KR100602196B1 - Method for producing non-inflammable pre-expanded polystyrene beads that keeps its shape when it burnt - Google Patents

Abstract

The present invention relates to a method for producing non-flammable flame retardant polystyrene foam resin particles, and more specifically, to the polystyrene foam particles obtained by foaming expanded polystyrene resin particles obtained by a conventional suspension polymerization technique to a certain specific gravity, the weight of the foam particles 100 10 to 80 parts by weight of the metal hydroxide compound, 10 to 300 parts by weight of the thermosetting liquid phenolic resin and 0.02 to 30 parts by weight of the curing catalyst with respect to 100 parts by weight of the phenol resin, and the porous Char (carbonized core) during combustion. It relates to a method for producing a nonflammable flame retardant polystyrene foam resin particle in which a fire prevention layer is formed.

Description

Method for producing flame retardant polystyrene foam resin particles having incombustibility {METHOD FOR PRODUCING NON-INFLAMMABLE PRE-EXPANDED POLYSTYRENE BEADS THAT KEEPS ITS SHAPE WHEN IT BURNT}

The present invention relates to a method for producing non-combustible flame retardant polystyrene foam resin particles, and more particularly, to manufacturing a flame-retardant polystyrene foam resin particle prepared by coating and curing a metal hydroxide compound, a thermosetting liquid phenol resin, and a curing catalyst on a polystyrene foam particle. It is about a method.

As a method for improving the heat resistance and flame retardancy of polystyrene foam, a method of manufacturing polystyrene foam resin particles having heat resistance and flame retardancy by coating polystyrene foam particles with a heat resistant or flame retardant material has been developed.

Japanese Patent JP2001-164031A discloses a method of coating a mixture of a boron-based inorganic compound and a thermosetting resin in a porous foamed resin in order to produce a porous molded body having heat resistance and flame resistance. This method is expected to provide a certain effect in terms of providing fire-resistant, anti-inflammatory and form-preservation to the porous foam resin, but in order to obtain sufficient incombustibility, the amount of boric acid-based inorganic compounds such as boric acid is excessively used, coating Drying of the expanded foam particles, the inorganic compounds used in the molding process caused a problem that is easily released. The separation of these minerals is a harmful component to the human body causes a decrease in workability, and also causes a decrease in flame retardant effect. In addition, in order to prevent flame retardancy deterioration due to the separation of the inorganic material during the molding process, when a large amount of additional inorganic material is added, the problem that the fusion of the product is further lowered.

Therefore, without such a problem, there has been a continuing need for a method for producing new flame retardant polystyrene foam resin particles capable of exhibiting the same flame retardant effect.

It is an object of the present invention to provide a novel flame retardant polystyrene foamed particle having improved non-flammability and improved fusion, strength, workability, etc. of a molded article, which are important properties as a heat insulating material.

Another object of the present invention is to provide a novel flame retardant polystyrene foam particles prepared by coating and curing a metal hydroxide compound, a thermosetting liquid phenol resin, and a curing catalyst on the polystyrene foam particles.

Another object of the present invention is to provide a method for producing a novel panel comprising the production of a novel flame-retardant polystyrene foam particles prepared by coating and curing a metal hydroxide compound, a thermosetting liquid phenol resin, and a curing catalyst on the polystyrene foam particles. will be.

Another object of the present invention is to provide a novel flame retardant polystyrene foam particles prepared by coating and curing a metal hydroxide compound, a thermosetting liquid phenol resin, and a curing catalyst on the polystyrene foam particles.

Another object of the present invention is to provide a panel prepared using the novel flame retardant polystyrene foam particles prepared by coating and curing a polyhydroxy foam particle with a metal hydroxide compound, a thermosetting liquid phenol resin, and a curing catalyst.

In order to achieve the above object, the present invention relates to 100 parts by weight of polystyrene foam particles, 10 to 80 parts by weight of a metal hydroxide compound, 10 to 300 parts by weight of a thermosetting liquid phenolic resin, and 0.02-to a curing catalyst based on 100 parts by weight of the phenol resin. It consists of the manufacturing method of a flame-retardant polystyrene foam resin particle characterized by coating and crosslinking 30 weight part.

In the present invention, the polystyrene foam particles are made by foaming of expandable polystyrene resin particles. In the practice of the invention, the expandable polystyrene resin particles may be prepared using a variety of known methods, for example, emulsion polymerization, or suspension polymerization. It is preferable to use spherical expandable polystyrene particles produced by the suspension polymerization method. In one embodiment of the present invention, the expandable polystyrene resin particles may be used in the polymerization process, the expanded polystyrene resin particles to which a small amount of flame retardant is added, or the expanded polystyrene resin particles to which the flame retardant is not added may be used.

In the present invention, in order to obtain the polystyrene foam particles, a method for foaming the expandable polystyrene particles is known to those skilled in the art. The specific gravity of the expanded polystyrene foam particles may be adjusted depending on the intended use, but is preferably maintained at 0.03 to 0.01.

In the present invention, the metal hydroxide compound forms crystalline water (H 2 O) during combustion of the product. Crystal water generated during product combustion removes the heat of the combustion point, thereby suppressing the combustion phenomenon, which enables the high nonflammability of the product in a relatively small amount, and consequently improves the fusion of the product. . In the practice of the present invention, the metal hydroxide compound is preferably used 10 to 80 parts by weight based on 100 parts by weight of polystyrene foam particles. If the amount of use is less than 10 parts by weight, the combustion inhibitory effect is lowered. If the amount is used more than 80 parts by weight, the fusion of the molded product is lowered. In a preferred embodiment of the invention, the metal hydroxide compound is selected from aluminum hydroxide (Al (OH) ₃), magnesium hydroxide (Mg (OH) ₂), and mixtures thereof.

In the present invention, in order to prevent the poor fusion of the molded article, the thermosetting liquid phenol resin, it is preferable to use a water-soluble liquid phenol resin or oil-soluble liquid phenol resin. More preferably, it is a liquid phenol resin whose non-volatile content is 25-85 weight%. Methods of preparing the liquid phenolic resins are known to those skilled in the art and are also commercially available. In the practice of the present invention, there is a disadvantage that the solid phenol resin, for example, powder phenol resin is relatively hard to be hardened by a curing catalyst compared to the liquid phenol resin, which causes a problem that the product becomes sticky in a later processing process. . In addition, when a high curing temperature of the curable resin, for example, urea resin, or melamine resin is coated on the foam particles, the sticky viscosity may cause agglomeration between the foam particles, resulting in poor filling and fusion of the molded body Defects can occur.

In one preferred embodiment of the present invention, the water-soluble liquid phenolic resin or oil-soluble liquid phenolic resin having a nonvolatile content of 25 to 85%, preferably 10 to 300 parts by weight based on 100 parts by weight of polystyrene foam particles. If the amount is less than 10 parts by weight of the coating coating efficiency is not enough to act as a binder, and when used more than 300 parts by weight agglomeration between foam particles may cause problems in transport and molding.

In the present invention, the curing catalyst is not limited to the theory, but it is preferable to use from 0.02 to 30 parts by weight based on 100 parts by weight of the phenol resin so that the phenol resin can be sufficiently cured during processing to increase the bonding strength. In the practice of the present invention, the curing catalyst may be selected from ammonium chloride, methane sulfonic acid, phenol sulfonic acid, p-toluene sulfonic acid, phosphoric acid and the like. If the amount is less than 0.02 parts by weight based on 100 parts by weight of phenolic resin, the reaction rate to be cured is too slow to obtain the effect of the present invention. The binder efficiency of thermosetting resin is inferior.

In the present invention, a halogen-based flame retardant may be used in order to enhance the flame retardant effect by trapping radicals generated when the metal hydroxide compound, the thermosetting liquid phenol resin, and the curing catalyst are cured and coated products are burned. . In one embodiment of the invention, the halogen flame retardant may be selected from hexabromocyclododecane (HBCD), tetra bromo cyclo octane (TBCO), tetra bromophenylaryl ether (TPA), and the like, polystyrene foam 10-90 weight part is used with respect to 100 weight part of granules. If the amount is 10 parts by weight or less, a sufficient flame retardant effect is not seen, and if it is 90 parts by weight or more, there is a problem that the fusion resistance and heat resistance of the molded body are lowered.

In the present invention, the coating can be made using a conventional coating method, there is no particular limitation. In one embodiment of the present invention, the coating is made of aluminum hydroxide Al (OH) ₃ or magnesium hydroxide (Mg (OH) to 100 parts by weight of the foamed particles of the expanded polystyrene resin produced by the suspension polymerization method to a specific gravity of 0.03-0.010 ) 2, or 10 to 80 parts by weight of the metal hydroxide compound selected from the two mixtures, 10 to 300 parts by weight of the thermosetting liquid phenolic resin, and 0.02 to 30 parts by weight of the curing catalyst with respect to 100 parts by weight of the thermosetting liquid phenolic resin, and a flame retardant effect. Halogen-based flame retardant can be maximized by 10 to 90 parts by weight of the mixture can be made by stirring.

In the present invention, the film-coated foam particles are cured by adjusting the drying temperature and time according to the amount of catalyst used to obtain foam particles. In one embodiment of the present invention, the curing process is obtained by drying the foamed granules to which the curing catalyst is added at a temperature of as low as 35 ℃ to 70 ℃, as short as 5 minutes to 1 hour.

The expanded particles obtained by the present invention form a molded article such as a panel by a known panel production method or the like.

Such a molded article obtained by the present invention is uniformly and firmly coated on the surface layer of the foamed granules, thereby providing a non-flammability by forming a fired layer by porous Char (carbonized core) immediately from the coated surface layer upon combustion of the molded body. In addition, due to the proper combination of the combustion inhibiting function of the metal hydroxide compound applied in the present invention, the proper binder function of the thermosetting liquid phenol resin cured with the catalyst, and the function of the halogen flame retardant which blocks the oxygen by generating the incombustible gas, the molded body is flamed. Even if it is received on the front side, it is extinguished immediately by the formation of the fireproof layer by the porous char (carbonized core), and no further shape collapse is caused by heat.

The present invention will be described in more detail with reference to the following Examples. Example 1

300 g of polystyrene foamed granules obtained by pre-expanding the expanded polystyrene resin particles at 100 times (specific gravity = 0.010) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly. 100 g of aluminum hydroxide (Al (OH) ₃) and 300 g of water-soluble phenolic resin (phenolic resin with 85% solids) are taken in advance, 5 g of p-toluene sulfonic acid is mixed, and 30 g of hexabromocyclododecane is mixed separately. Mix well into

When the mixture is stirred at 200 rpm for about 30 minutes, the added mixture is uniformly coated on the foam particles. When the thus obtained foamed granules are dried in a 40 ° C. dryer for about 5 minutes, a flame retardant polystyrene foam resin particle having a nonflammability as the object of the present invention can be obtained.

Coated flame-retardant polystyrene foam resin particles were molded into the building's thermal insulation material or the building's panel insulation material, and then tested according to the test method for flame retardancy of the interior materials and structures of the building (KS F2271).

As a result, even if the flame was applied to the front surface, the non-combustible class 3 was shown due to the formation of a fireproof layer made of porous char (carbonized core) on the film of the interior material.

Example 2

300 g of polystyrene foamed granules obtained by pre-expanding the expanded polystyrene resin particles at 80 times (specific gravity = 0.012) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly. 100 g of magnesium hydroxide (Mg (OH) ₂), 200 g of water-soluble phenolic resin (phenolic resin with 80% solids), and 10 g of phenol sulfonic acid are mixed in advance, and 50 g of hexabromocyclododecane is placed in a separate container. Mix well and add.

After stirring at 200 rpm for about 30 minutes in the blender, the added mixture is uniformly coated on the foam particles. When the thus obtained foamed granules are dried in a 40 ° C. dryer for about 5 minutes, a flame retardant polystyrene foam resin particle having a nonflammability aimed at in the present invention can be obtained.

Coated flame-retardant polystyrene foam resin particles were molded into the thermal insulation material of the building or the panel insulation material of the building and tested according to the test method of flame retardancy of the interior materials and structure of the building (KS F2271).

As a result, even if the flame was applied to the front, a fireproof layer formed by porous char (carbide core) was immediately formed on the coating of the interior material, and thus showed non-combustibility according to the flame retardant class 3.

Example 3

300 g of polystyrene foam granules obtained by pre-expanding the expanded polystyrene resin particles at 70 times (specific gravity = 0.014) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly. 15 g of magnesium chloride is added to 150 g of magnesium hydroxide (Mg (OH) ₂) and 300 g of a water-soluble phenolic resin (phenol resin having 78% solids), and 100 g of hexabromo cyclododecane is well mixed in a separate container. Mix and add.

When the mixture is stirred at 200 rpm for about 30 minutes in the blender, the added mixture is uniformly coated on the foam particles. When the thus obtained foamed granules are dried in a 40 ° C. dryer for about 5 minutes, a flame retardant polystyrene foam resin particle having a nonflammable target of the present invention can be obtained.

Coated flame-retardant polystyrene foam resin particles were molded into the thermal insulation of the building or the panel insulation of the building, and then tested according to the test method for flame retardancy of the interior materials and structures of the building (KS F2271).

As a result, even if the flame was applied to the front, a fireproof layer formed by porous char (carbide core) was immediately formed on the coating of the interior material, and thus showed non-combustibility according to the flame retardant class 3. Example 4

300 g of polystyrene foamed granules obtained by pre-expanding the expanded polystyrene resin particles at 60 times (specific gravity = 0.016) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly.

50 g of aluminum hydroxide (Al (OH) ₃), 40 g of magnesium hydroxide (Mg (OH) ₂), 300 g of oil-soluble phenol resin (75% solids), and 3 g of methane sulfonic acid were mixed in advance, and 100 g of tetrabromocyclooctane was mixed. Mix well in a separate container.

After 30 minutes of stirring at 200rpm in the blender, the added mixture is uniformly coated on the foam particles. When the thus-obtained foamed granules are dried for 5 minutes in a 60 ° C. dryer, flame-retardant polystyrene foam resin particles having a non-flammability as the object of the present invention can be obtained.

Coated flame-retardant polystyrene foam resin particles were molded into the thermal insulation of the building or the panel insulation of the building, and then tested according to the test method of flame retardancy of the interior materials and structures of the building (KS F2271).

As a result, even if the flame was applied to the front, a fireproof layer formed by porous char (carbide core) was immediately formed on the coating of the interior material, and thus showed non-combustibility according to the flame retardant class 3.

Example 5

300 g of polystyrene foamed granules obtained by pre-expanding the expanded polystyrene resin particles at 50 times (specific gravity = 0.02) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly.

100 g of aluminum hydroxide (Al (OH) ₃), 40 g of magnesium hydroxide (Mg (OH) ₂), 300 g of oil-soluble phenol resin (75% solids), and 13 g of methane sulfonic acid are mixed in advance, and 100 g of bromophenylaryl ether is separately mixed. Mix well into the container.

When the mixture is stirred at 200 rpm for about 30 minutes, the added mixture is uniformly coated on the foam particles. When the thus obtained foamed granules are dried in a 60 ° C. dryer for about 5 minutes, a flame retardant polystyrene foam resin particle having a nonflammable target of the present invention can be obtained.

Coated flame-retardant polystyrene foam resin particles were molded into the thermal insulation material of the building or the panel insulation material of the building, and then tested according to the test method for flame retardancy of the interior materials and the structure of the building (KS F2271).

As a result, even if the flame was applied to the front, a fireproof layer formed by porous char (carbide core) was immediately formed on the coating of the interior material, and thus showed non-combustibility according to the flame retardant class 3.

Example 6

 300 g of polystyrene foamed granules obtained by pre-expanding the expanded polystyrene resin particles at 30 times (specific gravity = 0.030) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly.

30 g of aluminum hydroxide (Al (OH) ₃), 100 g of magnesium hydroxide (Mg (OH) ₂), 300 g of water-soluble phenolic resin (70% solids), and 13 g of methane sulfonic acid are mixed in advance, and 100 g of bromophenylaryl ether is separately mixed. Mix well into the container.

 When the mixture is stirred at 200 rpm for about 30 minutes, the added mixture is uniformly coated on the foam particles. When the thus obtained foamed granules are dried in a 60 ° C. dryer for about 5 minutes, a flame retardant polystyrene foam resin particle having a nonflammable target of the present invention can be obtained.

Coated flame-retardant polystyrene foam resin particles were molded into the thermal insulation of the building or the panel insulation of the building, and then tested according to the test method for flame retardancy of the interior materials and structures of the building (KS F2271).

As a result, even if the flame was applied to the front surface, a fireproof layer formed by porous char (carbide core) was immediately formed on the coating of the interior material, and thus showed a nonflammability similar to that of flame retardant class 3.

Comparative Example

 300 g of polystyrene foam granules obtained by pre-expanding the expanded polystyrene resin particles at 80 times (specific gravity = 0.012) with a pressurized batch foaming machine are introduced into a 100L blender equipped with a stirrer and stirred slowly. Here, 300 g of boron-based inorganic material and 400 g of phenol resin are taken, mixed in advance, mixed well in a container, and mixed with 30 g of hexabromo cyclododecane in a separate container.

When the mixture is stirred at 200 rpm for about 30 minutes, the added mixture is uniformly coated on the foam particles. The foamed granules thus obtained are dried in a 50 ° C. dryer for about 50 minutes to obtain flame-retardant polystyrene foam resin particles. Thus obtained foam granules were dried at 50 ° C. for at least 50 minutes.

The resin particles obtained by the method of the comparative example were molded into a heat insulating material of a building or a panel heat insulating material of a building, and then tested according to the test method for flame retardancy of the interior material and structure of the building (KS F2271).

Due to the stickiness of the phenolic resin, agglomeration of the foamed particles occurred, and powder detachment occurred severely from the surface of the foamed grain.As a result, when the flame was received to the front, the shape collapse of the molded body occurred even though the flame did not occur. It did not show a level of incombustibility.

Example 7 Adhesion Test

After the 100 x 50 x 200 mm specimens were prepared from the samples obtained in Examples 1-6, the specimens were bent and crushed with the same force. The cross section of the crushed specimen was visually observed to indicate the fusion of the molded article by indicating the number of cracked or broken foamed granules as a percentage of the total foamed grains. If the adhesion is good, the fraction of the crushed foam granules is high, and vice versa.

Example Adhesiveness (%) Example 1 71 Example 2 75 Example 3 80 Example 4 75 Example 5 76 Example 6 77 Comparative Example 30

According to the present invention, there is provided a novel method for preparing a panel comprising the steps of preparing a new flame retardant polystyrene foam particle prepared by coating and curing a metal hydroxide compound, a thermosetting resin, and a curing catalyst on a polystyrene foam particle and a metal hydroxide on the polystyrene foam particle. Provided are novel flame retardant polystyrene foam particles prepared by coating and curing compounds, thermosetting liquid phenolic resins, and curing catalysts.

Also provided by the present invention is a panel made of novel flame retardant polystyrene foam particles prepared by coating and curing a metal hydroxide compound, a thermosetting resin, and a curing catalyst on a polystyrene foam particle. Flame-retardant polystyrene foam resin particles obtained by the present invention as a thermal insulating material or a panel insulation material of the building has a feature that can be used without significant difference in terms of workability and general physical properties compared to the conventional styropol insulation.

Claims (7)

10 to 80 parts by weight of a metal hydroxide compound selected from the group consisting of aluminum hydroxide (Al (OH) ₃), magnesium hydroxide (Mg (OH) ₂), and mixtures thereof, 100 parts by weight of polystyrene foam particles, and a thermosetting liquid phenol resin 10-300 parts by weight, and coating and crosslinking 0.02-30 parts by weight of a curing catalyst based on 100 parts by weight of the phenolic resin, the method of producing a flame-retardant polystyrene foam resin particles. delete The method for producing flame retardant polystyrene foam resin particles according to claim 1, wherein the thermosetting liquid phenol resin is a water-soluble or oil-soluble liquid phenol resin having a nonvolatile content of 25 to 85% by weight. The method of claim 1, wherein the curing catalyst is selected from the group consisting of ammonium chloride, phosphoric acid, methane sulfonic acid, phenol sulfonic acid, p-toluenesulfonic acid, and mixtures thereof. The halogenated flame retardant according to claim 1, wherein the halogenated flame retardant is selected from the group consisting of hexabromo cyclododecane (HBCD), tetrabromo cyclooctane (TBCO), tetra bromophenylarylether (TPA) and mixtures thereof. -Method for producing a flame-retardant polystyrene foam resin particles further comprising 90 parts by weight. The method of claim 1 wherein the foamed polystyrene specific gravity is 0.03-0.010. Flame-retardant polystyrene foam resin particles prepared by the method of claim 1.