KR20110012099A - Polyurethane and polyurethane foam - Google Patents

Abstract

PURPOSE: A composition for preparing polyurethane is provided to suppress the generation of poisonous gas and harmful chemical substance and to rapidly treat harmful chemical substance and poisonous gas by porous loess. CONSTITUTION: A composition for preparing polyurethane with excellent smoke inhibition property and flame retardant characteristic is obtained by: mixing polyol 25~45 weight%, loess 5~30 weight%, inorganic flame retardant liquid 3~20 weight% at a room temperature; or mixing polyol 25~45 weight%, expanded graphite 5~30 weight% and inorganic flame retardant liquid 3~20 weight% at a room temperature; or polyol 25~45 weight%, loess 2.5~15 weight%, expanded graphite 2.5~15 weight% and inorganic flame retardant liquid 3~20 weight% at a room temperature.

Description

Polyurethane foam manufacturing composition having excellent anti-flammability and flame retardancy and its polyurethane foam {Polyurethane and Polyurethane foam}

The present invention relates to a composition for producing polyurethane foam (Polyurethane Foam) excellent in deterrence and flame retardancy, and a porous ocher and / or drug having excellent adsorption and deodorizing function of toxic gases and harmful chemicals Highly flame retardant is achieved by expanded graphite that blocks oxygen (O ₂ ) inflow by self-extinguishing by blocking the inflow of oxygen (O ₂ ) at high temperature above 700 ℃ and generates harmful chemicals and toxic gases In addition to being suppressed, the generated harmful chemicals and toxic gases are rapidly adsorbed by the porous loess.

In general, polyurethane foam has the advantages of excellent energy absorption ability, molding of complex parts, low specific gravity and low processing cost, and easy processability, such as automobile seats, insulation, building flooring, furniture, bed, clothing, etc. It is used in various industries such as sealing materials, sound absorbing materials, heat insulating materials and vibration damping materials.

Polyurethanes are polypropylene polyols and / or polyester polyols (PPG) such as main raw materials, polyhydric glucols (PPG), isomers such as isocyanates (foaming catalysts), and other additives such as surfactants. Polyurethane foam (Polyurethane Foam) is foamed by the urethane reaction by mixing them.

Polyurethane bonds having a three-dimensional bond structure by reacting polyether polyols and / or polyester polyols with isocyanates are called urethane reactions, and polyols having ether bonds in molecular structures such as oxypropylene ether polyols and oxyethylene-propylene ether polyols The polyol obtained by the reaction of a polybasic acid such as phthalic acid and adipic acid and a polyalcohol is called a polyether polyol, and a polyol polyol (80 to 90%) has been used in recent years.

The polyether polyol is prepared by an epoxide polymerization reaction of a hydrocarbon oxide such as ethylene oxide or propylene oxide as an alkali hydroxide and a polymerization initiator.

As the blowing agent (catalyst) used in the urethane reaction of isocyanate and polyether polyol, various bases such as dimethylethanolamine, triethylamine, triethylenediamine, hexamethylenetetraamine, and cobalt naphthenate are used, but an amine catalyst is mainly used. .

The characteristic of the polyurethane foam is that there is no seam, there is an advantage to obtain a heat dissipation layer of the averaged layer freely without depending on the shape of the object, in the case of urethane spray foam (95%) as a fine independent bubble of 95% It has a stable structure, no deformation, excellent penetration resistance except some solvents such as acetic acid, sulfuric acid, etc. It is also very good in moisture proof, soundproof, dustproof, electric, heat transfer, weather resistance, physical strength and concrete, Excellent adhesion to panel metals and, above all, excellent heat insulation, and the maximum heat insulation effect can be obtained with a thinner construction thickness than other heat insulators.

On the other hand, it is not only vulnerable to fire but also has a problem of killing human life by melting or generating various toxic gases at a certain temperature or higher, and even if the flame retardant is mixed or coated, it is effective for the initial fire, but has a self-extinguishing function. If the flame is in contact for a long time or the initial flame is large, there is a disadvantage that the flame retardancy is not properly exhibited.

The substances that occur when polyurethane foam is burned include carbon dioxide, carbon monoxide, hydrogen chloride, hydrogen cyanide, and hydrogen bromide, which irritate the eyes, nose, respiratory system, affect the nervous system, liver, lungs, kidneys, and carcinogenesis. It has been reported to cause reproductive toxicity such as toxicity, embryotoxicity.

In addition, these toxic gases are known to cause discomfort and aversion by stimulating the human sense of smell even at low concentrations. As a result of analyzing the components of toxic gases generated when 100 g of polyurethane is burned, 420 ppm of deadly poisonous gas is generated. At this level, it is known as a lethal dose in which people suffocate and die unconscious or die within 5 minutes. Therefore, there is an urgent need for polyurethanes and foaming agents having excellent self-extinguishing, anti-depressive and flame retardant properties.

The present invention is self-extinguishing by blocking the inflow of oxygen (O ₂ ) by 200 to 250 times the volume expansion of porous loess and / or high temperature of about 700 ℃ excellent excellent adsorption and deodorization of toxic gases and harmful chemicals Highly flame retardant properties are achieved by self-expanding expanded graphite and the generation of harmful chemicals and toxic gases is suppressed, and the generated hazardous chemicals and toxic gases are rapidly adsorbed by porous yellow soil. It is an object to provide a composition for producing polyurethane foam (Polyurethane Foam) excellent in the decompression and flame retardancy.

Another object of the present invention is to provide a polyurethane foam in which ocher color is expressed by the mixed addition of ocher powder or ocher solution.

Another object of the present invention is characterized in that when preparing the polyurethane composition, the expanded graphite, ocher and flame retardant are effectively mixed by ultrasonic action.

The present invention is a composition for producing polyurethane tanfoam composed of a resin premix containing a polyol and other additives; A liquid polyurethane composition is formed by mixing 25 to 45% by weight of polyol, 5 to 30% by weight of ocher, and 3 to 20% by weight of inorganic flame retardant, and a foaming agent (foaming catalyst) is 25 to 45% by weight (reaction) The ratio of 1: 1 to 1: 1.6) is mixed to prepare a polyurethane foam.

In another aspect, the present invention is a composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; Polyol 25 to 45% by weight, expanded graphite 5 to 30% by weight, inorganic flame retardant 3 to 20% by weight at room temperature to form a liquid polyurethane composition, a foaming agent (foaming catalyst) 25 to 45% by weight ( The reaction ratio of 1: 1 to 1: 1.6) is mixed to prepare a polyurethane foam.

In another aspect, the present invention is a composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; A liquid polyurethane composition is prepared by mixing 25 to 45% by weight of polyol, 2.5 to 15% by weight of ocher, 2.5 to 15% by weight of expanded graphite, and 3 to 20% by weight of inorganic flame retardant, and a foaming agent (foaming catalyst) ) 25 to 45% by weight (reaction ratio 1: 1 to 1: 1.6) is mixed to prepare a polyurethane foam.

In another aspect, the present invention is a composition for producing a polyurethane foam composed of a resin premix containing an isocyanate, other additives; 5-30% by weight of 200mesh ~ 1,000mesh loess is mixed with isocyanate or resin premix to the resin premix weight to prepare a liquid polyurethane composition, and 25 ~ 45% by weight of blowing agent (foaming catalyst) Polyurethane foam is produced.

In addition, the present invention is a composition for producing a polyurethane foam composed of a resin premix containing an isocyanate, other additives; 5 to 30% by weight of the expanded graphite of 60 mesh to 150 mesh is mixed with the isocyanate or resin premix to the weight of the resin premix to prepare a liquid polyurethane composition, and 25 to 45% by weight of the blowing agent (foaming catalyst) is mixed with poly Urethane foam is produced.

In addition, the present invention is a composition for producing a polyurethane foam composed of a resin premix containing an isocyanate, other additives; A liquid polyurethane composition is prepared by mixing 2.5 to 15% by weight of polyisocyanate or resin premix with 200 to 1,000 mesh of ocher and 60 mesh to 150 mesh of expanded graphite, respectively, based on the resin premix weight, and a foaming agent (foaming catalyst). 25 to 45% by weight of the polyurethane foam is prepared.

In the present invention, the isocyanate has a specific gravity of 1.08 and a viscosity of 100 to 1,000 cps / 25 ° C.

In addition, the present invention is foamed molding the composition for preparing a liquid polyurethane foam with a foaming agent to obtain a polyurethane foam excellent in deterrentability and flame retardancy.

In addition, in the polyurethane foam of the present invention, the ocher powder or the ocher solution is mixed and added, and the ocher color is expressed.

The present invention is a porous ocher and excellent in the control of humidity and adsorption and deodorization of toxic gases and harmful chemicals and / or by blocking the inflow of oxygen (O ₂ ) by 200 to 250 times the volume expansion at a high temperature of more than about 700 ℃ Highly flame retardant is achieved by expanding graphite which extinguish fire, and the generation of toxic gas including soot is suppressed, and the generated harmful chemicals and toxic gases are adsorbed by porous yellow soil. have.

In addition, the present invention, by mixing a predetermined amount of flame retardant liquid, ocher powder and / or expanded graphite and other additives in the polyurethane composition has excellent detergency, flame retardancy and self-extinguishing, and excellent mechanical and chemical properties It is effective to foam the foam.

In addition, the present invention is a high flame retardancy that does not burn (flame) or change the physical properties of the polyurethane foam even when exposed to a direct fire temperature of about 1,000 ℃ 10 minutes by ocher and / or expanded graphite fixed to the foamed polyurethane foam And semi-combustibility is provided.

In addition, the present invention is environmentally friendly because it uses a natural inorganic material, porous ocher, not only to suppress the generation of harmful chemicals and toxic gases in the fire, but also quickly adsorbed and removed even if they occur, high thermal insulation, soundproof, dustproof, moisture-proof effect Larger, there is an effect of emitting far infrared rays, beneficial to air purification, insect repellent and human body.

In addition, the present invention has the effect of solving the environmental pollution problems, such as sick house syndrome because the amount of formaldehyde emitted from the urethane foam is almost eliminated or greatly reduced by the action of ocher.

In addition, the polyurethane foam of the present invention has the effect that the ocher powder or the ocher solution is mixed with the ocher color is expressed.

In addition, the ocher and / or expanded graphite of the present invention is a water-soluble or inorganic material that does not use an organic solvent, so it is a very useful invention that does not generate toxic gases or dusts and thus is harmless to humans and does not generate pollutants.

Hereinafter, exemplary embodiments of the present invention will be described in detail.

In the present invention, the main liquid B (transparent liquid) for preparing polyurethane foam may include polyether polyol and / or polyester polyol, and is a blowing agent (foaming catalyst). Examples of the liquid (black liquid) include isocyanates.

The polyols are in addition to polyether polyols and polyester polyols, and have various types of molecular weights.

Examples of the isocyanate (Diisocyanate) include diphenylmethane diisocyanate (MDI = Diphenylmethane Diisocyanate) or toluene diisocyanate (TDI = Toluene Diisocyanate).

The polyol and the isocyanate and other additives that foam the polyurethane foam by reacting with the polyol are the same or similar to those used in the related art and are well known in the polyurethane foam manufacturing art, and thus detailed descriptions thereof will be omitted.

In the present invention, the ocher and / or expanded graphite is mixed in a predetermined amount to the polyol (liquid B) as in Examples 1, 2 and 3 below, or isocyanate (foaming catalyst) as a blowing agent (foaming catalyst) as in Examples 4, 5 and 6 A)) or a predetermined amount of the polyol (B liquid) and isocyanate (A liquid) can be mixed in a predetermined amount to prepare a polyurethane foam composition, by mixing the A liquid and the B liquid Polyurethane foam is produced.

The ocher mixed in the liquid A or liquid B, or liquid A and liquid B is in the range of 200 mesh to 1,000 mesh, and expanded graphite is in the form of liquid colloid even when mixed in the range of 60 mesh to 150 mesh.

In the present invention, the properties of the resin premix (Resin Premix) is as shown in Table 1 below, when the foaming with polyurethane foam, the mixing ratio is as shown in Table 2 below, the isocyanate has a specific gravity of 1.08 and viscosity of 100 ~ 1,000cps / 25 ℃ Isocynate was used, and the mixing ratio of A liquid (MDI) and B liquid (PPG) was 1: 1 to 1: 1.6.

Table 1: Characteristics of Resin Premix

Characteristics Measures Viscosity 100 to 1,000cps / 25 ℃ Exterior Transparency Specific gravity, 25 ℃ 1.08 Foaming agent type H ₂ O F.R.D (㎏ / ㎥) 36 ± 3

<Table 2: Foaming Ratio>

MDI (A liquid) PPG (B amount) Liquid temperature (℃) 18-22 18-22 Compounding cost 100 100-160 C.T (sec) 6 ± 1 G.T (sec) 15 ± 2 T.F.T (sec) 20 ± 3

Liquid A is black isocyanate and resin B is transparent polyol in the resin premix composition.

When foaming the polyurethane foam in the present invention, the resin premix and the isocyanate composition are blended in the mixing ratios illustrated in Table 1, and the resin premix (B liquid) and the isocyanate composition (A liquid) are mixed to foam the polyurethane foam. .

That is, according to the present invention, when ocher and expanded graphite are added to a polyurethane having excellent self-extinguishing and chemical properties, a polyurethane having excellent deterrence and flame retardancy is obtained, and the foam is molded into a predetermined shape and a predetermined size and A predetermined volume of polyurethane foam (polyurethane foaming agent) is foamed.

Example 1

In the composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; Polyol (B liquid) 25 to 45% by weight, 5 to 30% by weight ocher, 3 to 20% by weight of inorganic flame retardant is mixed at room temperature to prepare a liquid polyurethane composition, isocyanate (foaming catalyst) isocyanate ( A solution) 25-45 weight% (reaction ratio 1: 1-1: 1.6) are mixed, and a polyurethane foam is manufactured.

And other additives, such as a crosslinking agent and surfactant, are mixed in small amounts with the said A liquid and / or B liquid.

In the first embodiment, the ocher solution may be mixed instead of the ocher (ocher powder).

For example, when the ocher powder is mixed with the polyol (B liquid), 25 to 45% by weight of the polyol (B liquid) and 5 to 30% by weight of the ocher are mixed separately to form a colloidal ocher solution and then mixed to prepare a liquid polyurethane composition. Ocher may be added by the method of preparation.

In addition, it is possible to add ocher by preparing a liquid polyurethane composition by mixing colloidal ocher solution separately by mixing 3 to 20 wt% of inorganic flame retardant and 5 to 30 wt% of ocher.

In addition, ocher may be added by preparing a liquid polyurethane composition by mixing a liquid crosslinking agent and 5 to 30 wt% of ocher and mixing colloidal ocher solution separately.

In addition, ocher may be added by preparing a liquid polyurethane composition by mixing a liquid surfactant and 5 to 30 wt% of ocher and mixing colloidal ocher solution separately.

Example 2

In the composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; Polyol (B liquid) 25 to 45% by weight, expanded graphite 5 to 30% by weight, inorganic flame retardant 3 to 20% by weight is mixed at room temperature to prepare a liquid polyurethane composition, wherein the foaming agent (foaming catalyst) 25 to 45% by weight of isocyanate (Liquid A) (reaction ratio 1: 1 to 1: 1.6) is mixed to prepare a polyurethane foam.

And other additives, such as a crosslinking agent and surfactant, are mixed in small amounts with the said A liquid and / or B liquid.

Example 3

In the composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; A liquid polyurethane composition is prepared by mixing 25 to 45% by weight of polyol (B liquid), 2.5 to 15% by weight of ocher, 2.5 to 15% by weight of expanded graphite, and 3 to 20% by weight of inorganic flame retardant at room temperature. Polyurethane foam is manufactured by mixing 25-45 weight% (reaction ratio 1: 1: 1: 1.6) of isocyanate (A liquid) which is a blowing agent (foaming catalyst).

And other additives, such as a crosslinking agent and surfactant, are mixed in small amounts with the said A liquid and / or B liquid.

In the third embodiment, the ocher solution may be mixed instead of the ocher (ocher powder).

For example, when the ocher powder is mixed with the polyol (B liquid), 25 to 45% by weight of the polyol (B liquid) and 2.5 to 15% by weight of ocher are mixed to form a colloidal ocher solution and then mixed to prepare a liquid polyurethane composition. Ocher can be added in the same manner.

In addition, when the ocher powder is mixed with the expanded graphite, the ocher may be added by preparing a liquid polyurethane composition by mixing colloidal ocher solution by mixing the expanded graphite 2.5-15 wt% and the ocher 2.5-15 wt%. .

In addition, it is possible to add ocher by preparing a liquid polyurethane composition by mixing colloidal ocher solution by mixing 3 to 20 wt% of inorganic flame retardant and 2.5 to 15 wt% of ocher.

In addition, ocher may be added by preparing a liquid polyurethane composition by mixing a colloidal ocher solution by mixing a liquid crosslinker and 2.5 to 15 wt% of ocher.

In addition, ocher may be added by preparing a liquid polyurethane composition by mixing a colloidal ocher solution by mixing a liquid surfactant and 2.5 to 15 wt% of ocher.

Detailed manufacturing process according to Examples 1, 2 and 3 are as follows.

①. A loess flame retardant is prepared by mixing ocher and an inorganic flame retardant.

②. The ocher flame retardant is stirred with the solution A at room temperature. At this time, ocher flame retardant and liquid A have little reactivity, so they can be stored for a long time regardless of temperature in a sealed state and are easy to handle.

③. Expanded graphite is added thereto and stirred uniformly.

The expanded graphite has a role of filler and a flame retardant effect at the same time for uniform mixing of the ocherite flame retardant and A (isocyanate) solution.

④ The polyurethane solution is prepared by mixing the A solution and the B (polyol) solution.

In the reaction between the ocher flame retardant and the liquid B, rapid curing proceeds and the addition is continued at a constant ratio.

①, ②, ③ for the above manufacturing process does not matter if the order is reversed.

That is, ocher and expanded graphite can be added to both A and B liquids, and may be added separately. Since the ocher and / or the expanded graphite and the flame retardant are rarely reactive, the handling is easy and preferable.

In the present invention, the strength of the polyurethane foam is changed depending on the ocher added to the A, B liquid, and if the amount of ocher addition is increased, the strength of the polyurethane foam is increased, so it can be easily applied to building interior materials requiring strength.

Examples 4, 5 and 6 below may be prepared by mixing ocher and / or expanded graphite in a predetermined amount with an isocyanate (A liquid), which is a blowing agent (foaming catalyst), to prepare a polyurethane foam composition, wherein a polyol (B liquid ), The polyurethane foam is foamed.

Example 4

Polyurethane foam manufacturing composition composed of a resin premix containing isocyanate and other additives, wherein the polyurethane and the flame retardancy are greatly improved by adding 5 to 30% by weight of ocher to the isocyanate or resin premix by adding to the resin premix weight. A foam manufacturing composition is prepared, and a polyol (B liquid) is mixed at 25 to 45% by weight (reaction ratio 1: 1 to 1: 1.6) to foam the polyurethane foam.

And other additives, such as a crosslinking agent and surfactant, are mixed in small amounts with the said A liquid and / or B liquid.

In the fourth embodiment, the ocher solution may be mixed instead of the ocher (ocher powder).

For example, 5 to 30% by weight of a colloidal ocher solution in which ocher powder is mixed with at least one of a polyol, an inorganic flame retardant solution, a liquid crosslinking agent, and a liquid surfactant is mixed with an isocyanate or resin premix with ocher in a resin premix. The ocher can be added by producing the polyurethane composition.

Example 5

Polyurethane foam manufacturing composition composed of resin premix containing isocyanate and other additives, wherein the expanded graphite is added to the isocyanate or resin premix by mixing 5-30 wt% of the resin premix weight to improve the determinism and flame retardancy. A urethane foam manufacturing composition is prepared, and the polyol (B liquid) is mixed at 25 to 45% by weight (reaction ratio 1: 1 to 1: 1.6) to foam the polyurethane foam.

And other additives, such as a crosslinking agent and surfactant, are mixed in small amounts with the said A liquid and / or B liquid. It is created.

Example 6

In the composition for preparing polyurethane foam composed of resin premix containing isocyanate and other additives, 2.5 to 15 wt% of ocher and expanded graphite are added and mixed with isocyanate or resin premix to the resin premix weight, respectively, to prevent retardance and flame retardancy. A greatly improved composition for preparing a polyurethane foam is prepared, and a polyol (B liquid) is mixed at 25 to 45% by weight (reaction ratio 1: 1 to 1: 1.6) to form a polyurethane foam.

And other additives, such as a crosslinking agent and surfactant, are mixed in small amounts with the said A liquid and / or B liquid. It is created.

In Example 6, instead of the ocher (ocher powder) it can be composed by mixing the ocher solution.

For example, the colloidal ocher solution obtained by mixing the ocher powder with at least one of polyol, an inorganic flame retardant, a liquid crosslinking agent, and a liquid surfactant together with 2.5 to 15 wt% of ocher and 2.5 to 15 wt% of expanded graphite is used as the isocyanate or resin. The ocher may be added by preparing a liquid polyurethane composition by mixing the ocher with the resin premix in the premix.

In the present invention, a polyurethane foam may be foamed into a two-pack form by mixing A liquid and B liquid, or polyurethane foam may be foamed by reacting A liquid with urethane with pentane gas or freon gas.

The loess used in the present invention is natural ocher in the form of commercialized microparticles, and is a commercially available commodity. Therefore, the process description of taking natural ocher to remove foreign substances, sterilizing, pulverizing and processing to obtain fine particles, etc. Is omitted.

The expanded graphite used in the present invention is also a commercially available product in the form of a fine powder, and thus descriptions of manufacturing processes and the like are omitted.

The ocher is a fine size that can be evenly mixed with the polyurethane liquid of the colloidal ecology, for example, the fine particles of 200 mesh ~ 1,000 mesh, the expanded graphite is also fine particles of 60 mesh ~ 150 mesh, even if mixed with the liquid A and / or liquid B Remain colloidal.

The loess is easy to obtain, the porosity is very large as 50 ~ 55%, in particular, the adsorption, deodorization function, humidity control function of toxic gases, including harmful chemicals. In addition, since a large amount of far infrared rays are generated, it has a beneficial effect on the surroundings and the human body, has an antibacterial and sterilizing effect, is environmentally friendly and inorganic, and thus does not generate harmful substances in case of fire.

The loess and expanded graphite are excellent in heat stability as an inorganic material having high heat resistance. In addition, the polyol containing the ocher and expanded graphite may be reused because the physical properties do not change without being precipitated even when not used for a long time.

In the present invention, the polyurethane foam is characterized in that the ocher color is naturally expressed as shown in FIGS. 14 and 15 by mixing ocher powder or ocher solution.

In the present invention, a small amount of a surfactant such as alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, etc. within a range that does not change the physical properties of the polyurethane so as to facilitate the mixing of the flame retardant with ocher and expanded graphite. Mixed additives may be added, and other known additives may be used in combination to assist in improving determinability and flame retardancy.

In the present invention, when the flame retardant and the ocher and the expanded graphite and the polyurethane are mixed, the ultrasonic vibration with a plurality of ultrasonic vibrators causes the respective surface tensions to be dispersed or degraded and more effectively mixed. The ultrasonic waves refer to vibrations of 20,000 Hz or more outside the actual audible frequency in the range of 20 kHz to 20,000 kHz. When ultrasonic waves are irradiated into the water, an innumerable cavitation occurs and disappears. When the vibration of the bubble is generated, the micro-current is generated, causing the mass agitation, and when the resonance is extinguished, the energy is expanded to hundreds of thousands to millions of times, and the pressure and temperature of the bubble rise, resulting in micro thermal action and dispersion. This action promotes the physical and chemical reactions in the medium.

In the present invention, this phenomenon is repeated about 20,000 to 2,000,000 (20 ㎑ to 2 MHz) times per second, while the expanded graphite and / or the ocher and the flame retardant are dispersed by resonating by the ultrasonic vibrator, and are evenly distributed with the A liquid and / or B liquid. Are mixed. In particular, since the medium is a liquid, there is little energy reduction and it is mixed efficiently.

Polyurethane flame-retardant treatment according to the present invention is a mixture of expanded graphite harmless to the human body and ocher and flame retardant harmless to the human body is not only excellent in determinism and flame retardancy, but also adsorption and removal of harmful chemicals and toxic gases by ocher And far-infrared radiation, excellent heat insulation, antibacterial and flame retardant, humidity control and deodorizing effect.

In the present invention, in the case of polyurethane treated only with flame retardant, thermal deformation occurs even when exposed for several seconds in direct heat of several hundred degrees Celsius. In the case of the polyurethane foaming agent of the present invention, which greatly improves in decompression and flame retardancy, it does not burn even when heated for 10 minutes with a gas torch of about 1,000 ° C.

The present invention is excellent in mold resistance and moisture permeability due to the action of loess, so that mold does not occur, and it has excellent adsorption and deodorization effect due to its porous structure, which can be used as a good material for various construction materials. It is excellent for compressive strength, thermal conductivity, mold resistance, moisture permeability and deodorizing effect, so it is harmless to human body and can be used for various building materials such as flooring, ceiling, interior and exterior materials.

In the present invention, the flame retardant is added to the inorganic flame retardant is possible to form a high flame-retardant and more environmentally friendly polyurethane foam, it is possible to serve as a filler of the polyurethane foam is possible to control the density and strength according to the addition amount.

Expanded graphite can be completely mixed evenly due to the low density and specific gravity when mixed with ocherite flame retardant and solution A, or with expanded graphite with ocherous flame retardant solution and liquid B, wherein the expanded graphite is a liquid colloidal state.

Polyurethane prepared by the manufacturing method of the present invention has a good adhesion to the metal sheet (metal outer shell) during foaming is very effective in sandwich panel production and its productivity is improved.

Since the polyurethane of the present invention is a liquid mixture of ocher and expanded graphite, it is constructed by mixing foaming catalysts, such as spraying, spraying, spraying, spraying, foaming, BOARD, etc. can do.

In the present invention, in the case of one-part type (A-type), the polyurethane foam is heat-cured by adding a blowing agent such as pentane or butane and simultaneously generates bubbles to make polyurethane foam, about 95% of the volume is air, and 3% is ocher and / or expanded graphite and the remaining 2% is resin.

And in the case of the two-component type consisting of a polyol and an isocyanate, a polyurethane foam is made by mixing them.

Polyurethane foam (polyurethane foaming agent) foamed with the polyurethane is light, excellent in water resistance, heat insulation, sound insulation and cushioning, etc. It is widely used as wall and ceiling materials, and conventional polyurethane foam is weak to heat, and its large shrinkage deformation is large, and the overall shape is changed instantly by small embers, leading to large fires, and generating a lot of poisonous smoke during combustion. In the present invention, there is a problem of killing lives, but in the present invention, polyacrylonitrile has excellent determinism and flame retardancy due to a complex mechanism of yellow clay having excellent adsorption to harmful chemicals and toxic gases generated in a fire, and expanded graphite having excellent flame retardancy and self-extinguishing. Urethane and its foaming agent (polyurethane foam) are obtained, and the flame as well as the fire are exposed for a long time. Or it has excellent ductility and flame retardance billion and advantages that self-digestion is achieved even if the initial flame is greater.

The present invention is excellent in non-toxicity (Ds value) of 200 or less.

Starting materials used in the preparation of the polyol in the present invention include propylene glycol, ethylene glycol, glycerin, methyl glucoside, glucose, trimethylol propane, pentaerythritol, pentaerythritol, ethylene diamine, The substance which has polyhydric hydroxyl groups, such as toluenediamine, sugar, sorbitol, etc. are mentioned.

Examples of the unit monomers of the polymer include substances having epoxide groups such as ethylene oxide, propylene oxide, and butylene oxide, and the catalysts include basic catalysts such as sodium hydroxide, potassium hydroxide, cesium oxide, trimethyl amine, triethylamine, and the like. , Metal catalysts such as AlCl ₃ , ZnCl ₂ , FeCl ₃ , BF ₃ , BCl ₃ , BeCl ₂ , FeBr ₃ , SnCl ₄ , TiCl ₄ , ZrCl ₄ , ZnCl ₂ , and Al (OR) ₃ , Mg (OR) Epoxy reaction may be performed with ₂ , Zn (OR) ₂ , Al (I-Pr) 3-ZnCl ₂ , Fe (Oet) ₃ , AlEt ₃ , and the like.

Reactive catalysts used in the production of polyurethane foams include amine catalysts and metal catalysts.

Crosslinking agents and chain extenders used in the production of polyurethane foams include diols / triols having a polyhydroxyl group having a molecular weight of 17 to 600, alkanolamines and amines.

In the present invention, a surfactant, a flame retardant, a filler, a dye, a stabilizer, etc. may be used to impart a special function in manufacturing the polyurethane foam. Surfactants used to control the structure of the cell to the appropriate size during foam foaming include organosilicon compounds, alkylphenols (ethoxylated alkyl phenol), aliphatic alcohol (ethoxylated fatty alcohol), paraffinoils, perm oil (castor oil).

Flame retardants for polyurethane foam include tricresyl phosphate, tris- (1,3-dichloropropyl phosphate), tris (2,3-dibroropropyl Phosphorus-based flame retardants such as tris (2,3-dibromopropyl) phosphat and tetrakis (2-chloroethyl) ethylene diphosphate, aluminum oxide hydrate and antimony trioxide Inorganic flame retardants such as antimony trioxide and melamine cyanurate are used.

In the present invention, the combustion experiment by horizontally heating a flame of about 1,000 ℃ with a polyurethane foam having greatly improved deterrence and flame retardancy using a gas torch, the conventional flame-retardant conventional polyurethane foam is melted within a few seconds with heating Polyurethane foam of the present invention continuously ignited, but treated with ocher and expanded graphite exhibits self-extinguishing and semi-incombustible that does not collapse even when directly exposed to a gas fire flame of about 1,000 ℃ for 10 minutes, wherein the flame retardant and ocher and expanded graphite In addition, the generation of harmful chemicals and toxic gases is suppressed as much as possible, and the generated hazardous chemicals and toxic gases are quickly adsorbed and removed into the porous soil of the loess to prevent the expansion of fire and to generate harmful chemicals and toxic gases. And release is suppressed and minimized.

1 is a graph showing the results of measuring the deodorization rate of ocher (HT) and portland cement (PC: portland cement) mixed and applied to the present invention, X-axis is the deodorization rate of the ocher (tested with ammonia gas) The X axis represents the reaction time. As can be seen in Figure 1 it can be seen that the deodorization rate of the loess is significantly higher and gradually increases over time.

Figure 2 is a measurement of the adsorption performance of volatile organic compounds (formaldehyde), one of the environmental performance of the ocher CLC, the Y-axis shows the concentration of formaldehyde and the X-axis shows the time, as can be seen from the results VOC adsorption performance It can be seen that ocher ALC and ocher CLC have greater adsorption capacity than ocher mortar, which is known to be large.

This is considered to be due to the adsorption effect of the micro-pores on the C-S-H bond in addition to the adsorption effect of the microstructure of ocher.

Figure 3 is a graph showing the amount of gas emissions and smoke density reduction, the squares and circles represent ocher and other SIO ₂ reactants, Smoke Density is the toxic gas (smoke) density, A-COY is the amount of gas emissions As it is shown, it can be seen that the gas emission and smoke density decreases as the concentration of ocher increases.

4 is an enlarged photograph of a microporous structure formed in diatomaceous earth with a microscope, and a black portion is a porous portion.

5 is an enlarged photograph of the microporous structure formed in the zeolite under a microscope, the black portion being a porous portion.

6 is an enlarged photograph of a microporous structure formed on a fly ash under a microscope, and a black portion is a porous portion.

7 is an enlarged photograph of the microporous structure formed in the slag under a microscope, the black portion is a porous portion.

8 is a microscopic image of the microporous structure formed on the yellow soil, the black portion is a porous layer, it can be seen that far more than the porous layer formed on the diatomaceous earth, zeolite, fly ash, slag, due to the adsorption, moisture absorption, It can be seen that it can absorb the harmful gas and smoke best.

9 is an enlarged photograph of the microstructure of ocher, showing that most of the fine porous layer having excellent adsorption rate of soot, VOC, toxic gas, etc., shows the highest deodorization rate and adsorption characteristics. .

10 to 22 is a comparison picture of the fire characteristics, general polyurethane foam (a) treated with a flame retardant solution, polyurethane foam (b) treated with ocher and flame retardant, ocher, expanded graphite and flame retardant The treated polyurethane foam (c) and the expanded graphite and the flame retardant polyurethane foam (d) are listed in this order.

Looking at the characteristics of each fire, when the general polyurethane foam (a) of Figure 11 burned with a gas torch as shown in Figure 12 melts badly (convex portion melts in the upper center of Figure 11), there is no self-extinguishing function As shown in the right picture of FIG. 13, the fire is burning and burning, whereas the polyurethane foam (b) treated with ocher and flame retardant as shown in the left picture of FIG. 13 can be seen to have evolved by self-extinguishing.

As shown in Fig. 14, the polyurethane foam treated with ocher and flame retardant solution (b) is much less melted as shown in the left photo of FIG. 13 or the photo of FIG. Due to the excellent porosity of the loess, toxic gases such as VOCs are absorbed (absorbed) or removed, and a carbon film is formed on the surface as shown in FIG. The toxic gas generated is absorbed and removed.

Polyurethane foam (c) treated with ocher, expanded graphite, and flame retardant as shown in Figure 16 is a carbon film formed on the surface as shown in Figure 22 to show the properties of suppressing flame retardancy and smoke as well as VOC by adsorption of porous ocher The toxic gas of is adsorbed and removed, and as shown in the ignition picture, as shown in FIG. 17, as the expanded graphite rapidly expands, a carbon film is formed on the surface to form a fire barrier or a fire barrier, or self-extinguishing.

18 is a photograph of a self-extinguishing state after ignition, the left side is a polyurethane foam (c) treated with ocher, expanded graphite and flame retardant, the right side is a polyurethane foam (d) treated with expanded graphite and flame retardant In the case of the left polyurethane foam (c) containing porous ocher, which has excellent adsorption of gas and gas, most of the fumes and toxic gases are adsorbed by the ocher porous and no longer diffuse (disperse) to the outside. In the right picture treated with the polyurethane foam (d) it can be seen that the fumes generated by the burning and the toxic gas contained in the fumes continue to diffuse outside without adsorption.

In the present invention, the flame retardant is an inorganic flame retardant and does not generate a highly toxic halogen gas, so there is almost no risk of asphyxiation.

In the present invention, when only the clay is mixed, the adsorption rate is excellent, but the self-extinguishing capacity falls, and the mixed carbon is expanded to form a carbon dioxide (CO ₂ ) film by rapid and rapid expansion of the expanded graphite in the event of inflow of external oxygen (O ₂ ). This is blocked and self evolution is achieved.

In the expanded graphite, chemicals contained by heat generate gas, and as a result, scaly graphite rapidly expands and forms a stable layer (CO ₂ barrier) on heat and chemicals, thereby improving flame retardancy and self-extinguishing characteristics in a solid phase manner. The larger the particles, the larger the expansion volume and the expansion start temperature is determined by the chemicals used.

The present invention as described above is not limited to the present embodiment and the accompanying drawings, various substitutions, modifications and changes are possible within the scope without departing from the technical spirit of the present invention, which is usually in the art It is self-evident for those who have knowledge.

1: Deodorization rate graph of the loess and Portland cement in the present invention.

2 is a graph measuring the adsorption performance of loess in the present invention.

3 is a graph showing the amount of gas discharge and smoke density reduction in the present invention.

4: An enlarged photograph of diatomaceous earth under a microscope.

5: A photograph taken by magnifying a zeolite under a microscope.

Figure 6 is a photograph of a fly ash magnified under a microscope.

7: Magnified photograph of the slag under the microscope.

8: An enlarged photograph of an ocher under a microscope.

9: An enlarged photograph of an ocher microstructure under a microscope.

10: In order to compare the fire characteristics in the present invention, a general polyurethane foam (a), a polyurethane foam treated with ocher and flame retardant (b), and a polyurethane foam treated with ocher, expanded graphite and flame retardant ( c) and photographs listing the expanded graphite and polyurethane foam treated with flame retardant (d).

11 is a photograph of a general polyurethane foam (a).

12: Photo after digestion of general polyurethane foam (a).

Fig. 13: Photo of the ignition state of the polyurethane foam (b) treated with ocher and flame retardant and general polyurethane foam (a) The polyurethane foam (b) treated with ocher and flame retardant is in a self-extinguishing state.

14 is a photograph of polyurethane foam (b) treated with ocher and flame retardant.

15 is a photograph of polyurethane foam (b) treated with self-extinguishing loess and flame retardant.

Figure 16: Photograph of polyurethane foam (c) treated with ocher and expanded graphite and flame retardant.

Figure 17: Photo of the ignition state of the polyurethane foam (b) treated with ocher and flame retardant, and the polyurethane foam (c) treated with ocher and expanded graphite and flame retardant.

18 is a photograph after self-extinguishing of polyurethane foam (b) treated with ocher and flame retardant, and polyurethane foam (c) treated with expanded graphite and flame retardant, with polyurethane foam treated with ocher and flame retardant ( In b), the toxic gas was adsorbed and removed, but the expanded graphite and the flame retardant liquid-treated polyurethane foam (c) were in a toxic gas state.

Figure 19: Photographs after self-extinguishing of ocher and expanded graphite and polyurethane foam (c) treated.

20: Photograph of expanded graphite and polyurethane foam (d) treated with flame retardant solution.

Fig. 21: Pictures after self-extinguishing of expanded graphite and flame retardant liquid-treated polyurethane foam (d).

Figure 22: Photograph of a carbide film formed on the surface of polyurethane foam by expanded graphite.

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

(a)-General Urethane

(b)-Polyurethane treated polyurethane foam

(c)-Polyurethane foam treated with ocher and expanded graphite

(d)-Polyurethane foam with expanded graphite

Claims (15)

In the composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; Polyurethane 25-45% by weight, loess 5-30% by weight, inorganic flame retardant 3 to 20% by weight at room temperature mixed with excellent polyurethane foam composition for producing excellent flame retardancy. In the composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; A composition for producing polyurethane foam having excellent determinability and flame retardancy obtained by mixing 25 to 45 wt% of polyol, 5 to 30 wt% of expanded graphite, and 3 to 20 wt% of inorganic flame retardant at room temperature. In the composition for producing a polyurethane foam composed of a resin premix containing a polyol, other additives; Polyol 25 to 45% by weight, ocher 2.5 to 15% by weight, expanded graphite 2.5 to 15% by weight, inorganic flame retardant 3 to 20% by weight of the composition for producing a polyurethane foam excellent in incombustibility and flame retardancy. The method of claim 1 or 3; Polyurethane foam manufacturing composition excellent in anti-flammability and flame retardant by mixing ocher solution instead of loess. Polyurethane foam excellent in the determinativity and flame retardancy obtained by foaming the composition of any one of Claims 1-3 with a foaming agent. The method according to claim 5; Polyurethane foam is a polyurethane foam with excellent deterrence and flame retardancy, characterized by the appearance of ocher color by the mixed addition of ocher. The method according to claim 5; Reaction ratio of the composition and the foaming agent is 1: 1 to 1: 1.6 polyurethane foam, characterized in that excellent in flame retardancy and flame retardancy. In the composition for producing a polyurethane foam composed of a resin premix containing an isocyanate, other additives; A composition for producing polyurethane foam having excellent anti-flammability and flame retardancy obtained by mixing 5-30 wt% of loess at room temperature with respect to the weight of resin premix. In the composition for producing a polyurethane foam composed of a resin premix containing an isocyanate, other additives; A composition for producing polyurethane foam having excellent deterrence and flame retardancy obtained by mixing 5 to 30% by weight of expanded graphite with respect to the weight of resin premix at room temperature. In the composition for manufacturing polyurethane foam composed of resin premix containing isocyanate and other additives; A composition for producing polyurethane foam having excellent anti-flammability and flame retardancy obtained by mixing 2.5-15 wt% of ocher and expanded graphite with respect to the weight of resin premix at room temperature. The method of claim 8 or 10; Polyurethane foam manufacturing composition excellent in anti-flammability and flame retardant by mixing ocher solution instead of loess. The method according to claim 1 or 3 or 8 or 10; Loess is a composition for producing polyurethane foam with excellent decompression and flame retardancy, characterized in that 200mesh ~ 1,000mesh. The method according to claim 2 or 3 or 9 or 10; Squeezed graphite is a composition for producing polyurethane foam having excellent deterrence and flame retardancy, characterized in that 60mesh ~ 150mesh. A polyurethane foam having excellent decompression and flame retardancy, wherein the composition according to any one of claims 8 to 10 is mixed with a polyol to obtain a polyurethane foam. The method according to claim 14; Polyurethane foam composition with excellent retardancy and flame retardancy, characterized in that the reaction ratio of 1: 1 to 1: 1.6.

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