KR100660082B1 - Improved Phenolic Foam Using Novolak Type Phenolic Resin and its Method and the Composition - Google Patents

Abstract

The present invention relates to a phenol foam and a method and a composition which improves the performance of flame retardancy and the like by using a novolak-type phenol resin, and in particular, greatly improves the flame retardancy of the phenol foam molded body, It is an environmentally friendly phenolic foam that has almost no emission and does not use any CFCs, CFC substitutes or chemical foaming agents, and thus does not generate harmful substances. In the present invention, (a) 10 to 100 parts by weight of boric acid or borax; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; Mixing 200 parts by weight of water to form a flame-retardant composition in a homogeneous slurry solution, and mixing and coating the flame retardant composition with 100 parts by weight of a novolak phenolic resin powder, followed by drying, and (b) the dried mixture obtained in (a). 5 to 60 parts by weight of a boron peroxide and 1 to 20 parts by weight of a curing agent were added to the foaming agent, stirred and mixed, followed by foam molding, and (c) the foamed molded product obtained in (b) was 10 to 10 to a heat dryer at 150 to 230 ° C. There is provided a method for producing a phenol foam comprising the step of aging for 100 minutes. Phenolic foam of the present invention can be widely used to replace the existing heat insulating material as an excellent heat insulating material that solves all the problems of the organic compound-based foamed heat insulating material such as styrofoam, urethane foam, urea foam, PIR foam and commercialized phenolic foam have.

Phenolic Foam, Phenolic Resin, Novolac Phenolic Resin, Flame Retardant, Insulation, Foam

Description

Improved Phenolic Foam Using Novolak Type Phenolic Resin and its Method and the Composition}

The present invention relates to a phenol foam and a method and a composition which improves the performance of flame retardancy and the like by using a novolak-type phenol resin, and in particular, greatly improves the flame retardancy of the phenol foam molded body, It is an environmentally friendly phenolic foam that has almost no emission and does not use any CFCs, CFC substitutes or chemical foaming agents, and thus does not generate harmful substances.

As insulation for construction, organic compound foams such as styrofoam, urethane foam, urea foam, and PIR foam are mainly used. Such organic compound-based foams have advantages such as ultra-light weight, low thermal conductivity, economical efficiency, and ease of construction, while being weak in heat, decomposing in fire, generating harmful fumes, carbon monoxide, and cyanide, which are harmful to the human body, and cannot be recycled. Since there are many problems such as causing a secondary environmental pollution, its use is gradually regulated at home and abroad.

As a product that can replace these organic compound insulation materials, glass wool, rock wool, etc. made by melting waste glass and ore at high temperature are used, but this is a non-flammable material, but fine dust that irritates the skin during construction. It is weak to the occurrence and moisture of the thermal conductivity is lowered, there is a problem such as the collapse of the form, the secondary can not cause recycling, environmental pollution.

Phenolic foam has flame retardancy, heat resistance, low smoke resistance and lowest thermal conductivity compared with conventional organic compound insulation materials.Carbon film is formed on the surface when it is in contact with the flame, so that propagation of flame is blocked, and the carbon is maintained after combustion. There are advantages such as not changing. In foreign countries, phenolic foam is commonly used as a building insulation material, especially a ceiling material. Most of the phenolic foams are prepared using a resol type phenolic resin, especially a reaction molar ratio (F / P) of 1 to 3 and basic catalysts such as NaOH and NH3. The resol type phenol resin manufactured is used.

However, the phenolic foam formed using such a resol-type phenolic resin may be released to the outside when unreacted formaldehyde remains in the body other than the bubbles in the molded body, resulting in minute cracking due to heating or impact. In addition, since resol type phenolic resin is used to produce phenolic foam, organic or inorganic acid is used as a catalyst as a curing agent, so that acidic components remain in the body of the molded body and are released to the outside from fine gaps of the molded body after construction. Problems such as corrosion of contact surfaces have been published in early 1990 by the Canadian Association of Ceiling Structures.

In addition, as a blowing agent used for the formation, initially used compounds such as CFC-11, 12, 113, but its use is regulated by the environmental convention for the prevention of ozone layer destruction, alternatively HCFC-22, 123, 141b, etc. HFC-134a and 152a are used, and recently, relatively stable low boiling point organic compounds such as HFC-365mfc, pentane, butane and isobutane are used. There is a risk of large fires.

As a related art related to the production of phenolic foams using a resol type phenolic resin, Korean Laid-Open Patent Publication No. 2001-23571 describes a method for producing a phenolic foam using a blowing agent such as a resol type phenolic resin and saturated hydrocarbons such as pentane and butane, Korean Unexamined Patent Publication No. 1989-3857 describes a method for preparing phenol foam using a resol type phenol resin, vinyl acetate monomer, and a polymerization initiator, and Korean Unexamined Patent Publication No. 2000-11139 has a compound having a resol type phenol resin and a silane group. It describes a process for producing a foamed phenol foam from room temperature to relatively low temperature by addition crosslinking reaction based on hydrosilylation reaction. US Patent No. 4,539,338 discloses a method of using a Freon gas as a blowing agent and mixing the emulsifier and foam stabilizer at 5 ° C. or less, followed by foam molding at 45 ° C., and US Patent 4,396,563 describes ethyl chloride as a blowing agent. Using a silicone-based mixture as an emulsifier and a sulfonate salt such as toluene, xylene, etc. as a curing agent is mixed at low temperature and then foamed at 60 ℃. Regarding flame retardancy, Japanese Patent No. 00241530 describes a method for producing a flame retardant phenol foam using aluminum hydroxide and boric acid as a flame retardant in a resol type phenol resin, and European Patent 04681902 adds chlorine to a resol type phenol resin. Describes a method for producing a flame retardant phenol foam by adding a mixed diphenyl oxide and an organophosphorus compound, European Patent 04122045 is a phenol foam that prevents corrosion with flame retardant by adding borax to the resol-type phenol resin It describes.

Novolak-type phenolic resins having different characteristics from resol-type phenolic resins are pale yellow powders, which are cured at 150 to 160 ° C. In this case, amines are used as hardeners, and hexamethylenetetramine is mainly used. As a blowing agent, N, N'- dinitrosopentamethylenetetramine, azodicarbonamide, etc. are typically used, and it foams instantaneously at about 130-150 degreeC, and forms foam. These foaming agents have a problem of generating ammonia gas and formaldehyde while forming bubbles to contaminate the surrounding environment during the production of the molded body. In addition, when manufacturing phenolic foam using novolak phenolic resin, the process is simpler than the resol type, but because the resin is in powder form, dust is generated during handling, and it is difficult to store it for a long time due to its excellent water adsorption power, and it is different in specific gravity when mixed with blowing agent. There is such a problem that uniform mixing is difficult.

Japanese Patent Laid-Open Publication No. Hei 2-173131 discloses a phenolic foam in which a novolak resin and a blowing agent are slurryed in a mixed organic solvent having a boiling point of 120 ° C. or lower in a room temperature and foamed by heating. Japanese Laid-Open Patent Publication No. 59-227933 describes a method for producing phenol foam foamed using a novolak resin and thermally expandable microspheres. Using N, N'-dinitrosopentamethylenetetramine as a blowing agent, a method of dissolving a novolak-based phenolic resin in an organic solvent such as alcohol, stirring and mixing with a blowing agent, and then foaming curing at 150 ° C, In Japanese Patent Laid-Open No. 11-255939, N, N'-dinitrosopentamethylenetetramine is used as a blowing agent, and hexamethylenetetramine is used as a curing agent. And a method of foam curing at 150 ° C., and Japanese Patent Application Laid-Open No. 2000-44770 prepared a phenol foam by using hexamethylenetetramine as a curing agent and foaming by adding a polysiloxane ethylene oxide addition compound without using a blowing agent. It describes how to do it.

The novolak-based phenolic foam produced by the above method generates a large amount of ammonia gas and formaldehyde by decomposition by heating in the foaming process by using a chemical blowing agent and a curing agent as described above. At this time, the generated ammonia gas and formaldehyde are mixed and remain in the structure of the foamed molded product as a crosslinking agent, and others are released into the atmosphere or remain in the bubbles of the foamed molded product. As such, formaldehyde remaining in the structure or foam of the foamed molded article is released slowly at room temperature, is released by damage to the surface of the foamed molded article, or when the temperature becomes high for some reason, the bubbles or the structure are burned and the release is accelerated. Removal or reduction is important.

As described above, phenolic foams prepared using resol-type or novolak-type phenolic resins have more excellent flame retardancy and lower smokeability than other organic compound-based insulating materials, but foam molded bodies alone are still domestic and international flame retardant standards. Can not meet. Accordingly, in order to increase the flame retardancy of foreign commercialized products, aluminum foil or sheet, flame retardant film, flame retardant nonwoven fabric, mineral flame retardant sheet, etc. may be attached to the surface of the foamed molded product to meet the flame retardant specification. In some cases, flame retardants may be attempted by mixing fillers such as mineral powders.

The present invention removes a source of ammonia gas, formaldehyde, etc. due to thermal decomposition of the conventional chemical blowing agent in the process of manufacturing phenolic foam using a novolak-type phenolic resin to implement a clean manufacturing line and at the same time inside the foam molded body It is intended to produce a phenol foam suitable for the flame retardant standards, in particular semi-combustible material at home and abroad, so that the above-mentioned substance is hardly contained in the foam molded article alone.

To this end, the present inventors have studied boron-based materials as a substance that can replace the existing chemical blowing agent that is a source of formaldehyde and ammonia gas, and can act as a blowing agent without generating such harmful gases during thermal decomposition. A method of using peroxide was developed.

In addition, the present inventors modify the surface of the novolak phenolic resin particles into a flame retardant composition to improve the flame retardancy, for example, a method of modifying the particle surface by spray coating a flame retardant composition in a solution state to the novolak phenolic resin particles, and foam As a result of applying the method of heat aging the molded body, it has been found that the flame retardancy can be greatly improved, and that ammonia gas or formaldehyde is hardly generated and no soot is generated in the manufacturing process or during flame contact, thereby completing the present invention.

The ultimate object of the present invention has the function as an alternative to solve the problems of styrofoam, urethane foam, urea foam, PIR foam, etc., which is currently used organic compound insulation, and at the same time improved to solve the problem of commercially available phenol foam It is to provide phenolic foam.

Other objects and advantages of the present invention will be described below and will be better understood by practice of the present invention.

In the present invention,

(a) 10 to 100 parts by weight of boric acid or borax; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; Mixing 200 parts by weight of water to make a flame-retardant composition in the form of a homogeneous slurry solution, mixing and coating the flame-retardant composition with 100 parts by weight of a novolak phenolic resin powder and drying it;

(b) adding 5 to 60 parts by weight of a boron peroxide and 1 to 20 parts by weight of a curing agent to the dried mixture obtained in (a) with a foaming agent, stirring and mixing, followed by foam molding;

(c) There is provided a method for producing a phenol foam comprising the step of aging the foamed molded product obtained in (b) for 10 to 100 minutes in a heat dryer at 150 ~ 230 ℃.

In another embodiment of the invention,

(a) 10 to 100 parts by weight of TEOS; 1-20 parts by weight of ammonia water; Adding 200 parts by weight of novolak phenolic resin powder to a solution of 10 to 100 parts by weight of water, stirring and mixing to modify the surface of the novolak phenolic resin by sol-gel reaction, and then drying;

(b) adding 5 to 60 parts by weight of a boron peroxide and 1 to 20 parts by weight of a curing agent to the dried mixture obtained in (a) with a foaming agent, stirring and mixing, followed by foam molding;

(c) There is provided a method for producing a phenol foam comprising the step of aging the foamed molded product obtained in (b) for 10 to 100 minutes in a heat dryer at 150 ~ 230 ℃.

Moreover, in this invention, 10-100 weight part of boric acid or borax is contained in 100 weight part of novolak phenol resin powders; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; Provided is a flame retardant method of a novolak type phenolic resin comprising a step of mixing and coating a flame retardant composition in a homogeneous slurry solution state containing 200 parts by weight of water.

In another embodiment of the present invention, 10 to 100 parts by weight of TEOS; 1-20 parts by weight of ammonia water; Flame retardant method of novolak type phenolic resin comprising adding 200 parts by weight of novolak phenolic resin powder to a mixed solution of 10 to 100 parts by weight of water, stirring and mixing to modify the surface of the novolak phenolic resin by sol-gel reaction and then drying This is provided.

Moreover, in this invention, 10-100 weight part of boric acid or borax is contained in 100 weight part of novolak phenol resin powders; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; A flame retardant composition comprising 200 parts by weight of water is mixed and coated, followed by drying, and 5 to 60 parts by weight of boron peroxide and 1 to 20 parts by weight of a curing agent are added to the foamed molding composition.

In the present invention, a method for producing a phenolic foam using a novolak-based phenolic resin is a step of greatly flame retarding a novolak-type phenolic resin (Step I), and a step of adding foaming agent to the flame-retardant phenolic resin to foam molding ( Process II) and the process of heat-aging a foamed molded object of the said process (process III). Hereinafter, the phenol foam manufacturing method and the flame retardant method of the novolak phenol resin of the present invention will be described in detail for each process.

I. Flame Retardant Process of Novolac Phenolic Resin

First, 10 to 100 parts by weight of boric acid or borax; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; 200 parts by weight of water are mixed to form a flame retardant composition in the form of a homogeneous slurry solution. Numerical limitations and preferred embodiments of each flame retardant component constituting the present flame retardant composition are all related to flame retardant performance and physical properties of foamed or molded phenolic foam. In other words, each flame retardant component is less than the range can be used if the flame retardant performance is lowered, if used more than the range may cause problems in the physical properties of the foam molding or molded phenolic foam. The boric acid is preferably used after being pulverized ortho boric acid to 200 to 400 mesh in advance. The boric acid or borax is preferably used in 20 to 60 parts by weight. The aluminosilicate or aluminum hydroxide or boric acid is preferably used in an amount of 20 to 60 parts by weight.

The flame retardant composition is mixed and coated with 100 parts by weight of the novolak phenolic resin powder, followed by drying. Preferably, the flame retardant composition is added to a stirring mixer while stirring at 1,000 to 1,500 rpm, and the flame retardant composition is removed from the top of the stirring mixer. Spray by coating. After completion of the stirring mixing, the mixed composition is dried under reduced pressure while heating at about 40 to 50 ° C, more preferably at about 45 ° C.

In another embodiment of the invention, 10 to 100 parts by weight of tetra ethyl ortho silicate (TEOS); 1-20 parts by weight of ammonia water; 200 parts by weight of the novolak phenolic resin powder was added to a solution containing 10 to 100 parts by weight of water, and stirred and mixed to modify the surface of the novolak phenolic resin by sol-gel reaction and then dried.

II. Foaming Process

To the dried mixture obtained in step I, 5 to 60 parts by weight of boron peroxide and 1 to 20 parts by weight of a curing agent were added as a foaming agent, stirred and mixed, and then foamed into a mold. The amount of foaming agent and hardener used is related to the physical properties of the foamed or molded phenolic foam. If each component is used less than or less than the range, the foaming may not be performed well or the physical properties of the foamed phenolic foam may be caused. Preferably, the boron peroxide is used by grinding to 200 to 400 mesh, it is used in 25 to 50 parts by weight.

As the curing agent, a known curing agent may be used. For example, hexamethylenetetramine may be used.

Preferably, boron peroxide and a curing agent are added to the dried mixture obtained in the above process, stirred and mixed at 1,000 to 1500 rpm for about 60 minutes, and then filled into a molding mold having a predetermined size, such as a molding mold having a size of 200 × 200 × 50 mm. The mold is sealed and heated to 150-170 ° C. in a heat drier, followed by foam molding. Preferably, the mold is maintained at that temperature for 20 to 40 minutes to achieve complete foaming.

III. Heating aging process

The foamed molded product obtained in Step II was aged in a heat dryer at 150 to 230 ° C. for 10 to 100 minutes to obtain phenol foam having improved flame retardancy. More preferably, the foamed molded product is aged for 20 to 40 minutes in a heat dryer at 180 to 200 ° C.

In the embodiment of the present invention is a novolak-type phenolic resin, but is not particularly limited, but the melting point 80 ~ 90 ℃, the flow rate of 125 ~ 27 27mm, curing temperature 155 ~ 160 ℃, vitrified phenol content 2.5% or less, curing agent Novolac phenolic resins having a physical property of 8% or less in content were used.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the scope of the present invention is not limited by the following examples, and those skilled in the art to which the present invention pertains should be within the equivalent scope of the technical concept of the present invention and the claims to be described below. Of course, various modifications and variations are possible.

Example 1

First, 50 parts by weight of ortho boric acid and 50 parts by weight of aluminosilicate, which had been pre-milled with 325 mesh, were mixed, added to 200 parts by weight of water, and stirred at 500 to 1,000 rpm to form a flame-retardant composition in a homogeneous slurry solution state. 100 parts by weight of the novolak phenol resin powder was placed in a stirring mixer, and the flame retardant composition was sprayed from the top of the stirring mixer while stirring at 1,000 to 1500 rpm, followed by stirring and mixing. After completion of the stirring mixing, the stirring mixture was reduced in pressure while heating to 45 ° C. to dry the stirred mixture in a wet state.

Example 2

To 200 parts by weight of the dried mixed composition obtained in Example 1 was added 20 parts by weight of boron peroxide and 10 parts by weight of hexamethylenetetramine pulverized to 325 mesh with a foaming agent, followed by stirring and mixing at 1,000 to 1500 rpm for 60 minutes. 230 weights of the uniformly mixed composition were filled into a molding mold having a size of 200 × 200 × 50 mm, sealed, and then foamed by heating at room temperature to 170 ° C. at a temperature rising rate of 4 ° C./min in a drying dryer and held at the temperature for 30 minutes. To be completely foamed. The foamed molded phenol foam was aged in a heat dryer controlled at 200 ° C. for about 30 minutes, and then cooled to room temperature to prepare a completed phenol foam.

Example 3

Completed in the same manner as in Example 2 except that the product was sealed in a molding mold and sealed, and then foamed by heating for 30 minutes in a heat dryer pre-adjusted at 170 ° C. and aged in a heat dryer adjusted at 200 ° C. for about 30 minutes. Phenolic foam was prepared.

Example 4

200 parts by weight of a non-flame retardant novolak type phenol resin, 50 parts by weight of TEOS (tetra ethyl ortho silicate); 10 parts by weight of aqueous ammonia (10% aqueous solution); 50 parts by weight of water was added to the mixed solution, followed by stirring and mixing at 1,000 to 1500 rpm for 30 minutes to modify the surface of the novolak phenol resin by sol-gel reaction. The resultant homogeneous slurry was placed in a heat dryer controlled at 45 ° C., dried under reduced pressure and evaporated to dryness. Then, 20 parts by weight of boron peroxide pulverized to 325 mesh and 10 parts by weight of hexamethylenetetramine were added with a foaming agent, and 1,000 to 1,500 rpm. Stirred and mixed for 60 minutes. 230 weight of the obtained mixed composition was filled in a molding mold having a size of 200 × 200 × 50 mm, sealed, and heated in a heat dryer at a temperature rising rate of 4 ° C./min from room temperature to 170 ° C. for foam molding, and maintained at that temperature for 30 minutes. Complete foaming was achieved. The foamed molded phenol foams were aged in a heat dryer controlled at 200 ° C. for about 30 minutes and then cooled to prepare a completed phenol foam.

Example 5

The same process as in Example 4 was applied except that the resultant was sealed in a molding mold and completely foamed in a heat dryer pre-adjusted at 170 ° C., and then aged for 30 minutes in a heat dryer controlled at 200 ° C. It was carried out to prepare a finished phenol foam.

Example 6

First, 50 parts by weight of borax and 50 parts by weight of aluminum hydroxide, which had been pre-milled with 325 mesh, were mixed, added to 200 parts by weight of water, and stirred at 500 to 1,000 rpm to form a homogeneous slurry solution. 100 parts by weight of the novolak phenol resin powder was placed in a stirring mixer, and the flame retardant composition was sprayed from the upper portion of the stirring mixer while stirring at 1,000 to 1500 rpm, followed by stirring and mixing. After completion of the stirring mixing, the mixture was reduced in pressure while heating to 45 ° C. to dry the mixture. To the dried mixture, 20 parts by weight of boron peroxide and 10 parts by weight of hexamethylenetetramine, which were pulverized to 325 mesh as a foaming agent, were added and stirred and mixed at 1,000 to 1500 rpm for 60 minutes. 230 weights of the homogeneously mixed composition were filled into a 200 x 200 x 50 mm molding mold, sealed, and heated in a heat dryer at a temperature rising rate of 4 ° C./min from room temperature to 170 ° C. for 30 minutes at the temperature. To be completely foamed. The foamed molded phenol foams were aged for about 30 minutes in a heat dryer controlled at 200 ° C., and then cooled to prepare a completed phenol foam.

Example 7

Except that the resultant was sealed in a molding mold and sealed for 30 minutes in a heat dryer pre-adjusted at 170 ° C. to complete foaming, and then the molded phenol foam was aged in a heat dryer adjusted at 200 ° C. for about 30 minutes. In the same manner as in Example 6, a completed phenol foam was prepared.

Example 8

First, 50 parts by weight of borax and 50 parts by weight of boric acid zinc premixed with 325 mesh were mixed, and then 200 parts by weight of water were added and stirred at 500 to 1,000 rpm to form a homogeneous slurry solution. 100 parts by weight of the novolak phenol resin powder was placed in a stirring mixer, and the flame retardant composition was sprayed from the top of the stirring mixer while stirring at 1,000 to 1500 rpm, followed by stirring and mixing. After completion of the stirring mixing, the stirring mixture was heated to 45 ° C. under reduced pressure to dry the stirred mixture, and 20 parts by weight of boron peroxide and 10 parts by weight of hexamethylenetetramine were pulverized to 325 mesh with a foaming agent, and 1,000 to 1,500 rpm. Stirred and mixed for 60 minutes. The obtained mixed composition was filled into a 200 × 200 × 50 mm molding mold and sealed, and then heated in a heat dryer at a temperature of 4 ° C./min from a normal temperature to 170 ° C. for foaming, and maintained at that temperature for 30 minutes for complete foaming. It was made to be. The foamed molded phenol foam was aged in a heat drier controlled at 200 ° C. for about 30 minutes and then cooled to prepare a finished phenol foam.

Example 9

Except that the resultant was sealed in a molding mold and sealed for 30 minutes in a heat dryer pre-adjusted at 170 ° C. to complete foaming, and then the molded phenol foam was aged in a heat dryer adjusted at 200 ° C. for about 30 minutes. In the same manner as in Example 8, a completed phenol foam was prepared.

Comparative Example 1

100 parts by weight of novolac phenol resin not flame retarded; 35 parts by weight of N.N'-dinitrosopentamethylenetetramine; 15 parts by weight of hexamethylenetetramine were placed in a stirring mixer, stirred for about 30 minutes at 1,000 to 1,500 rpm, and mixed uniformly. The mixed composition was filled into a molding mold having a size of 200 × 200 × 50 mm, sealed, and adjusted to 170 ° C. Maintained in a heated dryer for 30 minutes to achieve a complete foaming, the foamed phenol foam was aged for about 30 minutes in a heat dryer adjusted to 200 ℃ and cooled to prepare a completed phenol foam.

Comparative Example 2

100 parts by weight of novolac phenol resin not flame retarded; 35 parts by weight of modified azodicarbonamide; 15 parts by weight of hexamethylenetetramine were placed in a stirring mixer and stirred for about 30 minutes at 1,000 to 1,500 rpm to mix uniformly. The mixed composition was filled into a molding mold having a size of 200 × 200 × 50 mm, sealed, and then adjusted to 170 ° C. It was maintained for 30 minutes in a heat dryer to form a complete foaming, and the molded phenol foam was aged for about 30 minutes in a heat dryer adjusted to 200 ℃ and cooled to prepare a completed phenol foam.

Test Example

The physical properties and the smokeability of the phenol foams prepared in Examples and Comparative Examples were tested and the results are shown in Table 1 below. The density was calculated by dividing the unit weight by volume, the porosity was measured by a porosi meter, and the thermal conductivity was calculated by a thermal analyzer. In addition, in the process of heating and fully carbonizing 50 g of each phenolic foam, the smoke was evaluated with or without smoke, and the cracked gas was measured by using a gas detector tube and G / C.

As a result of the test, the phenolic foams of Examples 2 to 9 prepared according to the present invention were found to be mostly incombustible, and even when the decomposition gas was hardly generated or generated in the carbonization process, ammonia was 1/3 of the comparative examples. Below, formaldehyde appeared in extremely small amounts up to less than 1/13. These results show that the phenolic foam prepared according to the present invention is suitable for quasi-noncombustible flame retardant standards at home and abroad. In addition, although the foaming was performed using a boron peroxide as a foaming agent instead of the conventional chemical foaming agent, it exhibited comparable physical properties in terms of density, porosity, thermal conductivity, and the like, compared with conventional phenolic foams. This shows that there is no problem in terms of physical properties in using the phenolic foam of the present invention to replace the existing phenolic foam.

Phenolic foam according to the present invention has superior performance than the products currently commercialized, flame retardant and suitable for domestic and international flame retardant standards, in particular, semi-combustible flame retardant standards at home and abroad, without the use of a complex use, such as attaching other flame retardant materials Has low smoke characteristics. In addition, since no chemical blowing agent is used in the production of the phenolic foam of the present invention, no ammonia gas is generated in the manufacturing process, so that an eco-friendly clean manufacturing line can be realized, and formaldehyde is almost never left in the foam molding itself, thereby releasing formaldehyde. This almost eco-friendly building material can be used as a safe building material to the human body that does not generate toxic gases or smoke in the event of fire. Therefore, the phenolic foam of the present invention can be greatly utilized as an excellent heat insulator that solves all the problems of phenolic foam commercialized with the problems of the conventional styrofoam, urethane foam, urea foam, PIR foam and other organic compound-based foam insulation, It also has the secondary advantage that it is possible to recycle not only the waste before and after use but also the carbonized material left after the fire.

Claims (13)

(a) 10 to 100 parts by weight of boric acid or borax; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; Mixing 200 parts by weight of water to make a flame-retardant composition in the form of a homogeneous slurry solution, mixing and coating the flame-retardant composition with 100 parts by weight of a novolak phenolic resin powder and drying it; (b) adding 5 to 60 parts by weight of a boron peroxide and 1 to 20 parts by weight of a curing agent to the dried mixture obtained in (a) with a foaming agent, stirring and mixing, followed by foam molding; (c) A method for producing a phenol foam comprising the step of aging the foamed molded product obtained in (b) for 10 to 100 minutes in a 150 ~ 230 ℃ heat dryer. The method of claim 1, wherein the boric acid is characterized in that the ortho boric acid is pulverized to 200 to 400 mesh. The method according to claim 1, wherein in the step (a), the novolak phenolic resin powder is placed in a stirring mixer, and the flame retardant composition is sprayed from the top of the stirring mixer and coated while stirring at 1,000 to 1,500 rpm. The method according to claim 1, wherein the boron peroxide is pulverized to 200 to 400 mesh. The method according to any one of claims 1 to 4, wherein step (b) is performed by foaming by heating to 150 to 170 ° C. (a) 10 to 100 parts by weight of TEOS; 1-20 parts by weight of ammonia water; Adding 200 parts by weight of novolak phenolic resin powder to a solution of 10 to 100 parts by weight of water, stirring and mixing to modify the surface of the novolak phenolic resin by sol-gel reaction, and then drying; (b) adding 5 to 60 parts by weight of boron peroxide and 1 to 20 parts by weight of a curing agent with a foaming agent, stirring and mixing, and then foaming the mixture obtained in (a); (c) A method for producing a phenol foam comprising the step of aging the foamed molded product obtained in (b) for 10 to 100 minutes in a 150 ~ 230 ℃ heat dryer. The method according to claim 6, wherein the boron peroxide is pulverized to 200 to 400 mesh. The method according to claim 6 or 7, wherein the step (b) is performed by foaming by heating to 150 to 170 ° C. delete delete 10 to 100 parts by weight of boric acid or borax, in 100 parts by weight of a novolak phenol resin powder; 10 to 100 parts by weight of aluminosilicate or aluminum hydroxide or boric acid; A phenol foam composition formed by mixing and coating a flame retardant composition containing 200 parts by weight of water and then foaming by adding 5 to 60 parts by weight of boron peroxide and 1 to 20 parts by weight of a curing agent. The composition of claim 11, wherein the boric acid is pulverized ortho boric acid to 200 to 400 mesh. 13. The composition of claim 11 or 12, wherein the boron peroxide is ground to 200 to 400 mesh.