when the binder resin contained in the refractory layer is burned by the action of the flame, it is carbonized to form a carbonized layer, and the carbonized layer serves as a heat insulating material to prevent a high temperature from acting on the base material. Things. And when the flame acts on the refractory layer and the binder resin in the refractory layer is carbonized, the resin shrinks, but the sand contained in the refractory layer expands due to the heat of the flame, and the resin shrinks. Thus, it is possible to prevent the refractory layer from shrinking. Therefore, it is possible to prevent cracks caused by shrinkage of the refractory layer,
It is possible to prevent the flame from penetrating through the refractory layer from the crack portion. Also, even if cracks occur in the refractory layer, since the refractory layer expands due to the expansion of the sand, the gap created by the crack will be closed by this expansion, and at high temperatures, the sand will partially It is possible to prevent the development of cracks by melting into a glass state, thereby preventing the flame from entering from the cracked portions. As described above, sand is used to prevent the refractory layer from shrinking even when the binder resin is carbonized and shrunk. Therefore, the amount of the sand is 15 to 100 parts by weight of the binder resin contained in the refractory material. It is necessary to set it to a weight part or more. However, as the amount of the sand increases, the content of the carbon powder decreases and the refractory performance of the refractory layer deteriorates. Therefore, the upper limit of the amount of the sand is about 1150 parts by weight.

【Example】

Next, the present invention is illustrated by Examples and Comparative Examples. Comparative Example 1 A reaction vessel was charged with 770 parts by weight of phenol, 1328 parts by weight of 37% formalin, 80 parts by weight of hexamethylenetetramine, and 1362 of flaky graphite powder having an average particle size of 5 μm.
90 parts by weight, 60 minutes while mixing and stirring
The reaction was continued for 3 hours. After cooling, it is filtered and dried to obtain spherical graphite.
A phenolic resin self-curing composite was obtained. This self-curing composite material has an average particle size of 130 μm and a graphite powder content of 6 μm.
It was 5% by weight. This graphite / phenol resin self-curing composite material was used as a refractory material. Example 1 1000 parts by weight of flattery silica sand having an average particle size of 173 μm was heated to 160 ° C. or more in a heating furnace, and the mixture was charged into a mixer to obtain
Adjust the temperature to 50-160 ° C., start kneading with a mixer, and simultaneously add 30 parts by weight of the solid novolak type phenol resin, and then, after 60 seconds, add a mixed water of 15 parts by weight of water and 4.5 parts by weight of hexamethylenetetramine. 30 seconds after confirming the collapse, 1 part by weight of calcium stearate was added,
After 30 seconds, the resin was discharged to obtain a self-hardening resin-coated sand in which the surface of the silica sand was covered with a phenol resin. This resin coated sand has an average particle size
It was 180 μm, and the content of silica sand was 96.8% by weight. Then, 90 parts by weight of the graphite-phenol resin self-curing composite material obtained in Comparative Example 1 was added, and 10 parts by weight of resin-coated sand was added thereto and mixed well to obtain a refractory material. Comparative Example 2 742 parts by weight of flaky graphite powder having an average particle size of 5 μm was placed in a kneader, and 65 parts of a solid resol type phenol resin was added thereto.
615 parts by weight of a methanol solution were added and kneaded for 30 minutes. After this kneading, air drying is performed to disperse the methanol, and then put in a drier set at 45 ° C., dried for 2 hours, and further pulverized with a coarse pulverizer to obtain a graphite-phenol resin self-curing composite material. Was. This self-curing composite has a particle size of under 1 mm and a graphite powder content of 65% by weight
Met. This graphite / phenol resin self-curing composite material was used as a refractory material. Comparative Example 3 1100 parts by weight of flaky graphite having an average particle size of 5 μm, 980 parts by weight of furfuryl alcohol, 405 parts by weight of 37% formalin, 500 parts by weight of water, and 500 parts by weight of a reaction vessel were further used as a reaction catalyst.
30% by weight of a 10% phosphoric acid aqueous solution was charged, and the mixture was reacted under reflux for 180 minutes while stirring. After cooling, the water was separated and then freeze-dried to obtain a graphite-furan resin self-curing composite material having some tackiness. This self-curing composite material had a graphite powder content of 61.8% by weight. This graphite / furan resin self-curing composite material was used as a refractory material. Example 2 The graphite-furan resin self-curable composite material obtained in Comparative Example 3 was used for 85
15 parts by weight of the range-coated sand obtained in Example 1 was added thereto and mixed well to obtain a refractory material. Comparative Example 4 1100 parts by weight of flaky graphite having an average particle size of 5 μm, 750 parts by weight of melamine, 960 parts by weight of 37% formalin, 1150 parts by weight of water, and 110 parts by weight of formic acid as a reaction catalyst were placed in a reaction vessel.
The parts by weight were charged, the temperature was raised to 70 ° C. in about 30 minutes, and the reaction was allowed to proceed for 240 minutes. This was cooled, filtered, and dried to obtain a spherical graphite / melamine resin self-curing composite material. This self-curing composite material had an average particle size of 280 μm and a graphite powder content of 58.5% by weight. This graphite-melamine resin self-curing composite material was used as a refractory material. Example 3 The graphite-melamine resin self-curing composite material obtained in Comparative Example 4 was used.
To 85 parts by weight, 15 parts by weight of the resin coated sand obtained in Example 1 was added and mixed well to obtain a refractory material. Example 4 A refractory material was obtained by taking 95 parts by weight of the graphite / phenol resin self-curing composite obtained in Comparative Example 1, adding 5 parts by weight of the resin-coated sand obtained in Example 1, and mixing well. Was. In this refractory material, 14.6 parts by weight of silica sand is blended with respect to 100 parts by weight of the resin. Example 5 A refractory material was obtained by taking 19 parts by weight of the graphite-phenol resin self-curing composite obtained in Comparative Example 1, adding 81 parts by weight of the resin-coated sand obtained in Example 1, and mixing well. Was. In this refractory material, 1179.1 parts by weight of silica sand was blended with respect to 100 parts by weight of the resin. The refractory material of each example and each comparative example obtained as described above was filled in a mold of 100 mm x 100 mm in length x width = 100 mm x 100 mm preheated to 160 ° C, and cured by heating and pressing for 10 minutes to form a fireproof layer. A plate having a thickness of 5 to 6 mm used as a material was formed. This plate was subjected to a flame penetration test. In the flame penetration test, when a high-temperature high-speed flame with a flame temperature of 1130 to 1300 ° C and a flame length of 150 mm was applied perpendicularly to the center of the surface of a plate held 100 mm away from the burner, the flame burned and the flame penetrated This was done by determining the time required to perform the heat treatment or the time required for the flame to penetrate due to the occurrence of cracks. The weight loss of each plate and the shrinkage of the plate were measured. These were calculated by comparing before and after the flame penetration test. Table 1 shows the results. As can be seen from Table 1, in each of the comparative examples in which the sand was not blended, cracks occurred in the places where the flame acted and the flame penetrated in a short time. It is confirmed that the flame can be shut off for a long time without generating cracks. Further, as seen in Example 4, the amount of the sand was 15 to 100 parts by weight of the binder resin.
If the amount is less than 1 part by weight, it tends to be difficult to prevent the occurrence of cracks. Conversely, if the amount of sand exceeds 1150 parts by weight with respect to 100 parts by weight of the binder resin as seen in Example 5, It is confirmed that the fire resistance tends to decrease.

【The invention's effect】

As described above, in the present invention, sand is added to a refractory material containing a carbon powder as a refractory filler and a resin as a binder, so that the refractory material formed by molding the refractory material is formed. Even if the flame acts on the layer and the binder resin in the refractory layer carbonizes and shrinks, the sand contained in the refractory layer expands by the action of the heat of the flame, and the refractory layer shrinks with the shrinkage of the resin. It can prevent the occurrence of cracks and can prevent the flame from penetrating through the cracks, and even if cracks occur in the refractory layer, The gap formed in the crack portion due to the expansion is closed, and it is possible to prevent the flame from penetrating from the crack portion. In addition, resin-coated sand in which the surface of the sand is coated with resin is mixed with the carbon-resin composite material prepared by reacting the resin raw material while mixing it with the carbon powder. And a resin-coated sand can be uniformly mixed with the carbon-resin composite material, so that the fire-resistant performance of the refractory material can be improved. Things.

Continuation of front page (72) Inventor Shuichi Kawai 70-35 Fukasakuyaguchicho, Fushimi-ku, Kyoto-shi, Kyoto (56) References JP-A-53-139400 (JP, A) JP-A-63-48319 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 21/02 C08K 3/04 C08L 101/00 E04B 1/94

Claims (2)

(57) [Claims] 1. A refractory material containing carbon powder and sand as a refractory filler and a resin as a binder, wherein the carbon-resin composite material is prepared by mixing and reacting a resin raw material with a carbon powder. A refractory material characterized by comprising, as sand, resin-coated sand in which the surface of sand is coated with a resin. 2. A method according to claim 2, wherein the sand is 15 parts per 100 parts by weight of the binder resin.
2. The refractory material according to claim 1, wherein the content is in the range of 1 part by weight to 1150 parts by weight.