KR101834824B1 - A method for preparing water-soluble fire-retardant liquid - Google Patents

Abstract

The present invention relates to a method for producing a flame retardant liquid which prevents flame-retardant components from being discharged together with water in a process of coating or applying on an object and drying, and specifically, to a method for producing a flame retardant liquid, in which a water-soluble flame retardant liquid is produced by mixing gelatin, ethylene vinyl acetate, ammonium phosphate monobasic, ammonium dihydrogenphosphate, sodium hydrogen carbonate, carboxymethylcellulose, sodium silicate and the like, and a pretreated flame retardant material, to prevent evaporation of the flame retardant components along with the water evaporated during the drying process, is used to enable the flame retardant material to exhibit partial water-insoluble property with water mixed therewith, thereby capable of preventing evaporation of water and evaporation of a flame retardant main material at the same time.

Description

[0001] The present invention relates to a water-soluble fire-retardant liquid,

The present invention relates to a process for producing a water-soluble flame-retardant, and more particularly, to a process for producing a flame-retardant liquid which prevents the flame-retardant material from being discharged together with water during the process of coating or coating the flame- .

More particularly, the present invention relates to a method for preparing a water-soluble flame retardant by mixing gelatin, ethylene vinyl acetate, ammonium phosphate monobasic, ammonium dibasic, sodium hydrogen carbonate, carboxymethyl cellulose, sodium silicate, The flame retardant is prevented from being evaporated along with the moisture, so that the flame retardant is prevented from being evaporated at the same time as the evaporation of the water due to the partial insolubility with water mixed with the flame retardant, To a process for producing the same.

Wood, wood substitute water, paper and fabric are light and strong, so they have high non-strength and easy to process. They are widely used for building materials because of strong electricity, heat and moisture. Organic building materials have the above-mentioned merits, but have disadvantages such as dimensional instability, combustibility, and thermal degradability.

Among the organic building materials, especially wood, chemical reaction with oxygen in the air shows the oxidation phenomenon that burns with heat and light. Therefore, when wood is heated in the air, decomposition starts at around 180 ° C. and combustible gas is generated as decomposition proceeds , There is a fatal disadvantage that the flash point is low and the inside of the building is instantly burned even in a small fire due to diffusive combustion in case of fire. Therefore, since it is required not only durability such as strength, but also preservation and fire resistance, it is necessary to study a proper refractory treatment technique and performance evaluation of wood which is widely used as a plywood as a member used for roof, wall board and flooring .

Techniques for improving flame retardancy and flame retardancy of these organic building materials have been developed, for example, flame retardants are widely used to suppress the combustion of wood. Generally, a flame retardant is a substance which is physically or chemically improved to easily combust and is added so as not to burn, and is separated into an organic and an inorganic type depending on the constituents of the flame retardant currently used.

The organic system is mainly classified into a halogen system, a phosphate system, a bromine system and a chlorine system, and the inorganic system is classified into an aluminum hydroxide system, an antimony system, and a magnesium hydroxide system. Particularly, the halogen-based flame retardant has a large influence on the human body, such as being harmful to the global environment due to the halogen component generated from the raw material and deteriorating the working environment during the treatment. In addition, And the like.

For this reason, researches on inorganic flame retardants have been continued. For example, magnesium hydroxide (Mg (OH) ₂ ), aluminum hydroxide (Al (OH) ₃ ), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ) Inorganic flame retardants are mainly used.

Various types of flame retardants are used, and they are mixed with a variety of subordinate materials for ease of use. Techniques related to the flame retardant prepared by mixing with the main materials are described in Patent Documents 1 to 3 below.

Patent Document 1 (Korean Patent Laid-Open Publication No. 10-2013-0042916) relates to a method for producing a core-shell type inorganic-organic composite flame retardant, and more particularly to a method for producing a core- The present invention relates to a method for producing an inorganic-organic composite flame retardant of core-shell type which is harmless to the human body and is environmentally friendly, by selecting and mixing at least one inorganic compound, stirring the mixture with an organic compound,

Patent Document 2 (Korean Patent Registration No. 10-0538554) discloses a process for producing a phosphorus-containing compound by mixing and sintering a phosphorus compound, a nitrogen-based compound, and a boron-based compound to prepare a solid component, Halogen-containing flame retardant containing 20 to 20% by weight, nitrogen of 1 to 25% by weight, and boron of 0.01 to 10% by weight,

In Patent Document 3 (Korean Patent Laid-Open No. 10-2003-0076806), 100 g of a mixture of 50 to 55% by weight of carboxymethylcellulose sodium, 30 to 40% by weight of sodium phosphate monobasic and 15 to 25% (B) was prepared by mixing 400 to 1200 g of silicon with the above solution (A) to prepare a mixed solution (B). The mixed solution (B) and the sodium silicate solution (2000) Based flame retardant and a water-soluble inorganic flame retardant for impregnation which has flame retardancy and water resistance.

However, since conventional inorganic flame retardants are not water-soluble, flame retardant components are precipitated when they are dispersed in water. When coated on a substrate, coating defects are caused by inorganic flame retardant particles, .

In order to overcome such disadvantages, the inventor of the present application developed the flame retardant of Patent Document 4.

Patent Document 4 (Korean Patent Registration No. 10-0636876) discloses a method for producing a flame retardant, which comprises dissolving 1 to 2% by weight of gelatin in 98 to 99% by weight of water to prepare an aqueous gelatin solution; The gelatin aqueous solution is prepared by adding 15 to 20% by weight of ethylene vinyl acetate, 8 to 11% by weight of ammonium phosphate monobasic, 8 to 11% by weight of dibasic ammonium phosphate, 3 to 4% by weight of sodium hydrogencarbonate, Mixing 3 to 4% by weight of cellulose (CMC); Mixing 90 to 95% by weight of the mixed mixture with 5 to 10% by weight of sodium silicate.

The water-soluble flame retardant of Patent Document 4 thus produced does not deteriorate the inherent physical properties of the interior and exterior materials, paper, and fabric when used as a flame retardant of the present invention, as well as the interior and exterior materials of buildings, paper, So as to delay the ignition point of the wood or the like by releasing the incombustible gas in the case of fire, and there is an advantage that the toxic gas and soot are hardly generated. However, the flame retardant of Patent Document 4 has a problem that the flame retardant effect of the object is deteriorated because the flame retardant is discharged like water during the drying process, and it is necessary to develop a new flame retardant that can improve the flame retardant.

Korean Patent Publication No. 10-2013-0042916 Korean Patent No. 10-0538554 Korean Patent Publication No. 10-2003-0076806 Korean Patent No. 10-0636876

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a method for manufacturing a water-soluble flame-retardant solution.

Particularly, the present invention relates to a method for producing a flame-retardant liquid by sequentially mixing a water-insoluble carboxymethyl cellulose and a water-soluble carboxymethyl cellulose in a flame-retarding matrix, and then mixing sodium silicate, The present invention also provides a method for manufacturing a water-soluble flame-retardant liquid, which is capable of maintaining the flame-retardant property as the flame-retardant material does not evaporate even when water evaporates during the process of applying the flame-retardant liquid to the object.

In order to achieve the above object, the present invention provides a method for producing a water-insoluble carboxymethyl cellulose, comprising the steps of: (1) heat treating carboxymethyl cellulose (CMC) to prepare water-insoluble carboxymethyl cellulose; (2) preparing a mixture by mixing ammonium phosphate monobasic, flameproof ammonium phosphate, sodium bicarbonate and carboxymethylcellulose, which are flame retardants in powder form, which mixture comprises ammonium phosphate monobasic, ammonium dibasic, sodium bicarbonate And water-insoluble carboxymethylcellulose prepared in the step (1), followed by secondary mixing of the water-soluble carboxymethyl cellulose to prepare a mixture; (3) mixing sodium silicate with the mixture prepared in the step (2); (4) preparing an adhesive by mixing gelatin and ethylene vinyl acetate, and mixing the prepared adhesive with the mixture of sodium silicate in step (3); And (5) mixing the mixture of the adhesive of step (4) and water. The method of manufacturing a water-soluble flame-retardant liquid according to claim 1,

Further, the present invention provides a water-soluble flame retardant prepared by the above method.

The water-soluble flame retardant according to the present invention has an effect of preventing the flame-retardant component from being discharged together with water during the process of coating or applying the composition on a subject, followed by drying.

That is, the present invention provides a water-soluble flame-retardant solution prepared by using gelatin, ethylene vinyl acetate or the like as a flame retardant base material of ammonium phosphate monobasic, ammonium dibasic and hydrogencarbonate, Some of methylcellulose is water-soluble and then mixed with water-borne carboxymethyl cellulose to make it insoluble with water mixed with water, thereby preventing flame-retardant residues from being evaporated even when moisture is evaporated during drying process to maintain flame retardancy There is an effect that can be done.

While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the present invention will be described in detail with reference to examples.

The present invention has the effect of keeping the flame retardant effect by preventing the flame retardant from evaporating while moisture is evaporated when the flame retardant is applied to the object by drying after the flame retardant main material is made insoluble.

The method for producing a water-soluble flame retardant of the present invention having the above-

(1) heat-treating carboxymethylcellulose (CMC) to prepare water-insoluble carboxymethylcellulose;

(2) preparing a mixture by mixing ammonium phosphate monobasic, flameproof ammonium phosphate, sodium bicarbonate and carboxymethylcellulose, which are flame retardants in powder form, which mixture comprises ammonium phosphate monobasic, ammonium dibasic, sodium bicarbonate And water-insoluble carboxymethylcellulose prepared in the step (1), followed by secondary mixing of the water-soluble carboxymethyl cellulose to prepare a mixture;

(3) mixing sodium silicate with the mixture prepared in the step (2);

(4) preparing an adhesive by mixing gelatin and ethylene vinyl acetate, and mixing the prepared adhesive with the mixture of sodium silicate in step (3); And

(5) mixing the mixture in which the adhesive of the step (4) is mixed with water.

As in step (1) of the present invention, a part of carboxymethyl cellulose (CMC) serving as a viscosity modifier in the flame retardant solution is pretreated so as to be insoluble in water, and the flame retarding agent is mixed with water-insoluble carboxymethyl cellulose, By making the flame retardant liquid insoluble, it is possible to prevent the flame-retardant flask from being evaporated together with water during drying.

Therefore, when mixing flame-retardant monomers such as ammonium phosphate monobasic, ammonium dibasic, hydrogencarbonate and carboxymethylcellulose (CMC) as a viscosity controlling agent, water-insoluble carboxymethyl cellulose is first mixed with the flame- Thereby making the flame-retardant presintering material water-insoluble. By mixing water-soluble carboxymethyl cellulose with the water-insoluble primary mixture in this manner, a part of the flame-retardant host material mixture can be made water-insoluble.

The water-insoluble carboxymethyl cellulose and the water-soluble carboxymethyl cellulose may be contained in the mixture at a weight ratio of 40 to 60:40 to 60.

The mixing of step (2) may be carried out by mixing ammonium phosphate dibasic, ammonium dibasic, hydrogencarbonate and carboxymethyl cellulose, which are flame retardants, in powder form at a ratio of 8 to 11: 8 to 11: 3 to 4: Can be mixed.

The ammonium phosphate ((NH ₄ ) HPO ₄ ) added to the water-insoluble flame retardant host material adds a flame retardant function. When the addition rate of ammonium phosphate is less than the above range, the effect is insignificant. It is difficult to mix with a mixture of gelatin and water to be added subsequently, so it is preferable to add them in the above ratio.

In addition, the second ammonium phosphate ((NH ₄ ) H ₂ PO ₄ ) also adds a flame retarding function like the first ammonium phosphate. The ammonium phosphate emits ammonia, which is a noncombustible gas in the case of fire. It is preferable to blend them in the same manner as ammonium phosphate monobasic.

In addition, sodium bicarbonate (NaHCO ₃ ) increases the amount of flammable gas in the event of fire to delay the fire. Since the solubility in water of 100 g is about 8.8 g, it is most preferable to limit the compounding ratio to the above range.

In the step (3), the mixture of the flame retardant and carboxymethyl cellulose and the sodium silicate may be mixed at a ratio of 90 to 95: 5 to 10 by weight. The sodium silicate may be a commercially available sodium silicate solution, but is not limited thereto. Since the sodium silicate solution is an inorganic aqueous solution which is foamed by heat to form a heat-resistant refractory layer, the sodium silicate solution functions to prevent combustion and fire from proceeding in case of fire. If the addition amount of the sodium silicate is less than the above range, the effect is insignificant, and if it exceeds the above range, the effect is excessive.

The step (4) is preferably prepared by mixing gelatin and ethylene vinyl acetate in a ratio of 0.4 to 1.2: 15 to 20, and mixing the prepared mixture with 40 to 45 wt% can do.

The gelatin has a basic functional group such as alanine (alanine), glycine, proline, arginine and glutamic acid, which are chemically amino acid groups, and the chains are connected by carbon atoms If the gelatin is adsorbed on the surface of the combustion material, a large amount of ammonia (NH ₃ ), which is a nonflammable gas, is released, so that the concentration of the mixed gas around the combustible material is prevented from reaching the flammable limit, . In addition, there is a possibility of having a great influence on the flame retarding effect by inhibiting the approach of oxygen due to the presence of the already existing carbonized film, and the carbonized chains present in the gelatin may undergo oxidation reaction or heat transfer But also to prevent vaporization, which is the main cause of flame propagation.

The ethylene-vinylacetate (EVA) is excellent in stability and weatherability. When the wood, paper, non-woven fabric, fabric or the like is immersed in the flame retardant of the present invention or the flame retardant is applied to the product, And serves as an adhesive to ensure good adhesion. If the content of ethylene vinyl acetate is less than the above range, the adhesive serves little as an adhesive. If it exceeds the above range, it is not economical and an adhesive effect is not further increased. Therefore, it is preferable to use the blend ratio within the above range.

In the step (5), the mixture is mixed so as to contain 35 to 45% by weight of water. If the temperature of the water is less than 20 ° C, the solubility of the gelatin added to the mixture becomes poor. If the temperature of the gelatin exceeds 30 ° C, it is preferable to use water at 20 to 30 ° C since the gelatin aqueous solution tends to gel.

The present invention also provides a water-soluble flame retardant prepared by the above method. The water-soluble flame retardant can be used for various kinds of flammable materials such as paper, fiber, fabric, and styrofoam as well as wood, wood substitute for building materials, wood, paper, fiber, , Which can be used by applying the flame retardant of the present invention, thereby preventing rapid combustion and fire in the event of fire, thereby suppressing the fire at an early stage.

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

Example  One. Flame retardant  Produce

(1) Carboxymethylcellulose (CMC) was heat-treated at 80 캜 for 30 minutes to prepare water-insoluble carboxymethylcellulose. The mixture was prepared by mixing 9.5: 9.5: 3.5: 3.5 by weight of ammonium phosphate monobasic, ammonium bicarbonate, sodium hydrogencarbonate and carboxymethylcellulose (CMC), which are flame retardants in powder form. Insoluble carboxymethylcellulose prepared above is firstly mixed with ammonium phosphate monobasic, ammonium dibasic and hydrogencarbonate, and then water-soluble carboxymethylcellulose is secondarily mixed with the first mixture, . The water-insoluble carboxymethyl cellulose and water-soluble carboxymethyl cellulose used in the preparation of the mixture are used in a weight ratio of 50:50.

(2) Sodium silicate was mixed in the ratio of 92.5: 7.5 by weight to the mixture prepared in the step (1) to prepare a mixture of sodium silicate.

(3) An adhesive was prepared by mixing gelatin and ethylene vinyl acetate in a ratio of 0.8: 17.5 by weight, and 42.5% by weight of the adhesive prepared above was mixed in the mixture of sodium silicate prepared in step (2).

(4) To the mixture in which the adhesive of the step (3) was mixed, 25% of water was mixed so as to contain 40% by weight of water.

Comparative Example  One. Flame retardant  Produce

(1) Gelatin and water at 25 캜 were mixed and dissolved in a ratio of 1.5: 98.5 by weight to prepare an aqueous gelatin solution.

(2) An aqueous solution containing 56.5% by weight of the gelatin aqueous solution prepared in the above step (1), 17.5% by weight of ethylene vinyl acetate, 9.5% by weight of ammonium phosphate monobasic, 9.5% by weight of dibasic ammonium phosphate, 3.5% by weight of sodium hydrogencarbonate, And 3.5% by weight of cellulose were mixed to prepare a mixture.

(3) 97.5% by weight of the mixture prepared in the step (2) and 7.5% by weight of sodium silicate were mixed.

Experimental Example  1. Evaluation of solubility

In order to evaluate the degree of insolubilization of carboxymethyl cellulose according to the heat treatment, the sample was immersed in water at 20 ° C for 24 hours, filtered, and the filtrate was separated, and the remaining sample was dried to evaluate the weight reduction rate according to the following formula Table 1 summarizes the results.

Weight reduction rate (%) = (W ₀ -W ₁ ) / W ₀ 100

W ₀ : Initial weight, W ₁ : Dry weight after water treatment

Weight reduction rate (%) Heat treatment condition 10 minutes 30 minutes 1 hours 50 ℃ 88.42 84.02 80.32 80 ℃ 18.54 9.56 8.47 100 ℃ 22.57 18.20 14.35

The weight reduction rate of the water-soluble carboxymethyl cellulose before heat treatment was 100%, and the solubility was 100%. As a result of comparing the weight loss rate of carboxymethyl cellulose according to the heat treatment conditions, it was confirmed that insolubilization was hardly occurred at the temperature lower than 80 ° C., and the weight reduction rate was higher than that at 80 ° C. It was confirmed that the insolubilization efficiency was inferior. Therefore, it is considered that heat treatment at 80 캜 for 30 minutes or more is most preferable for the insolubilization of carboxymethyl cellulose.

Experimental Example  2. Carboxymethylcellulose  Different heat treatment conditions Flame retardant  Flammability evaluation

A flame retardant liquid prepared by the method of Example 1 and a flame retardant liquid by the method of Example 1 were prepared. The flame retardant was prepared from water-insoluble carboxymethylcellulose prepared by differently heating the carboxymethylcellulose in the step (1) Experiments were conducted. The flame retardancy test was carried out according to the type approval and testing standard of flame retardant for plywood wood provided by KFAS, and each flame retardant was applied to the wood under the same conditions and dried. The size of the sample was 29 × 19 cm And the test pieces were placed in a combustion tester, which is an experimental apparatus based on a 45 ° C micro-burner method. The flame retardant performance standard is as shown in Table 2 below. The flame retardance time is the time from when the flame is removed from the burner to the time when the flame is raised to the end of burning. The flame is not raised from the time when the flame of the burner is removed, And the time until the state is finished.

Evaluation of Flame Retardancy of Flame Retardant division Brine Time Burst time Carbonization length Carbonized area Reference value Within 10 seconds Within 30 seconds Within 20 cm Within 50 cm ² 80 ℃ 10 min 0 0 8.4 cm 29 cm ² 80 ℃ 30 minutes 0 0 6.2 cm 24 cm ² 80 ℃ 1 hour 0 0 7.0 cm 26 cm ²

As a result, in the case of the wood coated with the flame retardant liquid prepared by the different heat treatment conditions of carboxymethyl cellulose, the time of the afterglowing and the time of the decay were all 0 seconds. Carbonyl methylcellulose heat-treated at 80 ° C. for 30 minutes Was found to be the most effective for the flame retardant.

Experimental Example  3. Depending on the manufacturing conditions Flame retardant  Flammability evaluation

A flame retardant prepared by the method of Example 1 and a flame retardant by the method of Example 1 were prepared. First, water-soluble carboxymethylcellulose was firstly mixed in the step (1), and then water-insoluble carboxymethyl The flame retardancy of the flame retardant prepared in Comparative Example 2 and the flame retardant prepared in Comparative Example 1 were evaluated by the method of Experimental Example 2.

Evaluation of Flame Retardancy of Flame Retardant division Brine Time Burst time Carbonization length Carbonized area Reference value Within 10 seconds Within 30 seconds Within 20 cm Within 50 cm ² Example 1 0 0 6.2 cm 24 cm ² Comparative Example 1 0 0 9.8 cm 33 cm ² Comparative Example 2 0 0 9.0 cm 30 cm ²

As a result, as a result of the evaluation of the flame retardancy of the flame retardant solution with different manufacturing conditions, it was found that the flame retardant solution of Example 1, which was prepared using a mixture of water-insoluble carboxymethylcellulose and water-soluble carboxymethylcellulose, And the flame retardant of Comparative Example 1 exhibited the lowest flame retardant effect.

Claims (4)

(1) heat-treating carboxymethylcellulose (CMC) to prepare water-insoluble carboxymethylcellulose;
(2) preparing a mixture by mixing ammonium phosphate monobasic, flameproof ammonium phosphate, sodium bicarbonate, and carboxymethylcellulose, which are flame retardants in powder form, wherein the mixture comprises ammonium phosphate monobasic, ammonium bicarbonate, sodium bicarbonate And water-insoluble carboxymethylcellulose prepared in the step (1), followed by secondary mixing of the water-soluble carboxymethyl cellulose to prepare a mixture;
(3) mixing sodium silicate with the mixture prepared in the step (2);
(4) preparing an adhesive by mixing gelatin and ethylene vinyl acetate, and mixing the prepared adhesive with the mixture of sodium silicate in step (3); And
(5) mixing the water-miscible mixture with the adhesive of step (4) to prepare a water-soluble flame retardant. The method according to claim 1,
(1) heat-treating carboxymethylcellulose (CMC) at 70 to 90 캜 to prepare water-insoluble carboxymethylcellulose;
(2) Mixing of ammonium phosphate dibasic, ammonium dibasic, hydrogencarbonate and carboxymethylcellulose, which are flame retardants in powder form, at a ratio of 8 to 11: 8 to 11: 3 to 4: 3 to 4, Wherein the mixture is prepared by first mixing ammonium phosphate monobasic, ammonium bicarbonate, sodium bicarbonate and water-insoluble carboxymethylcellulose prepared in the step (1), and then mixing the water-soluble carboxymethylcellulose with the water to prepare a mixture ;
(3) mixing the mixture prepared in the step (2) with sodium silicate at a ratio of 90 to 95: 5 to 10 by weight;
(4) An adhesive is prepared by mixing gelatin and ethylene vinyl acetate in a weight ratio of 0.4 to 1.2: 15 to 20, and 40 to 45% by weight of the prepared adhesive is contained in the mixture of sodium silicate in step (3) Mixing; And
(5) The method of manufacturing a water-soluble flame-retardant liquid according to the above (4), wherein the water-based flame-retardant solution is prepared by mixing 35 to 45% by weight of water at 20 to 30 ° C. [3] The method according to claim 2, wherein the water-insoluble carboxymethyl cellulose and the water-soluble carboxymethyl cellulose in step (2) are contained in the mixture in a weight ratio of 40:60 to 40:60. A water-soluble flame retardant prepared by the method according to any one of claims 1 to 3.