KR100585218B1 - Incombustible coating material for styrofoom and the method thereof - Google Patents

Abstract

The present invention relates to a flame retardant coating agent and a method for producing the foamed styropol to solve the combustibility and harmful gas generation of the foamed styropol, and more specifically to the surface of the foamed styropol material that bubbles and non-combustible gas is released in response to the flame The foamed styropol, which is coated on the foam, expands on the material surface of the foamed styropol to form a heat insulating layer, thereby suppressing the diffusion and heat transfer of the combustion decomposition products and further extinguishing the flame by the generated incombustible gas. It relates to a flame retardant coating agent and a method for producing the same.

To this end, the present invention is a flame retardant method of forming a heat insulating layer by the surface expansion layer in addition to the carbonized layer in order to effectively prevent thermal transfer to the material from the principle that the effect of the heat insulating layer is sharply increased as the thickness of the bubble layer on the material surface is increased Has been redesigned. In addition, the formulation of a flame retardant coating agent for realizing such a flame retardant method includes (1) a flame retardant for flame retardant and low smoke-retardant effect, (2) a heat insulating layer forming agent for forming a carbonized layer and a bubble layer, and (3) a flame. Nonflammable gas generator which produces gas, such as nitrogen, ammonia and carbon dioxide, which is nonflammable, and has anti-inflammatory effect. (4) Inorganic filler which improves the mechanical strength and water resistance of flame-retardant coating and shape retention at high temperature. ( 5) The flame retardant coating agent is composed of a binder that serves to fix and adhere to the surface of the foamed styropol.

Fire, Explosion, Styrofoam, Flame Retardant, Hazardous Gases, Surface Expansion, Combustion Control

Description

Flame retardant coating of foamed styropol and its manufacturing method {Incombustible coating material for styrofoom and the method             

1 is an explanatory diagram of a state in which combustion is blocked when a flame is applied to a surface of a flame-retardant coated foamed styropol according to the present invention

Figure 2 is an experimental example when the flame is applied in the direction parallel to the surface of the flame-retardant coated foamed styrofoll according to the present invention

Figure 3 is an experimental example when the flame is applied in the vertical direction on the surface of the flame-retardant coated foamed styropol according to the present invention

Figure 4 is a comparison of the experimental example of the foamed styropol and the conventional foamed styropol according to the invention when the flame is horizontal

           <Explanation of symbols for the main parts of the drawings>

1. Flame retardant coated foamed styropol 2. Flame retardant coating layer

3. heat source 4. flame

5. Carbonized layer 6. Bubble layer

7. flammable gas 8. incombustible gas

9. Surface expansion interface 10. Decomposition layer interface

11. Expansion layer film

The present invention relates to a flame retardant coating agent and a method for producing the foamed styropol to solve the combustibility and harmful gas generation of the foamed styropol, and more specifically to the surface of the foamed styropol material that bubbles and non-combustible gas is released in response to the flame The foamed styropol, which is coated on the foam, expands on the material surface of the foamed styropol to form a heat insulating layer, thereby suppressing the diffusion and heat transfer of the combustion decomposition products and further extinguishing the flame by the generated incombustible gas. It relates to a flame retardant coating agent and a method for producing the same.

Conventional foamed styropol products are manufactured by mixing a blowing agent (combustible gas such as butane and pentane) with polystyrene, which is a non-flame retardant product, which is mostly a flammable resin, and pre-foaming a plurality of styrene raw particles to dry the pre-foamed raw particles. After maturation, a method of producing the prefoamed raw material particles by completely foaming again is used.

Recently, high insulation and high density are required to maximize energy saving and efficiency in buildings such as houses and buildings, and many insulation materials are used for walls and ceilings of almost all buildings. As these insulating materials, organic insulating materials such as expanded polystyrene, expanded polyethylene or polyurethane, which are excellent in terms of insulation performance, workability and cost, are widely used. However, since these organic insulating materials are combustible, when combustion is initiated by various ignition sources, they have combustion characteristics that are close to explosive combustion, which causes a fire and an explosion accident of a building. In addition, since the organic insulating material generates toxic gases such as cyanide and carbon monoxide depending on the type of material and the combustion state, there is also a risk of gas poisoning. Among the organic insulation materials, expanded polystyrene is widely used as a brand name of foamed styrofoam or styrofoam. Currently, the production of foamed styropol is millions of tons per year in Korea and the world, and it is widely consumed in containers, protective buffers for products, and building insulation materials. And production is increasing every year. Such foamed styropol has excellent problems such as light weight, ease of processing, high insulation, impact resistance, water resistance, etc., but high combustibility, toxicity during combustion, and deformation of the shape by combustion.

On the other hand, inorganic and organic flame retardants are used in conventional flame retardant products. Inorganic flame retardants include antimony and its substitutes. For example, barium metaborate (Ba (BO ₂ ) ₂ H ₂ O) corresponds to this, and antimony flame retardants form a glass film to block air to prevent flame retardancy. It acts to raise. Organic-based flame retardants include halogen compounds such as bromine and chlorine and phosphate esters. Halogen compounds block the supply of air and lower the temperature of the combustion system, which is highly flame retardant, but it is known that there is a possibility of destruction and warming of the global ozone layer. In addition, bromine compounds have been pointed out in the risk of the formation of bromine-based dioxins according to treatment methods, and the development of appropriate treatment methods is necessary due to the possibility of carcinogenic substances during combustion. have.

Looking at the recent invention related to the flame retardant of foamed styropol, a production method of flame retardant treatment of the flame retardant containing boric acid-based inorganic material on the surface of the foamed styropol particles was developed (Japanese Patent No. 3163282), which is applicable to foamed styropol. to be. The foamed styropol prepared by this method forms a large amount of carbide layer on the surface of the flame-retardant foamed styropol particles when subjected to heat, and maintains little deformation and heat resistance. Hazardous gases may be generated because the foamed styropol particles are easily melted and thermally decomposed to heat and burn in the thin air supply film.The combustion of the spherical foamed styropol in the film causes the inside of the foamed styropol to void and the carbonized layer. The film is structurally weak and can easily deform and deform due to external forces. In fact, from the combustion test results of the sample by this technique, it was possible to observe aesthetic problems caused by the formation of a severe carbonized layer on the combustion surface of the foamed styropol, and a bad smell caused by combustion gas generation. In addition, this technique requires a flame-retardant coating on the pre-expanded raw material particles, so that a separate new manufacturing process must be added in the middle of the conventional foamed styropol manufacturing process, and thus high cost new equipment investment is indispensable. In addition, since the flame-retardant coating method on the entire surface of each one of the pre-expanded raw material particles, there is a problem in dissemination and practical use due to the high cost of manufacturing the flame retardant chemicals.

In addition, a method of making a flame-retardant insulation material by spraying and attaching the mixture of the foamed styrofoll and the flame retardant to the heat insulating material by using cement, crushed particles of foamed styropol and organic binder (Japanese Patent Laid-Open No. 2002-226250). This flame retardant method relates to the recycling of discarded foamed styrofoam, which is suitable for the formation of soft and flexible soft urethane foam, by spraying cement, foamed styropol pulverized particles and flame retardant together directly on the building's concrete wall at the construction site. The method of attaching is used. Therefore, it is difficult for the general public to use easily, and it is not suitable for the flame retardant method of molded articles of foamed styropol, and its use is limited because it cannot be used outside of the building's outer wall.

An object of the present invention is to coat a flame retardant coating on the surface of the foamed styropol to prevent combustion of the foamed styropol, to minimize the deformation of the form by heating and to prevent the generation of toxic gases.

In order to achieve this purpose, flame retardant having adsorption and cooling effect of harmful substances, inorganic filler which maintains its shape at high temperature, and insulation layer forming agent which forms bubble layer and carbonized layer in response to flame and non-flammable gas are emitted A flame-retardant coating agent comprising a uniformly mixed agent and a binder is coated on the surface of the foamed styropol to expand the air bubbles on the material surface of the foamed styropol during combustion to form a heat insulating layer film having low thermal conductivity.

The present invention is coated with the surface of the foamed styropol by foaming and non-combustible gas generated by heating to foam on the material surface of the foamed styropol when contacted with the flame to form an expansion layer to hinder combustion and suppress heat transfer And, the flame is to be extinguished by the incombustible gas generated. That is, a non-combustible gas generated from a flame-retardant coating agent while allowing a low thermal conductive flame-retardant bubble layer to be generated in response to the flame on the surface of the foamed styropol and to prevent the radiant heat from the flame from being thermally conducted into the foamed styropol. It is a flame retardant coating agent of foamed styropol which prevents the combustion of combustible gas generated by thermal decomposition of a temporary material, suppresses the generation of combustion harmful gas, and has multiple combustion suppressing effects, and a manufacturing method thereof.

The flame retardant coating agent for forming a flame retardant film according to the present invention is as follows.

The flame retardant coating agent of the present invention is prepared by uniformly mixing a flame retardant, an inorganic filler, a heat insulating layer forming agent (surface expansion agent and bubble raising effect agent), a non-combustible gas generator, a binder with a blender, the flame retardant coating agent on the foamed styropol surface Spray or apply to form a flame retardant coating film.

<Flame retardant coating agent>

The flame retardant is 10 to 30 parts by weight of any one or a mixture of two or more of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, antimony molybdate. In particular, aluminum hydroxide (Al (OH) ₃ ) is heated to the foamed styropol, and when the temperature becomes higher than 600 ° C., the microporous is changed into a myriad of activated aluminas, which has adsorptive performance, and thus dioxin, hydrogen chloride gas (HCl), etc., generated during combustion. Adsorption of harmful substances, endothermic reaction during thermal decomposition, cooling effect, non-flammability, excellent water and acid resistance. In addition, by using the flame retardant in combination can be expected to improve the flame retardant effect.

Inorganic fillers are flame retardant clays such as magnesium silicate, titanium oxide, alumina, hollow ceramic powders, silica (SiO ₂ ), silicon nitride powders (Si ₃ N ₄ ), carbon fiber, and foamed hollows Use 5 to 30 parts by weight of any one of volcanic ash powder (Maarlite (trade name), Shiras balloon (trade name), diatomaceous earth, talc, or a mixture of two or more thereof. do. The inorganic filler improves the mechanical strength, water resistance, and shape retention performance of the foamed styropol at high temperatures of the flame retardant coating. The volcanic ash powder (Maarlite or Shiras balloon) is an artificial volcanic agent fired at a high temperature of 1000 ° C. or higher, and its main components are silicon oxide (SiO ₂ ) and aluminum oxide (Al ₂ O ₃ ), which are light, porous, absorbent and stable. With the strength of the material, it is possible to improve the filling resistance, heat insulation, fire resistance, durability, acid resistance, alkali resistance, water resistance, etc. of the flame retardant. In addition, when the ceramic is also hollow (porous) ceramic powder is used, the thermal barrier ability is improved.

The heat insulating layer forming agent is a surface expander and a bubble synergistic effect agent, and the surface expander is a microcapsule-type ammonium polyphosphate, poly melamine phosphate, melamine phosphate, ammonium phosphate, or a mixture of two or more thereof 5 to 20 5 parts by weight of any one of parts by weight, and the bubble synergist, dextrin, pentaerythritol, polyvinyl acetate resin, arabitol, vinyl acetate, glucose, maltose.

The surface expanding agent and the bubble synergistic effector form a bubble layer to enhance the thermal insulation effect by the gas insulation layer other than the carbonized layer.

In addition, 0.2 to 1.5 parts by weight of any one of manganese acetate, zinc acetate, manganese lactate, and zinc lactate may be added to the heat insulation layer forming agent as an assistant for promoting heat insulation layer formation and stabilizing effect.

The non-combustible gas generator is added 5-12 parts by weight of any one of dicyanide (Dicyandiamide), melamine, glycine (Glycine), guanidin (Guanidin), urea.

The non-combustible gas generator has an anti-inflammatory effect by generating non-combustible nitrogen (N ₂ ), ammonia (NH ₃ ), carbon dioxide (CO ₂ ), etc. when the flame-retardant coated surface of the foamed styropol comes into contact with the flame.

The binder is 10-40 parts by weight of three kinds of sodium silicate 37 to 40% aqueous solution and a lithium silicate 24 to 30% aqueous solution, or any mixture of two kinds. The binder serves to fix and adhere the flame retardant coating agent to the foamed styropol. In addition, one of 6 to 18 parts by weight of zinc borate and 2 to 10 parts by weight of sodium tripolyphosphate may be added to control the curing time of the binder and to prevent water solubility after curing, and to improve only the curing time of the binder, sodium hydrogen carbonate, 5-10 weight part of potassium hydrogencarbonate can also be added. In addition, 0.1-2.0 parts by weight of one of alkyl naphthalene sulfonate and sodium aialkyl sulfsuccinate may be used to increase the fixing ability of the binder.

In addition, it is also possible to use 2 to 20 parts by weight of water depending on the viscosity required when mixing and applying the flame retardant coatings.

Referring to the operation of the present invention.

The flame-retardant coating layer (2) coating coated with the flame-retardant coated foamed styrofoil with a thickness of 0.5 to 1.0 mm as shown in FIG. Combustion occurs, in which a carbide layer 5 is formed on the material surface. In addition to the carbonization layer 5 which prevents thermal transfer to the material to some extent, in the present invention, in order to form a more efficient heat insulating layer, a bubble raising effect agent is added to the flame retardant film and the surface of the flame retardant film is expanded to form the bubble layer 6. Do it. As the thickness of the bubble layer 6 increases, the effect of the heat insulating layer increases exponentially, so that a flame of a very high temperature is required to sustain combustion of the material. For example, if the thickness of the bubble layer 6 is 1mm, the external flame temperature for maintaining combustion should be 743 ° C. For 7mm, there must be a continuous flame supply of 1500 ° C and 4600 ° C for 10mm. Combustion can be maintained. In the case of a general house or building fire, a flame temperature of 700 to 1200 ° C. is generated, and in order to cope with this, it is necessary to form a bubble layer 6 of 5 mm or more on the surface coating of the foamed styropole. In addition, since it is necessary to cope with the expansion of the flame due to the combustible gas 7 generated by the thermal decomposition of the material, it is not combustible such as carbon dioxide (CO ₂ ), nitrogen gas (N ₂ ), ammonia gas (NH ₃ ) by thermal decomposition. The generation of harmful gases is reduced by adding a component that emits the gas 8 and a flame retardant such as aluminum hydroxide having a large smoke suppression effect (low smoke effect). In this way, the surface expansion interface 9 of the flame retardant coating layer 2 film forms the expansion layer surface 11 via the decomposition layer interface 10 while thermally decomposing by the flame and constitutes the bubble layer 6.

The present invention in which the flame-retardant coating layer (2) is formed when the flame (4) direction acts in the horizontal direction (FIG. 2) or the vertical direction (FIG. 3) with respect to the surface of the foamed styropole 1 by the flame-retardant treatment according to the present invention. The foamed styropole 1 retains its original shape without being deformed or collapsed. However, the conventional foamed styropol or self-extinguishing flame retardant foamed styropol (manufactured by Nippon Nishi Chemical Co., Ltd.) collapses or shrinks or deforms as shown in FIG. Can be.

<Example 1>

150 g of aluminum hydroxide as a flame retardant and 40 g of magnesium hydroxide, 50 g of foamed hollow volcanic ash powder (Maarlite) manufactured as an inorganic filler, 150 g of ammonium polyphosphate as a surface swelling agent, 100 g of pentaerythritol as a bubble-boosting effect, non-combustible gas Each powder, such as melamine 50 g and urea 50 g, is mixed as a generator, and 400 g of sodium silicate three 40% aqueous solution and 100 g of water are used as a binder, and the above flame retardant, inorganic filler, surface expander, bubble raising effect agent, and nonflammable gas generator are used. The mixture was stirred in a stirrer with a mixture for 2 hours at 500rpm to be uniformly mixed, coated on a foamed styropol surface with a thickness of 1.0 mm and naturally dried for at least 24 hours.

<Example 2>

200 g of aluminum hydroxide as a flame retardant, 180 g of titanium oxide as an inorganic filler, 110 g of polyphosphate melamine as a surface expander, 100 g of pentaerythritol as a bubble-increasing effect agent, 10 g of manganese acetate as an auxiliary agent for promoting and stabilizing insulation layers, 50 g of melamine as a non-combustible gas generator, and After mixing each powder, such as 50 g of urea, sodium silicate as a binder 100 g of three 40% aqueous solution, 200 g of lithium silicate 24% solution, and 120 g of water are mixed in a stirrer and mixed uniformly, and then the flame retardant, inorganic filler, bubble raising effect agent, thermal insulation layer formation and stabilization effect aid, and nonflammable gas generator The mixture was sufficiently stirred for 2 hours at 500 rpm to be uniformly mixed with the mixture, and then coated on a foamed styropol surface with a thickness of 1.0 mm and naturally dried for at least 24 hours.

<Example 3>

150 g of aluminum hydroxide as a flame retardant, 150 g of foamed hollow volcanic ash powder (Maarlite, Japan), as a surface expander, 150 g of polyphosphate melamine as a surface expander, 100 g of pentaerythritol as a bubble-raising effect agent, as a heat insulation layer formation promoting and stabilizing aid After mixing 15 g of manganese acetate and 50 g of melamine as a nonflammable gas generator, sodium silicate as a binder 200 g of three 40% aqueous solution, 100 g of lithium silicate 24% solution, 150 g of water, 150 g of zinc borate and 5 g of alkylnaphthalene sulfonate as an electrodeposition agent for increasing the fixing ability of the binder as a curing agent for controlling the curing time of the binder and after curing. After homogeneous mixing, the mixture of the flame retardant, surface expander, bubble raising effect agent, thermal insulation layer formation promoting and stabilizing aid, nonflammable gas generating agent and the like are mixed in the same manner as in Example 2 and 0.5 mm thick on the foamed styropol surface. After coating it is allowed to dry for at least 24 hours.

<Experiment Result>

As a result of the combustion test on the flame-retardant foamed styropol prepared in Examples 1, 2 and 3 with a gas burner flame of 1000 ° C. similar to a general building fire temperature, the examples 1, 2 and 3 flame-retarded according to the present invention. All of the foamed styropols had no combustion, no shape collapse, and no smoke was generated. In particular, the flame retardant foamed styropol prepared in Example 2 had a good flame retardant coating and the flame retarded foamed styropol prepared in Example 3 was a flame retardant. It can be seen that the drying rate and adhesion state of are very good. In addition, the flame-retardant foamed styropol prepared in Example 1 of the present invention and the conventional foamed styropoles were heated under the same conditions for 30 seconds, respectively, as shown in FIG. Foamed styrofoam and self-extinguishing flame-retardant foamed styropol are shown in the results of self-extinguishing flame-retardant foamed styropol (in the case of Nippon Hyosung Co., Ltd.), which loses its shape (in the case of general foamed styropole) or is completely burned down and deformed. Could.

According to the present invention, the surface expansion layer of the flame-retardant coating of the flame-retardant coating of the foamed styrofoll forms an insulating layer to prevent the expansion of the combustion to the foamed styropol, prevents the inflammable gas from generating an anti-inflammatory action, and adsorbs the toxic gas to collapse the shape of the foamed styropol. It has the effect of blocking and minimizing the generation of harmful combustion gases.

Claims (9)

In the method for producing a flame retardant foamed styropol, 10 to 30 parts by weight of any one or two or more kinds of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, antimony molybdate; Magnesium silicate (Sepiolite), titanium oxide, alumina, ceramic powder, silica (SiO ₂ ), silicon nitride powder (Si ₃ N ₄ ), carbon fiber, volcanic ash powder (Maarlite), diatomaceous earth, talc or any mixture of two or more Inorganic filler 5-30 parts by weight; 5 to 20 parts by weight of any one or two or more of a microcapsule-type ammonium polyphosphate, melamine phosphate, melamine phosphate, ammonium phosphate, or phosphate ester and a dextrin, pentaerythritol, polyvinyl acetate resin, 5-10 parts by weight of the bubble-raising effect agent which is any one of arabitol, vinyl acetate, lucose and maltose; 5 to 12 parts by weight of a non-combustible gas generator which is any one of dicyandiamide, melamine, glycine, guanidine, and urea; Sodium silicate Foaming, characterized in that a flame-retardant coating agent is prepared by uniformly mixing 10 to 40 parts by weight of any one of three kinds of 37-40% aqueous solution, lithium silicate 24-30% aqueous solution or two kinds of mixed binders uniformly. Method for preparing a flame retardant coating of styropol. In the method for producing a flame retardant foamed styropol, 10 to 30 parts by weight of any one or two or more kinds of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, antimony molybdate; Magnesium silicate (Sepiolite), titanium oxide, alumina, ceramic powder, silica (SiO ₂ ), silicon nitride powder (Si ₃ N ₄ ), carbon fiber, volcanic ash powder (Maarlite), diatomaceous earth, talc or any mixture of two or more Inorganic filler 5-30 parts by weight; 5 to 20 parts by weight of any one or two or more of a microcapsule-type ammonium polyphosphate, melamine phosphate, melamine phosphate, ammonium phosphate, or phosphate ester and a dextrin, pentaerythritol, polyvinyl acetate resin, 5-10 parts by weight of the bubble-raising effect agent which is any one of arabitol, vinyl acetate, lucose and maltose; 0.2 to 1.5 parts by weight of a manganese acetate, zinc acetate, manganese lactic acid, zinc lactate, promoting the formation of thermal insulation layer and stabilizing effect; 5 to 12 parts by weight of a non-combustible gas generator which is any one of dicyandiamide, melamine, glycine, guanidine, and urea; Sodium silicate 10 to 40 parts by weight of any one of three kinds of 37 to 40% aqueous solution and 24 to 30% lithium silicate aqueous solution or two kinds of mixed binders; Curing time of the binder which is any one of 6 to 18 parts by weight of zinc borate and 2 to 10 parts by weight of sodium tripolyphosphate and a water-soluble inhibitor after curing; 5 to 10 parts by weight of a curing time improving agent of any one of sodium hydrogen carbonate and potassium hydrogen carbonate; A flame retardant coating agent was prepared by uniformly mixing 0.1 to 2.0 parts by weight of a binder adhesion increasing agent, which is one of alkyl naphthalene sulfonate and sodium dialkyl sulfosuccinate, and applied to the foamed styropol surface. Method for producing a flame-retardant coating agent of the foamed styropol. In the flame-retardant foamed styropol, 10 to 30 parts by weight of any one or two or more of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, antimony molybdate; Magnesium silicate (Sepiolite), titanium oxide, alumina, ceramic powder, silica (SiO ₂ ), silicon nitride powder (Si ₃ N ₄ ), carbon fiber, volcanic ash powder (Maarlite), diatomaceous earth, talc or any mixture of two or more Inorganic filler 5-30 parts by weight; As an insulating layer forming agent, 5 to 20 parts by weight of any one or two or more of microcapsule-type ammonium polyphosphate, melamine phosphate, melamine phosphate, ammonium phosphate, and phosphate ester and dextrin, pentaerythritol, vinyl polyphosphate, 5 to 10 parts by weight of the foam-raising effect agent of any one of the Arabian framework, vinyl acetate, glucose, maltose; 5 to 12 parts by weight of a non-combustible gas generator which is any one of dicyandiamide, melamine, glycine, guanidine, and urea; Sodium silicate One of three kinds of 37-40% aqueous solution, lithium silicate 24-30% aqueous solution, or 10 to 40 parts by weight of a binder mixed with two kinds of the flame retardant coating agent, wherein the foamed styropol is coated on the surface of the foamed styropol. Flame retardant coatings. delete delete delete delete delete delete

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