KR100501797B1 - Fireproofing treatment method using water glass - Google Patents

Abstract

The present invention relates to a flame retardant treatment method using water glass, and more specifically, to a variety of fibers, fabrics, non-woven fabrics, sheets, paper, etc. which is required to impart flame retardancy by using water glass which is harmless to the human body and has excellent flame retardant effect as a flame retardant. It relates to a method of flame retardant treatment to have excellent durability to the material to be treated.

The flame retardant treatment method of the present invention includes a water glass treatment step of imparting water glass, which is a flame retardant component, to a treated material by a method such as spraying, dipping or applying; The water glass is chemically treated by treating the water glass-treated material with one or two or more reforming agents selected from alcohols, ketones, or ethers which react with silicate materials to introduce lipophilic groups, and an acid causing polymerization of the silicate material. Reforming and solidifying step of the water glass to solidify and at the same time give lipophilic; And drying the treated material to remove moisture.

Description

Fire retardant treatment method using water glass {Fireproofing treatment method using water glass}

The present invention relates to a flame retardant treatment method using water glass, and more particularly, using a water glass that is harmless to humans and has excellent flame retardant effect as a flame retardant, such as fibers, fabrics, nonwoven fabrics, sheets, paper, etc. The present invention relates to a method for performing flame retardant treatment to have excellent durability on various materials to be treated.

Fires in facilities used by the public, including large lodgings such as hotels, often lead to catastrophic disasters with the death of life. For this reason, in terms of prevention of damage caused by fire and respect for life, building materials used for large buildings such as lodging and hospitality, which are used by many people, etc. Regulations are being tightened, and accordingly, considerable interest in related industries is focused on the development of flame retardant materials and flame retardant technologies.

In order to comply with the regulations on flame retardancy specified in the Fire Protection Act, such materials have been found and widely used since ancient times. Although efforts have been made to develop such materials, all materials have been made continuously. Since it is practically impossible to select and use non-flammable or flame retardant by itself, in consideration of other required properties, the material itself is selected to be flammable, but at any stage of manufacturing or processing Is being adopted.

As a general method of imparting flame retardancy to a flammable material, a flame retardant method of treating a flame retardant on a surface of a material by coating or the like, a manufacturing process of a material such as a fiber spinning process or an extrusion process of a panel or sheet, etc. The method of adding a flame-retardant additive in the process of etc. is mentioned.

Various flame retardants to flame retardant additives used to impart flame retardancy as described above are, for example, non-durable flame retardants such as ammonium phosphate, borax, boric acid, sulfamic acid, such as insoluble phosphates or borate salts of tin, zinc, aluminum and stannic tin, agent Semi-durable flame retardants such as oxides of ferric, zinc, silicon and the like and durable flame retardants such as condensates of THPC and TMM.

However, in recent years, as the human hazards of some flame retardant materials or flame retardants are known, research efforts have been focused on the development of flame retardant materials or flame retardants having not only a simple flame retardant effect but also low toxicity, low smoke, low corrosion resistance, and heat resistance. In addition, since the provision of flame retardants involves additional costs, excessive burdens of the costs result in the avoidance of use of flame retardant materials, which still exposes the public unprotected to fire accidents. Increasingly, flame retardants are in need of low cost flame retardants.

Water glass has attracted attention as one of flame retardants having the above characteristics. As for water glass, soda water glass mainly containing sodium silicate is generally classified into water glass such as potassium water glass and soda potassium water glass, and the basic main raw materials are silicon oxide or silica sand or silica. Silica and silica can be obtained abundantly as a representative mineral present on the earth, and because it is a material that can be widely supplied as a product, water glass can be given flame retardancy at low cost, and its use value is very high.

Water glass is particularly used as a heat-resistant, corrosion-resistant and waterproof coating because it has a high thermal stability and no pollution problem, unlike the organic coating obtained from petrochemical as a representative inorganic coating. Since water glass has a sharp increase in the viscosity of the solution as the amount of water decreases and has an adhesive force, when the aqueous solution is treated on the surface of the material to be treated and dried, a film having a smooth surface like glass can be obtained. In addition, the water glass at the same time between the separation of water molecules and the condensation polymerization reaction of silica proceeds between about 100 ℃ to 200 ℃ and foamed to prevent the treated material from contact with oxygen and to perform adiabatic action to reduce the combustibility, about 500 ℃ to 700 ℃ In between, the crystallinity is increased, the physical properties are more solid, and added to the combustible material can be advantageously used to enhance the flame retardancy. In addition, water glass is known as a low-hazardous material and silica gel prepared by adding hydrogen cation to water glass has been widely used as a dehumidifying agent in the food industry.

Recently, as the unique properties and usefulness of the water glass, especially the flame retardant effect is known, efforts are being made to utilize it in human life.

However, simply dried water glass has a property that is easily soluble in water and has a poor durability. Therefore, as part of efforts to solve these problems, researches on scientifically revealing the process of converting silicate material and the conversion of water insolubility and improving physical properties are being conducted in depth.

For example, Calapati et al. (Bioresource Technology, 72, 99-106, 2000) extract amorphous silica present in the ash of rice hulls using an aqueous solution of caustic soda, and then concentrate and add isopropyl alcohol and some additives. It introduces a method for producing silica films with excellent flexibility and strength by uniformly mixing and drying.

Knobraich and Gerbery (J. of Non-Crystalline Solids, 283, 109-113, 2001) studied the coagulation characteristics of SiO ₂ in water glass aqueous solution by X-ray incineration scattering. It is reported that it is closely influenced by the hydrogen ion concentration of silver solution and rapidly forms water-insoluble silica gel when the pH of water-free aqueous solution is 2.2 to 5.8, and the reaction proceeds slowly when the pH is between 5.8-6.

On the other hand, U.S. Patent No. 6,303,234 discloses that water glass, such as cellulose, which has a chemical composition, is treated with water glass, and then treated with silicon monoxide or silicon dioxide vapor to provide excellent flame retardancy, high flexibility, and stable treatment with moisture. Introducing.

On the other hand, U.S. Patent No. 6,146,766 discloses excellent flame retardancy, strength and moisture resistance which are prepared by infiltration of sodium silicate and water-soluble flame retardant into cellulosic material through pressure and vacuum treatment, and polymerization by heat. Introduces the preparation of materials.

As such, a wide range of researches have been conducted to solve the problem that water glass is vulnerable to moisture and to use it as a flame retardant, and many technologies for manufacturing flame retardant products using water glass have been disclosed. However, all of these technologies are merely a simple application of the fact that the application of water glass can improve the flame retardancy, and most of them are extremely limited in applicability according to the material and structure of the material to be treated. There is no known technique for improving the properties of water glass that can be applied and made to have sufficient durability.

The present invention is to solve the above-mentioned durability problem, which is a problem in the flame retardant treatment method for imparting flame retardancy by treating water glass to the material to be treated that is required to impart flame retardancy, dust and excellent flexibility and durability using water glass It is an object of the present invention to provide a flame retardant treatment method that is free from water, is insoluble in water, has excellent flame retardancy, and provides smooth and dense surface characteristics.

The present inventors combine the material properties of silica prepared by using water glass with the treatment method to promote mass transfer, lipophilic reforming, and the condensation polymerization reaction of silica in a balanced manner, and the technique of sufficiently giving flexibility and water resistance by selecting optimum conditions. The present invention has been accomplished by developing a flame retardant treatment method that is widely applicable to various materials to be treated.

Flame retardant treatment method using water glass according to the present invention,

A water glass treatment step of imparting water glass, which is a flame retardant component, to the material to be treated by spraying, dipping or coating;

The water glass is chemically treated by treating the water glass-treated material with one or two or more reforming agents selected from alcohols, ketones, or ethers which react with silicate materials to introduce lipophilic groups and an acid causing polymerization of the silicate materials. Reforming and solidifying step of the water glass to solidify and at the same time give lipophilic; And

And drying the treated material to remove moisture.

According to the method of the present invention, an acid and an alcohol, a ketone, or an ether are mixed and added to a water glass known as a flame retardant component which is excellent in flame retardancy and is inexpensive and has low human health. Modification to lipophilic at the same time as the separation occurs, it is possible to obtain a flame retardant with improved water insolubility and flexibility. In addition, the modified flame retardant component is part of the hydroxyl group of the silica that causes thermal decomposition is blocked by an alkyl group introduced by alcohol or the like to have a stronger property to heat, thereby further improving the flame retardant effect.

The process will be described with reference to the prior art using the drawings as follows.

1 is a conceptual diagram schematically showing a process of producing water-insoluble silica by the acid addition, conventionally, Figure 2 is a process of generating a water-insoluble and lipophilic modified silica according to the method of the present invention. The conceptual diagram shown.

First, in the case of the conventional method, as shown in FIG. 1, when the silicate material (b) is dissolved in water (a) and an acid is added to the water glass (A) in which they are uniformly mixed, it is contained in the water glass (A). The silicate materials (b) are dispersed by water (a), so that the polymerization proceeds only between adjacent silicate materials (b), and as a result, after the moisture is removed by drying, the particles are separated into fine particles. Since the silica is solidified (C), the obtained silica has low coating properties and durability, and also has low water resistance and thus cannot be used for the purpose of imparting flame retardancy through coating of the flame retardant.

However, according to the method of the present invention, as shown in Fig. 2, when the silicate material (b) is dissolved in water (a) and an acid and an alcohol (modifying agent) are added to the water glass (A) where they are uniformly mixed, At the same time as the silica polymerization of the silicate material (b) contained in the water glass (A), alcohol (c) is bonded by a chemical reaction to form a lipophilic group, so that water (a) is released from the polymerized lipophilic silica (B). I will go out. Therefore, if the polymerization reaction is carried out while appropriately adjusting the composition selection of the acid and the reforming agent, it is converted into a lipophilic silica (B) having a relatively low water content, and even drying it suppresses the generation of voids due to evaporation of water (a). Material (C) having smooth surface properties is obtained. Therefore, according to the method of the present invention, it is possible to obtain a flame retardant which is free of dust and excellent in durability, particularly water resistance.

Preferably, in the flame retardant treatment method, water glass is applied and then dried to treat the mixed treatment agent. This is to remove water used in advance to dilute the water glass itself or the water glass to some extent, so that the release of water made in the lipophilic reforming by the reforming agent is made more smoothly.

On the other hand, in the flame retardant treatment method, the provision of the water glass and the mixed treatment agent can be made by a method such as spraying using a spray device of water glass or mixed treatment liquid, immersing in the solution or padding or applying by the edge or roller, The present invention is not limited to these methods, and various types of granting methods may be applied.

Next, the water glass used by the method of this invention is demonstrated. The chemical composition of the water glass is generally expressed as M ₂ O _m SiO _{2 ·} nH ₂ O. Here, M is an alkali metal, and Li, Na, K, Ru, Cs and quaternary ammonium bases are known. In fact, when M is Na, m = 0.54-4, when M = 2-3.8, and when Li It is known that the molar ratios such as m = 1.2 to 30 are wide when the ratio is 3.5 to 7.5 and quaternary ammonium base. And in water glass there are several kinds of (SiO ₄ ) ^4- , (Si ₂ O ₇ ) ^6- , (Si ₃ O ₉ ) ^6- , (Si ₄ O ₁₂ ) ^8- , (Si ₆ O ₁₈ ) ^12- It is known to contain silicate anions.

Such water glass is generally produced by heating and melting a mixture of silica sand and sodium carbonate at a temperature range of 1300-1500 ° C. to produce a glass, and treating it in a low pressure autoclave, and a colloidal silicic acid or diatomaceous earth and sodium hydroxide. It is manufactured by two methods of wet method of heating, reacting and dissolving in autoclave, detergent, detergent, penetrant, binder, adhesive, fire retardant, soil hardener, raw material for refractory cement, raw material for hardening softener, silica gel production It is used as a raw material and egg preservative.

Commercially available water glass has various manufacturing methods and compositions as described above, but the water glass used in the present invention is not particularly limited in its composition. Preferred examples of the water glass used in the present invention include an aqueous solution in which any one or two or more of the silicate materials such as sodium silicate, potassium silicate, potassium silicate, and the like prepared by using silicon oxide are dissolved in water. It is useful that the content is between 0.5 to 80% by weight, and considering the complete application conditions, productivity and flame retardancy to the treated material, preferably the silicate material is dissolved between 5 to 60% by weight, and the moisture is 94 to 39% by weight. It is preferable to use a composition containing between 0.01% by weight and 10% by weight of additives for the purpose of additional functionalization, and between 0.1% by weight and 10% by weight of other water-insoluble suspended substances and impurities.

On the other hand, additives for the purpose of imparting functionality, quaternary ammonium salts, antibacterial agents such as chitosan, anti-ultraviolet emitters such as clay, silica, jade, silicon, warmers such as ferrite, germanium, anions such as activated carbon or bamboo charcoal Release agents, deodorants such as charcoal or activated carbon, antimony trioxide, phosphate compounds, flame retardants such as boron, boric acid, aluminum oxide, conductive fillers or conductors such as carbon fibers.

The mixing treatment agent used in the present invention will be described. The mixed treatment agent has compatibility with water, promotes the release of moisture present in the water glass aqueous solution, alcohol compounds that can cause coupling reaction with silica, and ketones or ethers that can cause addition reaction. It is a mixture of an acid which can catalyze the condensation polymerization reaction of the reforming agent and silica, which is one or two or more substances selected from the compounds.

The reforming agent reacts with the water glass added to the material to be treated to modify the surface properties of the silica to be lipophilic, while acting as a plasticizer to lower the hardness of the silica and to enhance the flexibility, the acid is the polymerization reaction of the silica Promotes water resistance by making it water insoluble. Therefore, the flexibility and durability are improved by the modifying agent as a whole.

The silicate material contained in the water glass exists in an ionic state and a compound having both a functional group capable of chemically reacting with an anion of the silicate and a functional group capable of imparting a lipophilic property can be applied to the lipophilic modification of silica. However, it should be possible to promote the release of water through the mixing process with the water contained in the water glass and to be able to mix with the acid catalyst. Therefore, as alcohols, ketones and ethers used in the present invention, it is preferable to use those having a range of 1 to 8 carbon atoms. Too much carbon number is undesirable because of poor compatibility with water and low reactivity.

Examples of alcohols that simultaneously satisfy the above conditions include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclopropanol, cyclobutanol, phenol, benzyl alcohol, ethylene glycol, glycerol, sorbitol, polyvinyl alcohol, and the like. have.

Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, 2-methylcyclopentanone, methyl vinyl ketone, acetophenone, benzophenone, dicyclopropyl ketone, and the like. Methylethyl ether, diethyl ether, diphenyl ether, 2-methoxypentane, trans-2-methoxycyclohexanol, 1,3,5-trimethoxybenzene, 2-ethoxy-3-methylbutane, Dicyclopropyl ether, ethylene oxide, tetrahydrofuran, tetrahydropyran, 1, 4- dioxane, etc. are mentioned.

On the other hand, examples of the acid include organic acids such as acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propionic acid, succinic acid, hydroxyl acid, succinic acid, ascorbic acid, gluconic acid, tartaric acid, maleic acid, citric acid, glutamic acid, toluenesulfonic acid, sulfuric acid, Inorganic acids, such as phosphoric acid and nitric acid, are mentioned.

The material of the to-be-processed material to which the flame retardant treatment method of the present invention can be applied is not particularly limited, and nonwoven fabric, paper, knitted fabric, fabric, resin sheet, resin or wood panel or resin or wood board made of fiber or pulp It can be applied to the same various materials, in particular, it is expected that it can be widely applied to building materials regulated by fire law.

On the other hand, in the flame retardant treatment method, the water glass is used 2 to 300% by weight based on the weight of the material to be treated, the reforming agent is used 1 to 50% by weight based on the amount of water glass used, the acid is the mixed treatment agent as a whole Using 5 to 40% by weight of the weight, the pH range of the mixed treatment agent is 1 to 7.

Since the commercially available water glass as described above is not constant and varied, the amount of water glass required for imparting flame retardancy cannot be uniquely defined. However, if water glass having a composition in the above-mentioned range is generally used, When the amount of about 2% by weight is used, the flame retardancy is exerted, so that the above amount is used in consideration of the properties of the material itself and the required flame retardancy. However, the treatment of more than 300% by weight with respect to the weight of the material to be treated is very difficult depending on the material to be treated and economically undesirable, so it is preferable to use it in the following range.

The amount of reforming agent used also varies with the degree of lipophilicity depending on the number of carbon atoms, and the degree of reactivity with water glass varies depending on the type of reactor, the degree of lipophilicity of the side chain, and the like. It is difficult to define the amount of usage uniquely because the amount of usage needs to be determined differently according to the required flame retardancy.However, if it is added in the range of about 1 to 50% by weight based on the weight of water glass used, Desired lipophilic modification effect can be obtained, and preferably used in the range of about 10 to 20% by weight.

The amount of acid used should be determined in the same manner, taking into account the amount of water glass used, the amount of the modifying agent, the characteristics and shape of the material to be treated, the properties of the object to be treated, etc. Not only does this fall, but also appears to result in a poor water resistance, in consideration of the amount of use of the reforming agent added in the range of 5 to 40% by weight of the total weight of the mixed treatment agent, the pH of the mixed liquid is in the range of 1-7 To be More preferably, the pH range is adjusted to 3 to 7 in order to stably proceed the polycondensation reaction of silica and to obtain more smooth surface properties.

In the above, the flame retardant treatment method of the present invention has been described in detail, but in order to understand the principle of improving the surface properties and water resistance of the water glass by the method of the present invention, the mechanism of the chemical reaction expected between the water glass and the treatment agent will be described.

Enhancement of the lipophilic surface modification and flexibility of the silica contained in the water glass is understood to be achieved by a coupling reaction of the alcohol having a hydroxyl group (-OH) and active silica, as shown in Scheme 1 below.

In addition, when using a ketone compound, it is understood that the lipophilic surface modification of the silica contained in the water glass and the enhancement of the flexibility are achieved by the addition reaction of the ketone compound having a carbonyl group and active silica, as shown in Scheme 2 below.

On the other hand, it is understood that the improvement of water resistance of water glass is achieved by adding water insolubility and enhancing durability by addition of an acid releasing hydrogen cation which catalyzes the polymerization of silica by a polymerization reaction as in Scheme 3 or 4 below. . Scheme 3 below shows a polymerization reaction of silica when sulfuric acid is added to the water glass, and Scheme 4 shows a polymerization reaction of silica when hydrochloric acid is added.

Na ₂ SiO ₃ + H ₂ O + H ₂ SO ₄ → Si (OH) ₄ + Na ₂ SO ₄

Si (OH) ₄ + Si (OH) ₄ → (OH) ₃ -Si-O-Si (OH) ₃ + H ₂ O

Na ₂ SiO ₃ + H ₂ O + 2HCl → Si (OH) ₄ + 2NaCl

Si (OH) ₄ + Si (OH) ₄ → (OH) ₃ -Si-O-Si (OH) ₃ + H ₂ O

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

Example

Example 1: Flame Retardant Treatment of Nonwoven Fabric Using Water Glass

A flame retardant nonwoven fabric according to the method of the present invention was prepared through the following steps, and thermal properties were analyzed to test the flame retardancy of the nonwoven fabric treated by the flame retardant treatment method according to the present invention.

A. Preparation of Flame Retardant Nonwovens

Treatment of water glass

100cm of 5cm thick nonwoven fabric made of cotton fiber was immersed in water glass aqueous solution for 2 minutes at a temperature of 30 ° C and completely wetted, and then the pressure applied to the roller of the mangle was adjusted to 3㎏ / ㎠ to add-on water glass The excess solution was squeezed by adjusting the rate to 80%.

As the water glass aqueous solution used herein, commercially available SiO ₂ content is between 28% and 30%, Na ₂ O content is between 9% and 10%, and Fe ₂ O ₃ content is less than 0.03%. It was used to purchase the water and diluted 2 times by adding water.

Drying of nonwoven fabric

The water glass-treated water content of 50% of the nonwoven fabric was dried for 10 minutes at a temperature of 150 ℃ using a hot air dryer to adjust the content of water to 20%.

Modification of Treated Water Glass

2 kg of acetic acid was added to 8 kg of ethanol and stirred to prepare a uniformly mixed mixing agent. The nonwoven fabric dried by the water glass treatment was immersed in the mixed treatment solution for 1 minute, and then the excess treatment agent was removed using a mang roller. By this step, the liquid water glass contained in the nonwoven fabric was converted into modified silica having water insolubility, durability and flexibility.

Drying flame retardant nonwovens

The nonwoven fabric after the treatment was completed was dried for 20 minutes at a temperature of 150 ℃ using a hot air dryer to complete a flame-retardant nonwoven fabric.

B. Thermal Characteristic Analysis of Flame Retardant Nonwovens

The thermal stability of the flame-retardant nonwoven fabric was confirmed by thermal analysis using a thermogravimetric analyzer (TGA) using the flame-retardant nonwoven fabric prepared by the above method and the non-flammable untreated cotton nonwoven fabric as samples.

3 and 4 show the results, respectively.

Figure 3 shows the results of thermogravimetric analysis of the flame retardant nonwoven fabric prepared according to the present embodiment, it can be seen that only 40% weight loss occurs at a temperature of 450 ℃ and about 60% of the mass remains. On the other hand, Figure 4 shows the results of thermogravimetric analysis of the untreated cotton nonwoven fabric, the weight loss of about 90% occurs at a temperature of 450 ℃ leaving only 10% ash.

From the above results, it can be seen that the nonwoven fabric having excellent flame retardancy can be produced by the treatment method of the present invention.

Example 2, Comparative Examples 1 and 2: Changes in physical properties according to the treatment method of water glass

A. Preparation of Silica Film

Take 3 glass plates of 30 g of water glass each containing 28% to 30% SiO ₂ , 9% to 10% Na ₂ O, and 0.03% Fe ₂ O ₃ . After coating to a thickness of 1mm, and then solidified in each of the following three methods to prepare a silica film.

Example 2: The liquid mixed with 4 g of ethanol and 1 g of acetic acid was evenly applied using a sprayer, and then heated at a temperature of 150 ° C. for 10 minutes using a hot air dryer.

Comparative Example 1: Heated at a temperature of 150 ℃ using a hot air dryer for 10 minutes.

Comparative Example 2: 3 g of acetic acid was evenly sprayed using an atomizer, and then heated at a temperature of 150 ° C. for 10 minutes using a hot air dryer.

A part of the silica film obtained by the above method was retaken, and water solubility, dust generation, crystallinity, and heat resistance were respectively measured by the following methods.

B. Solubility Measurement

1 g of each of the silica films prepared by the methods of Example 2 and Comparative Examples 1 and 2 were taken and placed in a beaker, and 100 g of water was added thereto and stirred at room temperature for 1 hour using a stirrer. The undissolved residue was collected using a filter paper, dried and weighed to confirm water solubility. As a result of each measurement, the silica films prepared by the method of Comparative Example 2 were all dissolved and no residues were left. The silica films prepared by the method of Example 2 and the method of Comparative Example 2 remained as water-insoluble. Could.

C. Confirmation of Dust Generation and Surface Characteristic Analysis Using Electron Microscopy

Part 2 of the silica film prepared by the method of Example 2, Comparative Examples 1 and 2, respectively, the platinum ions are deposited to impart conductivity to the surface, and Example 2 was 3,000 times using an electron microscope, and compared with Comparative Example 1 Comparative Example 2 confirmed the surface characteristics and the presence of dust at a magnification of 2,000 times.

As a result, in Example 2 in which the water glass was solidified by mixing and adding 4 g of ethanol and 1 g of acetic acid, as shown in FIG. 5, not only the water contained in the water glass was appropriately substituted with ethanol, but also the lipophilic properties of silica. As a result of the modification, a polymerization reaction was carried out to obtain a silica film having high surface smoothness and no dust generation.

Moreover, also in the comparative example 1 which heated and solidified the water glass as it was, as shown in FIG. 6, it had a comparatively smooth surface and did not generate | occur | produce dust.

On the other hand, in Comparative Example 2 in which the water glass was solidified using an acid as a catalyst, as shown in FIG. 7, the polymerization reaction of silicate dissolved in water was selectively performed only between adjacent materials, As the separation occurs, the finally obtained silica film has the shape of particles.

D. Comparison of Crystallinity Using X-RAY Diffractometer

Part of the silica film prepared in Example 2, Comparative Examples 2 and 3, respectively, was taken, and then diffracted at a measurement rate of 2 ° / min from 3 ° to 35 ° using X-Ray generated from the copper electrode. Analysis was made to compare the crystallinity with each other.

Intensity and crystallinity of the diffraction X-Ray was confirmed that the silica film prepared in Comparative Example 1 has the lowest value as shown in Figure 9 has the most flexible structure.

In addition, in the case of the water-insoluble silica film prepared in Comparative Example 2, it was confirmed that the crystallinity is very high, as shown in Figure 10, having a very low flexibility structure. This high crystallinity and very low flexibility mean that it is difficult to apply to flexible materials, and is not suitable for flame retardant treatment of materials to be deformed due to external force applied during use. do.

On the other hand, in the case of the water-insoluble silica film prepared by the method of Example 2, as shown in Figure 8, it can be seen that a film having a certain degree of flexibility with a median value in crystallinity is obtained.

E. Thermal Resistance Comparison of Solidified Glass Using Thermogravimetric Analyzer

Part of the silica film prepared in Example 2 and Comparative Examples 1 and 2, respectively, was taken, and then heated by a thermogravimetric analyzer at a temperature rising rate of 20 ° C./min at a temperature of 50 ° C. to 850 ° C. at 20 ° C./min. Was measured to compare the heat resistance of the silica film.

As a result of the measurement, as shown in FIG. 11, in the case of the silica film prepared in Example 2 (A), about 80% of the initial weight remained at a temperature of 850 ° C., and it was confirmed that the heat resistance was the best. On the other hand, in the case of the silica film prepared in Comparative Example 1 (C), at the temperature of 850 ° C remained about 70% of the initial weight was the lowest heat resistance. On the other hand, in the case of the silica film prepared in Comparative Example 2 (B), about 75% of the initial weight remained at a temperature of 850 ℃, it was confirmed that the heat resistance shows a moderate degree.

The above analysis results are summarized in Table 1.

division Water solubility Dust generation Crystallinity Heat resistance Example 2 Water insoluble No dust middle height Comparative Example 1 receptivity No dust lowness lowness Comparative Example 2 Water insoluble Dust generation height usually

Examples 3 to 17: change in physical properties according to the composition of the treatment agent

Among alcohols, aldehydes, ketones, and ethers applicable to the lipophilic modification of the present invention, compounds that promote the release of water through mixing with water contained in water glass and are capable of mixing with acid catalysts and selecting compounds having low human toxicity are selected. Then, 4 g of the reforming agent and 1 g of acetic acid were mixed to prepare 5 g of each mixed treatment liquid. The types of reforming agents used in the examples are shown in Table 2.

5 g each of the same water glass as used in Example 1 was added to the saale, and 5 g of the mixed treatment solution of Table 2 was added thereto, followed by stirring for 10 minutes, and the solidification reaction of the water glass was observed to compare the reactivity. In addition, the reaction was allowed to sufficiently proceed for 1 hour in that state, and then surface hardness was measured to compare the flexibility.

The reactivity of the used modifier with water glass and the flexibility of the resulting film are summarized in Table 2 below.

division Modification Agent Reactivity with water glass Film flexibility Example 3 Methyl alcohol Very high middle Example 4 Ethyl alcohol Very high middle Example 5 Propyl Alcohol height middle Example 6 Isopropyl Alcohol middle middle Example 7 Butyl Alcohol lowness height Example 8 Isobutyl Alcohol lowness height Example 9 Cyclopropyl alcohol lowness height Example 10 phenol height height Example 11 Benzyl alcohol lowness Very high Example 12 Ethylene glycol height height Example 13 Glycerol middle height Example 14 Sorbitol middle height Example 15 Acetone Very high Very high Example 16 Methyl ethyl ketone Very high Very high Example 17 Tetrahydrofuran height middle

In the test results, alcohols generally showed higher reactivity with water glass as the hydrophilicity was higher, but the flexibility of the film was lower. In the case of benzyl alcohol of Example 11, the flexibility of the film was very high, but the reactivity was slow and the workability was inferior due to phase separation in the process of mixing with acid. On the other hand, ketones and ethers having different reactors were generally more reactive than alcohols, and had excellent film flexibility.

Examples 18 to 26: change in physical properties according to the composition change of the mixed treatment agent

In this embodiment, the flexibility and the water resistance of the silica film obtained according to the use ratio of the reforming agent for imparting lipophilic acid and the acid catalyzing the polymerization reaction were investigated by changing the use ratio.

Ethanol was used as the reforming agent and acetic acid was used as the acid, respectively, and the weight ratio was 1: 9 (Example 18), 2: 8 (Example 19), 3: 7 (Example 20), 4: 6 (Example Example 21), 5: 5 (Example 22), 6: 4 (Example 23), 7: 3 (Example 24), 8: 2 (Example 25), 9: 1 (Example 26) To prepare a mixed treatment agent.

5 g of the same water glass as used in Example 1 was added to Shale, and then 10 g of the mixed treatment agent mixed in each composition ratio was added thereto, and left for 1 hour to solidify the water glass. Then, using a hot air dryer for 30 minutes at a temperature of 150 ℃ to dry completely to obtain a silica film.

10 g of water was added to each of the silica films, and the wetness was repeated to measure the number of times the cracks occurred, and to compare the durability against moisture.

Table 3 shows the initial crack incidence and water resistance evaluation results for each example.

division Composition of treatment agent First crack occurrence Water resistance ethanol Acetic acid Example 18 One 9 0 Bad Example 19 2 8 0 Bad Example 20 3 7 0 Bad Example 21 4 6 One Bad Example 22 5 5 One Bad Example 23 6 4 2 Bad Example 24 7 3 31 Great Example 25 8 2 51 Very good Example 26 9 One 40 Great

As a result of the test, when the treatment agent was prepared by mixing ethanol and acetic acid, it was confirmed that the most durable flame retardant treatment was possible when the water glass was solidified using the treatment agent prepared at a weight ratio of 8: 2.

According to the flame retardant treatment method of the present invention, it is possible to impart excellent flame retardancy, but the durability and weakness does not have the flexibility of the problem of dust generation and the property of being easily soluble in water added to various treated materials to use the flame retardant to impart flame retardancy By adding a treatment agent that enhances flexibility, water insolubility, and heat resistance to water glass, which could not be utilized, there is an effect that can be applied to various treated materials. In addition, the technology of imparting flame retardancy by using water glass, which is relatively inexpensive, is provided so that it is possible to impart flame retardancy to various combustible materials at low cost, and thus various construction materials, coating materials, mechanical parts, automobile parts, aviation parts, etc. It is applied in the manufacturing process to enable the production of popular flame retardant materials without the risk of fire.

1 is a conceptual diagram schematically showing a reaction in which particulate silica is produced by condensation polymerization between silicate materials occurring during the polymerization of water glass by acid addition;

2 is a conceptual diagram schematically showing a reaction in which a modified silica is produced by a reaction of a silicate material, a modifying agent (alcohol) and an acid in a flame retardant treatment using water glass according to the method of the present invention;

Figure 3 is a graph showing the thermogravimetric analysis of the flame retardant nonwoven fabric prepared in Example 1;

4 is a graph showing the thermogravimetric analysis of an untreated cotton nonwoven fabric;

5 is an electron micrograph of the film-like material obtained in Example 2;

6 is an electron micrograph of the film-like material obtained in Comparative Example 1;

7 is an electron micrograph of the film-like material obtained in Comparative Example 2;

8 is an X-ray diffraction pattern of the film-like material obtained in Example 2;

9 is an X-ray diffraction pattern of the film-like material obtained in Comparative Example 1;

10 is an X-ray diffraction pattern of the film-like material obtained in Comparative Example 2;

11 is a graph showing the thermogravimetric analysis results of the film-like materials obtained in Example 2, Comparative Examples 1 and 2.

Claims (13)

A water glass treatment step of imparting water glass, which is a flame retardant component, to the material to be treated by spraying, dipping or coating; The water glass is chemically treated by treating the water glass-treated material with one or two or more reforming agents selected from alcohols, ketones or ethers which react with the silicate material to introduce a lipophilic group and an acid causing polymerization of the silicate material. Reforming and solidifying step of the water glass to solidify and at the same time give lipophilic; And Flame retardant treatment method using a water glass, characterized in that it comprises the step of drying the mixed treatment agent-treated material to remove moisture. The flame retardant treatment method according to claim 1, further comprising a drying step for lowering the moisture content after the water glass treatment step. The flame retardant treatment method using water glass according to claim 1 or 2, wherein the mixing treatment agent is applied by spraying, dipping or applying the mixed treatment liquid. The method of claim 1 or 2, wherein the material to be treated is any one of nonwoven fabric, paper, knitted fabric, woven fabric, resin sheet, resin or wood panel, or resin or wood board, which are made of fiber or pulp. Flame retardant treatment method. The water glass according to claim 1 or 2, wherein the water glass is an aqueous solution of at least one type of silicate material such as sodium silicate, potassium silicate, potassium potassium silicate, and the content of silicate material is 0.5 to 80% by weight. Flame retardant treatment method using. According to claim 5, wherein the water glass has a silicate material content of 5 to 60% by weight, water content of 94 to 39% by weight, quaternary ammonium salts, antimicrobial agents such as chitosan, far-infrared emitters such as clay, silica, jade, silicon, Warmers such as ferrite, germanium, anionic emitters such as activated carbon or bamboo charcoal, deodorants such as charcoal or activated carbon, antimony trioxide, phosphate compounds, boron, boric acid, flame retardants such as aluminum oxide, conductive fillers or carbon fibers Flame retardant treatment method using water glass, characterized in that the content of any one or two or more functional additives selected from the same conductor is 0.01 to 10% by weight, water insoluble suspended matter or impurity content 0.1 to 10% by weight. The alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclopropanol, cyclobutanol, phenol, benzyl alcohol, ethylene glycol, glycerol, sorbitol, and polyvinyl alcohol. Flame retardant treatment method using water glass, characterized in that the. The method of claim 1 or 2, wherein the ketones are selected from acetone, methyl ethyl ketone, cyclohexanone, 2-methylcyclopentanone, methyl vinyl ketone, acetophenone, benzophenone and dicyclopropyl ketone. Flame retardant treatment method using water glass. 3. The ether according to claim 1 or 2, wherein the ethers are methylethyl ether, diethyl ether, diphenyl ether, 2-methoxypentane, trans-2-methoxycyclohexanol, 1,3,5-trimeth. Flame retardant treatment method using water glass, characterized in that selected from oxybenzene, 2-ethoxy-3-methylbutane, dicyclopropyl ether, ethylene oxide, tetrahydrofuran, tetrahydropyran, 1,4-dioxane. 3. The method of claim 1 or 2, wherein the acid is acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propionic acid, succinic acid, fish acid, succinic acid, ascorbic acid, gluconic acid, tartaric acid, maleic acid, citric acid, glutamic acid, toluenesulfonic acid Flame retardant treatment method using water glass, characterized in that selected from organic acids or inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid. The flame retardant treatment method according to claim 1 or 2, wherein the water glass is used in an amount of 2 to 300% by weight based on the weight of the material to be treated. The flame retardant treatment method according to claim 1 or 2, wherein the reforming agent is used in an amount of 1 to 50% by weight based on the amount of water glass used. The flame retardant treatment method according to claim 1 or 2, wherein the acid is used in an amount of 5 to 40% by weight of the total weight of the mixed treatment agent, and the pH of the treatment agent is in the range of 1 to 7.