WO2004062815A1 - Fireproofing treatment method using water glass - Google Patents
Fireproofing treatment method using water glass Download PDFInfo
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- WO2004062815A1 WO2004062815A1 PCT/KR2003/000102 KR0300102W WO2004062815A1 WO 2004062815 A1 WO2004062815 A1 WO 2004062815A1 KR 0300102 W KR0300102 W KR 0300102W WO 2004062815 A1 WO2004062815 A1 WO 2004062815A1
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- water glass
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- fire retardant
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
Disclosed herein is a fire retardant treatment method using water glass. According to the fire retardant treatment method of the present invention, water glass having excellent fire retardant effects without posing any risk to humans is used as a fire retardant, and imparts more durable fire retardancy to various substrates such as fibers, fabrics, non-woven fabrics, sheets, papers and the like. The fire retardant treatment method comprises the steps of: treating a substrate with water glass as a fire retardant by a spraying, dipping or application process; treating the water glass-treated substrate with a treatment agent to chemically solidify the water glass and impart lipophilicity to the water glass, the treatment agent including at least one modifier selected from C1-8 alcohols, ketones and ethers and an acid capable of inducing a polymerization reaction of silica; and drying the resulting material to evaporate water.
Description
FIREPROOFING TREATMENT METHOD USING WATER GLASS
Technical Field
The present invention relates to a fire retardant treatment method using water glass. More particularly, the present invention relates to a method for imparting improved fire retardancy to various substrates, such as fibers, fabrics, non- woven fabrics, sheets, papers, panels and the like, using water glass as a fire retardant so that the substrates exhibit superior durability. The water glass is known to have excellent fire retardant effects without posing any risk to humans.
Background Art
Fire occurring in public facilities, including lodging accommodations (e.g., hotels), directly leads to a disastrous accident involving injuries and casualties. For this reason, in order to avoid damage to property by fire and save human lives from fire, governmental regulations (e.g, the Fire Service Act concerning fire retardancy) regarding the use of fire retardant materials as materials of construction for mass facilities such as lodging accommodations and service industry businesses have become increasingly stringent. Thus, recent interest has focused on the development of fire retardant materials and techniques in related industries.
In order to meet the regulations regarding fire retardancy defined in the Fire Service Act, many fire retardants have been developed and used hitherto. A number of efforts have been made to develop such fire retardants. In practice, selection and use of only fire retardants or incombustible materials is substantially impossible. Accordingly, processes for imparting fire retardancy by adding a fire retardant to a flammable material serving as a main material, in any step during manufacture or processing, have been employed. Considering other required properties, the flammable material is properly selected. Exemplary processes for imparting fire retardancy to a flammable material include fire retardant processes in which the surface of a flammable material is treated with a fire retardant, and fire retardant processes in which a fire retardant additive is added during manufacturing a material, e.g., spinning of a fiber or extrusion of a panel. Fire retardants and fire retardant additives used to impart fire retardancy can be divided into three groups: non-durable fire retardants such as ammonium phosphate, borax, boric acid, sulphamic acid, etc.; semi-durable fire retardants such
as insoluble phosphates and borates of tin, zinc and aluminum, and oxides of tin (II), iron (II), zinc and silicon, etc.; durable fire retardants such as condensates of THPC and TMM.
Since health harmfulness of some fire retardants has been discovered in recent years, investigations have been directed toward developing fire retardants having reduced toxicity and flammability, corrosion resistance, and excellent heat resistance other than fire retardancy. Since imparting fire retardancy involves increasing costs, the use of fire retardants is still avoided. Accordingly, the public is still exposed to fire hazards, possibly leading to a disastrous accident involving injuries and casualties. There is thus a need for low-price fire retardants.
As one of fire retardants having the above-mentioned properties, special attention has been paid to water glass. Water glass is generally soda water glass containing sodium silicate as a main component. Potassium water glass and soda potassium water glass also are classified into water glass. They contain silicon oxides, i.e. silica sand or silica, as basic raw materials. Silica sand and silica are representative minerals abundant in the earth and are commercially available as many products. Since water glass enables impartment of fire retardancy at low cost, it is very frequently utilized.
Since water glass, which is a representative inorganic coating agent, has excellent thermal stability and causes no pollution problems, unlike organic coating agents obtained from petroleum, it is widely used as a material for heat resistance, corrosion resistance and waterproofing coating. As the water content in water glass is low, the viscosity becomes high and thus adhesive force increases. Application of the aqueous solution on the surface of a substrate and subsequent drying enable the formation of a coated film with a smooth glass-like surface. At a temperature between 100°C and 200°C, water molecules contained in water glass are separated and at the same time a polycondensation of silica particles takes place. Thereafter, the water glass is foamed to prevent the substrate from contacting oxygen and to provide an insulating barrier, thereby decreasing the flammability. Further, the crystallinity is increased at a temperature between 500°C and 700°C to improve physical properties such as thermal properties. Accordingly, the addition of water glass to a flammable material is advantageously utilized in improving the fire retardancy. Furthermore, water glass is known to be a low toxicity material. For example, silica gel prepared by adding protons to water glass is widely utilized as a desiccant in the food industries.
Recently, as it is known that water glass has many useful properties such as above-mentioned properties, in particular, fire retardant effects, great efforts have
been undertaken to beneficially utilize water glass in human life.
However, since simply dried water glass is likely to be dissolved in water, it has a problem of poor durability. In an effort to solve this problem, novel preparation techniques of silicate materials, scientific identification of the water- insolubilization mechanism of water glass and studies on improvement of physical properties of water glass are extensively performed. For example, Kalapathy et al. introduced a method for preparing a silica film having superior flexibility and strength by extracting amorphous silica present in rice hull ash with an aqueous caustic soda solution, condensing the extract solution, adding isopropyl alcohol and some additives thereto, homogeneously mixing and drying (Bioresource
Technology, 72, 99-106, 2000).
Knoblich and Gerber investigated the agglomeration of SiO2 in water glass solution by the X-ray small angle scattering method, and as a result, they reported that the agglomeration is directly affected by the concentration of protons present in the aqueous solution, and that water-insoluble silica gel is rapidly formed at a pH of
2.2-5.8, whereas the reaction rate is low at a pH of 5.8-6, (J. of Non-Crystalline Solids, 283, 109-113, 2001).
U.S. Patent No. 6,303,234 discloses that when cellulose materials, including fabrics, papers, ply woods and similar materials, are treated with water glass and were further treated with silicon monoxide or dioxide vapor, excellent fire retardancy, high flexibility and stable treatment of water are attained.
Further, U.S. Patent No. 6,146,766 discloses a method for preparing a material having excellent fire retardancy, strength and moisture resistance. According to this method, sodium silicate and a water-soluble fire retardant are incorporated into the interior of various cellulose materials by using a vacuum/pressure technique, and are then heat polymerized.
In order to solve the vulnerability of water glass to water, extensive research has been recently conducted into the utilization of water glass as a fire retardant, and techniques for manufacturing fire retardant products using water glass are published. However, since these techniques are based only on the fact that the application of water glass can improve the fire retardancy, their applicability is limited according to the materials and structures of substrates used. Until now, no techniques have been established that can improve the physical properties of water glass applied to substrates having various structures and chemical compositions. The present invention has been made in view of the above problems, particularly poor durability, of the conventional fire retardant treatment methods for imparting fire retardancy to a substrate by treating the substrate with water glass.
Therefore, it is an object of the present invention to provide a fire retardant treatment method of a substrates using water glass which is capable of imparting water-insolubility, superior fire retardancy and smooth and dense surface characteristics to the substrate while providing excellent flexibility and durability without generating dust.
Disclosure of the Invention
The present inventor developed a fire retardant treatment method applicable to various substrates by combining a treatment method for concurrently performing material transfer of silica produced using glass water, lipophilical modification and polycondensation of silica, with a technique for sufficiently imparting flexibility and water resistance under selected optimum conditions, and as a result, accomplished the present invention.
In order to accomplish the above object of the present invention, there is provided a fire retardant treatment method using water glass, comprising the steps of: treating a substrate with water glass as a fire retardant by a spraying, dipping or applying process; treating the water glass-treated substrate with a treatment agent to chemically solidify the water glass and impart lipophilicity to the water glass, the treatment agent including at least one modifier selected from Cι~8 alcohols, ketones and ethers and an acid capable of inducing a polymerization reaction of a silicate material; and drying the resulting substrate to evaporate water.
According to the method of the present invention, an acid and an alcohol, ketone or ether are mixed with water glass, which is known to be a relatively low price fire retardant having excellent fire retardancy without posing any health risk to humans, in an appropriate mixing ratio to separate water contained in the water glass and lipophilically modify the water glass, thereby forming a water-insoluble fire retardant material with improved flexibility. In the fire retardant thus modified, portions of thermally decomposable hydroxyl groups of silica are blocked with alkyl groups of the modifier, thereby exhibiting better heat resistance and thus fire retardant effects are further improved.
Hereinafter, this procedure will be explained in detail with reference to the accompanying drawings while comparing with the prior art.
Fig. 1 is conceptual diagrams schematically showing the formation of water-insoluble silica by the addition of an acid in accordance with a prior art, and Fig. 2 is conceptual diagrams schematically showing the formation of water- insoluble and lipophilically modified silica in accordance with the method of the present invention;
First, the prior art will be explained below. Referring to Fig. 1, a silicate material b is dissolved in water a to form water glass A, and then an acid is added to the. water glass. Since the silicate material b contained in the water glass is dispersed in the water a, only adjacent silicate material particles b are polymerized (B). Thereafter, drying is carried out so that the water is evaporated and the silica is separated into fine particles and solidified (C). Since the silica exhibits poor coating property, durability and water resistance, it cannot be used for the purpose of imparting fire retardancy by coating the fire retardant.
In contrast, the method of the present invention will be explained below. Referring to Fig. 2, a silicate material b is dissolved in water a to form water glass
A, and then an acid and an alcohol as a modifier are added to the water glass (A). At this time, the silicate material b contained in the water glass undergoes a polymerization reaction of silica, and at the same time, the alcohol c is chemically bonded to the silicate material to form a lipophilic group, thereby separating the water a from the polymerized lipophilic silica (B). Accordingly, when the polymerization is proceeded while appropriately controlling the compositions of the acid and the modifier, the lipophilic silica B has a lower water content. Accordingly, since the formation of pores due to water evaporation is prevented despite drying, a material having smooth surface characteristics can be prepared (C). In conclusion, the method of the present invention can provide a fire retardant material having superior flexibility and durability without generating dust.
In a preferred embodiment of the method according to the present invention, drying is carried out after application of the water glass and before addition of the treatment agent. This drying is carried out to previously remove water originally contained in the water glass or used for diluting the water glass to some extent so that the separation of water during lipophilical modification by the modifier is facilitated.
Meanwhile, in the fire retardant treatment method of the present invention, the addition of the treatment agent and the water glass to the substrate may be carried out by, but is not especially limited to, spraying using a sprayer, dipping or padding in the water glass solution, or application using a shearing blade or roller.
Possible various techniques can be employed for the addition.
The water glass used in the method of the present invention will be described below. The chemical composition of the water glass is generally represented by the following formula M2OmSiO2-nH2O wherein M is an alkali metal selected from Li, Na, K, Ru and Cs, or a quaternary ammonium base, and m represents the molar ratio of the metal oxide and is in a broad range. For example, in the case that M is Na, m is in the range of 0.54-4. In the case that M is K, m is in the range of 2-3.8. In the case that M is Li, m is in the range of 3.5-7.5. In the case that M is a quaternary ammonium, m is in the range of 1.2-30. addition, it is known that water glass contains a variety of silicate anions including (SiO4)4", (Si2O7)6-, (Si3O9)6\ (Si4Oι2)8", (Si6O18)12" and the like.
The water glass is typically produced by a dry process wherein a mixture of silica sand and sodium carbonate is heated to 1, 300-1, 500°C to form glass, and is then treated in a low pressure autoclave, or by a wet process wherein a mixture of colloidal silicic acid or diatomite and sodium hydroxide is heated, reacted and dissolved in an autoclave. The water glass thus produced is currently used as a raw material for detergents, cleaning agents, permeating agents, binders, adhesives, fireproofing agents, soil hardeners and a raw material for fireproofmg cements, a raw material for water-softening agents, a raw material for silica gel, a preservative for eggs, etc. Commercially available water glass is produced from various compositions in accordance with a variety of processes as described above. However, the composition of the water glass used in the present invention is not particularly limited. A preferred example of the water glass used in the present invention is an aqueous solution prepared by dissolving at least one silicate material selected from sodium silicate, potassium silicate and soda potassium silicate in water. The content of the silicate material in the water glass is preferably in the range of 0.5-80% by weight. Taking conditions for completely applying on substrates, productivity and fire retardancy into consideration, the silicate material is preferably present in an amount of 5-60% by weight and the water is preferably present in an amount of 94-39% by weight. In addition to water and silicate material, additives for the purpose of imparting additional functions are present in an amount of 0.01-10%) by weight, and other water-insoluble suspended substances and impurities are present in an amount of 0.1-10% by weight.
Examples of the additives for the purpose of imparting additional functions include quaternary ammonium salts, antibacterial agents such as chitosan, far- infrared emitting materials such as loess, silica, jade and silicon, heating materials such as ferrite and germanium, anion-emitting materials such as activated carbon or
bamboo charcoal, deodorizing agents such as charcoal and activated carbon, fire retardants such as antimony trioxide, phosphate compounds, boron, boric acid and aluminum oxides, conductors such as conductive fillers and carbon fiber, and the like. Hereinafter, the treatment agent used in the present invention will be discussed. The treatment agent is a mixed solution comprising: at least one modifier selected from alcohol compounds capable of promoting the separation of water present in aqueous solution due to the high affinity for water and inducing a coupling reaction with silica, and ketone or ether compounds capable of inducing an addition reaction; and an acid capable of catalyzing a polycondensation of a silicate material.
The modifier reacts with the water glass applied on the substrate to make the surface characteristics of silica lipophilic, and acts as a plasticizer to lower the hardness and improve the flexibility of silica. The acid used in the present invention promotes a polymerization reaction of silica to make the silica water- insoluble, thus improving water resistance. Consequently, the treatment agent improves the flexibility and durability of the silica.
The silicate material contained in the water glass exists in an ion form. A compound having simultaneously a functional group capable of chemically reacting with anions of the silicate and a functional group capable of imparting the lipophilicity, can be applied to lipophilical modification of silica. However, the compound must promote the separation of water upon mixing with water contained in the water glass and must be well mixed with the acid catalyst. For these purposes, the alcohol, ketone and ether compounds used in the present invention preferably contain one to eight carbon atoms. When the number of carbon atoms is too large, the affinity of the compounds for water is undesirably poor and the reactivity is low.
Alcohols concurrently satisfying the above-mentioned requirements include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclopropanol, cyclobutanol, phenol, benzyl alcohol, ethylene glycol, glycerol, sorbitol, polyvinyl alcohol and the like.
Examples of suitable ketones include acetone, methylethylketone, cyclohexanone, 2-methylcyclopentanone, methylvinylketone, acetophenone, benzophenone, dicyclopropylketone, etc., and those of suitable ethers include methylethylether, diethylether, diphenylether, 2-methoxypentane, trans-2- methoxycyclohexanol, 1 ,3,5-trimethoxybenzene, 2-ethoxy-3-methylbutane, dicyclopropylether, ethylene oxide, tetrahydrofuran, tetrahydropyran, 1,4-dioxane,
etc.
Exemplary acids used in the present invention include organic acids such as acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propionic acid, succinic acid, oxalic acid, ascorbic acid, gluconic acid, tartaric acid, maleic acid, citric acid, glutamic acid, toluenesulfonic acid, etc., and inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.
Materials for the substrate include, but are not particularly limited to, non- woven fabrics obtained from fibers or pulps, papers, knitted fabrics, woven fabrics, resin sheets, panels made of resins or wood, boards made of resins or woods and the like. In particular, the fire retardant treatment method of the present invention is expected to be widely applied to construction materials regulated by the Fire Service Act.
Meanwhile, according to the fire retardant treatment method of the present invention, the water glass is used in an amount of 2-300% by weight, based on the weight of the substrate. The modifier is used in an amount of 1-50% by weight, based on the weight of water glass used. The acid is used in an amount of 5-40% by weight, based on the total amount of the treatment agent so that the pH of the treatment agent is adjusted to 1-7.
Since commercially available water glass has various compositions, the amount of water glass to be used cannot be defined in all cases. However, it is preferred that the water glass is used in the amount range defined in the present invention. When the water glass is used in an amount of more than 2% by weight, sufficient fire retardancy can be exerted. Accordingly, an amount more than 2% by weight is preferably used, considering the inherent properties of the materials and required fire retardancy. However, if the amount of the water glass used exceeds
300% by weight, the application of the water glass may be difficult depending on the type of the substrate and it is economically disadvantageous due to the excessive amount. Hence, it is preferred that the amount of the water glass used is limited to below 300% by weight. Although the amount of the modifier also cannot be defined in all cases because the reactivity with the water glass and the degree of lipophiHcity depend on the number of carbon atoms, the reactivity with the water glass depends on the kind of reactive groups and degree of lipophiHcity of side chains and characteristics and structures of the substrate and required fire retardancy also should be considered, the modifier is preferably added in an amount of 1-50% by weight, based on the weight of the water glass. At this range, desired lipophilical modification effects can be attained. More preferably, the modifier is used in an amount of about 10-20% by
weight.
The amount of the acid used is determined according to the amount of the water glass and the modifier, characteristics and structures of the substrate, desired properties of the fire retardant product and the like. As a result of experiments conducted by the present inventor, the use of an excess of acid results in poor flexibility and water resistance. Accordingly, considering the amount of the modifier used, the acid is used in an amount of 5-40% by weight, based on the total amount of the treatment agent so that the pH of the treatment agent is adjusted to 1-7. More preferably, the pH of the treatment agent is adjusted to 3-7 for stable polycondensation of silica and more smooth surface characteristics.
In order to better understand the principle that the surface characteristics and water resistance are improved by the method according to the present invention, a possible mechanism of chemical reactions between the water glass and the treatment agent will be explained below. It is understood that the improvement in lipophilical surface modification and flexibility of silica contained in the water glass is due to a coupling reaction between the alcohol having a hydroxyl group (-OH) and active silica, as depicted in Reaction Scheme 1 below:
Reaction Scheme 1
I 2 TT,0
When a ketone-based compound is used as a modifier, it is understood that the improvement in lipophilical surface modification and flexibility of silica contained in the water glass is due to an addition reaction between the ketone having a carbonyl group and active silica, as depicted in Reaction Scheme 2 below:
Reaction Scheme 2
HO
On the other hand, it is understood that the improvement in water resistance of the water glass is due to the addition of protons catalyzing a polymerization reaction of silica as depicted in Reaction Schemes 3 and 4 below:
Reaction Scheme 3
Na2SiO3 + H2O + H2SO4 → Si(OH)4 + Na2SO4 Si(OH)4 + Si(OH)4 → (OH)3-Si-O-Si(OH)3 + H2O
Reaction Scheme 4 Na2SiO3 + H2O + 2HC1 → Si(OH)4 + 2NaCl
Si(OH)4 + Si(OH)4 → (OH)3-Si-O-Si(OH)3 + H2O
Specifically, Reaction Scheme 3 depicts a polymerization reaction of silica upon addition of sulfuric acid to the water glass, and Reaction Scheme 4 depicts a polymerization reaction of silica upon addition of hydrochloric acid to the water glass.
Brief Description the Drawings
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
Fig. 1 is conceptual diagrams schematically showing the formation of silica through a polycondensation between silicate materials during polymerization of water glass by the addition of an acid;
Fig. 2 is conceptual diagrams schematically showing the formation of modified silica tlirough a reaction of a silicate material, a modifier and an acid in a fire retardant treatment method using water glass of the present invention;
Fig. 3 is a graph showing the results of thermogravimetric analysis of a fire retardant non- woven fabric produced according to Example 1 of the present invention;
Fig. 4 is a graph showing the results of thermogravimetric analysis of an untreated cotton non-woven fabric;
Fig. 5 is an electron microscope image of a film produced in Example 2 of the present invention;
Fig. 6 is an electron microscope image of a film produced in Comparative Example 1;
Fig. 7 is an electron microscope image of a film produced in Comparative Example 2;
Fig. 8 is an X-ray diffraction pattern of a film produced in Example 2 of the present invention; Fig. 9 is an X-ray diffraction pattern of a film produced in Comparative
Example 1;
Fig. 10 is an X-ray diffraction pattern of a film produced in Comparative Example 2; and
Fig. 11 is a graph showing the results of thermogravimetric analysis of films produced in Example 2, and Comparative Examples 1 and 2.
Best Mode for Carrying Out the Invention
Example 1: Fire retardant treatment of non-woven fabric using water glass
A fire retardant non-woven fabric was produced in accordance with the following procedure, and then the thermal characteristics were analyzed. Tests were conducted for fire retardancy of the non-woven fabric treated in accordance with the fire retardant treatment method of the present invention.
A. Production of fire retardant non-woven fabric
Treating with water glass solution
A 5 cm thick cotton non- woven fabric (area: 100cm2) was completely wetted in an aqueous water glass solution at 30°C for 2 minutes. Thereafter, while the pressure of a mangle roller was adjusted to 3kg/cm2 to control the add-on rate of the water glass to 80%, the remaining solution was squeezed out.
The aqueous water glass solution used herein was obtained by two-fold diluting commercially available water glass containing 28-30% of SiO2, 9%~10% of Na O and 0.03% or less of Fe2O3 with water. Drying
The non-woven fabric (water content: 50%) treated with the water glass was dried using a hot-air drier at 150°C for 10 minutes to adjust the water content to 20%.
Modification of treated water glass 2kg of acetic acid was added to 8kg of ethanol, and the resulting mixture was homogeneously mixed to prepare a treatment agent. The dried water glass- treated non-woven fabric was dipped in the treatment agent for 1 minute. An
excess of the treatment agent was removed using a mangle roller. Finally, the liquid water glass contained in the non-woven fabric was converted to a water- insolubly modified silica having superior durability and flexibility. Drying of fire retardant treated non-woven fabric The non-woven fabric treated with the treatment agent was dried using a hot-air drier at 150°C for 20 minutes to produce a final fire retardant non- woven fabric.
B. Analysis of thermal characteristics of fire retardant non-woven fabric Thermal analysis of the fire retardant non- oven fabric produced above and an untreated cotton non-woven fabric was conducted using a thermogravimetric analyzer (TGA).
The results are shown in Figs. 3 and 4.
Fig. 3 is a graph showing the results of thermogravimetric analysis of the fire retardant non- woven fabric produced according to Example 1 of the present invention. It was confirmed from Fig. 3 that the weight loss at 450°C was only about 40% and about 60% still remained. Fig. 4 is a graph showing the results of thermogravimetric analysis of the untreated cotton non-woven fabric. As can be seen from Fig. 4, the weight loss at 450°C reached about 90% and only about 10% of ash remained.
These results indicate that the non-woven fabric produced by the fire retardant treatment method of the present invention has excellent fire retardancy.
Example 2, and Comparative Examples 1 and 2; Variation in physical properties versus various treatments of water glass
A. Production of silica film
30g of water glass containing 28%~30% of SiO2, 9%~10% of Na2O and 0.03% or less of Fe2O3 was applied on three glass plates to a thickness of 1mm using a film forming machine, and then the resulting structures were solidified to produce silica films in accordance with the following three procedures:
Example 2: A liquid containing 4g of ethanol and lg of acetic acid was homogeneously applied on the glass plate using a sprayer, and then dried using a hot-air drier at 150°C for 10 minutes. Comparative Example 1: The glass plate was dried using a hot-air drier at 150°C for 10 minutes.
Comparative Example 2; 3g of acetic acid was homogeneously applied
on the glass plate using a sprayer, and then dried using a hot-air drier at 150°C for 10 minutes.
Pieces of the silica films thus produced were cut and then water solubility, occurrence of dust, crystallinity and heat resistance of the cut pieces were measured.
B. Measurement of water solubility lg of the silica films produced in Example 2, and Comparative Examples 1 and 2 were placed in respective beakers, and then lOOg of water was added thereto. Each solution was stirred using a stirrer at room temperature for 1 hour.
Undissolved residues were passed tlirough filter paper, collected, dried and weighed to measure the water solubility of the silica films. From these observations, the silica film produced in Comparative Example 2 was completely dissolved and no residue was left, whereas the silica films produced in Example 2 and Comparative Example 2 were undissolved, indicating that they are water-insoluble.
C. Examination of dust occurrence and analysis of surface characteristics by electron microscopy
Pieces of the silica films produced in Example 2, and Comparative Examples 1 and 2 were cut, and then Pt ions were deposited thereon to impart conductivity thereto. Dust occurrence was observed and surface characteristics were analyzed using electron microscopes (3,000x (Example 2), and 2,000x (Comparative Examples 1 and 2)).
As shown in Fig. 5, in the case of the silica film of Example 2 produced by adding a liquid containing 4g of ethanol and lg of acetic acid and solidifying the water glass, since water contained in the water glass was appropriately displaced with ethanol and the silica was polymerized while lipophilically modifying it, it was observed that the surface was smooth and no dust occurred.
In addition, it was observed that the silica film of Comparative Example 1 produced by heating the water glass to solidify it had a smooth surface and no dust occurred (Fig. 6).
In contrast, in the silica film of Comparative Example 2 produced by solidifying the water glass using an acid catalyst, since the polymerization of the silicate partially took place only between adjacent silicate particles and water was separated during drying, the silica film was produced in the form of particles and thus dust was generated. Accordingly, the silica film cannot be practically used as a fire retardant material.
D. Comparison of crystallinity using X-RAY diffraction analyzer
Pieces of the silica films produced in Example 2, and Comparative Examples 1 and 2 were cut, and were then analyzed at angles of from 3° to 35° and a rate of 2 minute using X-rays generated from a Cu electrode. Using the obtained results, the crystallinity of the silica films was compared.
As can be seen from Fig. 9, since the silica film produced in Comparative Example 1 had the lowest intensity of diffracted X-ray and crystallinity, it had the most flexible structure.
As can be seen from Fig. 10, since the water-insoluble silica film produced in Comparative Example 2 had a high crystallinity, it had poor flexibility. These results indicate that the silica film cannot be applied to highly flexible substrates and is not suitable for the fire retardant treatment method of substrates which may be deformed by an externally applied force.
In contrast, since the water-insoluble silica film produced in Example 2 had an intermediate crystallinity, it is apparent that the silica film had flexibility to some extent (Fig. 8).
E. Comparison of heat resistance of solidified water glass using thermogravimetric analyzer Pieces of the silica films produced in Example 2, and Comparative
Examples 1 and 2 were cut, and then the heat resistance of the silica films were determined by measuring weight loss using a thermogravimetric analyzer while heating from 5°C to 850°C at a ratio of 20°C/min.
As can be seen from Fig. 11, since 80% of the silica film produced in Example 2 remained relative to the initial weight at 850°C(A), it was concluded that it had the best heat resistance. On the contrary, since 70% of the silica film produced in Comparative Example 1 remained relative to the initial weight at 850°C(C), the silica film had the worst heat resistance. Further, since 75% of the silica film produced in Comparative Example 2 remained relative to the initial weight at 850°C (B), the silica film had an intermediate heat resistance.
The analytical results are summarized in Table 1 below.
Table 1
Examples 3~17: Variation in physical properties according to change in components of treatment agent
Among alcohols, ketones and ethers applicable to lipophilical modification, compounds which can promote the separation of water, be mixed with an acid catalyst and exhibit less damage to humans were selected as modifiers. 4g of the modifiers and lg of acetic acid were mixed to prepare 5g of each treatment agent. The modifiers used in Examples 3-17 are listed in Table 2 below.
Next, 5g of water glass identical to that used in Example 1 was placed on each Schale, and then 5g of the treatment agents listed in Table 2 were added thereto. Wliile the resulting mixtures were stirred for 10 minutes, the solidification of the water glass was observed. Based on the observation, the reactivity was compared. In addition, after the mixtures were allowed to stand for 1 hour to sufficiently progress the reaction, the surface hardness was measured to compare the flexibility.
The reactivity between the modifiers and the water glass, and the flexibility of the films are summarized in Table 2 below.
Table 2
As shown in Table 2, the higher the hydrophilicity of alcohols, the higher was the reactivity with water glass but the lower was the flexibility of films. Conversely, the higher the lipophiHcity of alcohols, the lower the reactivity but the higher the flexibility. In the case of benzyl alcohol used in Example 11, the flexibility of the film was very high, but the reactivity was low. In addition, it was observed that phase separation took place during mixing with acid, causing poor workability. On the contrary, in the case of ketones and ethers, the reactivity and flexibility were relatively high than those of alcohols.
Examples 18-26: Variation in physical properties according to change in compositions of treatment agent
In these examples, the flexibility and water resistance of silica films produced by varying the mixing ratio between a modifier for lipophiHcity impartment and an acid for polymerization catalysis were examined.
Ethanol was used as the modifier, and acetic acid was used as the acid. Treatment agents were prepared by varying the weight ratio of ethanol to acetic acid to 1:9 (Example 18), 2:8 (Example 19), 3:7 (Example 20), 4:6 (Example 21), 5:5 (Example 22), 6:4 (Example 23), 7:3 (Example 24), 8:2 (Example 25) and 9:1 (Example 26), respectively.
Next, 5g of water glass identical to that used in Example 1 was placed on each Schale, and then lOg of the treatment agents were added thereto. The resulting mixtures were allowed to stand for 1 hour to solidify the water glass. Thereafter, the mixtures were heated using a hot-air drier at 150°C for 30 minutes for complete drying to obtain silica films. lOg of water was added to the silica films to thoroughly wet them. This wetting procedure was repeated. The water resistance of the silica films was evaluated by recording the number of cycle where the first crack was observed. The results are summarized in Table 3 below.
Table 3
As can be seen from the data shown from Table 3, the silica film produced using the treatment agent having a weight ratio of 8:2 (ethanol: acetic acid) exhibited the best durability in the case that ethanol and acetic acid are used.
Although the present invention has been described herein with reference to its preferred embodiments, these embodiments do not serve to limit the invention, but are set forth for illustrative purposes. The scope of the present invention is defined by the claims that follow. Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims, and are within the scope of the present invention.
Industrial Applicability
Although water glass enables impartment of excellent fire retardancy, it has problems of water-solubility and occurrence of much dust due to its poor durability and flexibility. For these reasons, water glass as a fire retardant has been not applied to various substrates.
As apparent from the above description, according to the fire retardant treatment method of the present invention, a treatment agent capable of improving flexibility, water-insolubility and heat resistance is added to water glass, thereby enabling application to various substrates. Hi addition, since the present invention provides a fire retardant treatment method using relatively low price water glass, it enables impartment of fire retardancy to flammable materials at low cost.
Therefore, various construction materials, coating materials, mechanical components, automobile parts and aircraft parts can be manufactured at low costs in accordance with the present invention.
Claims
1. A fire retardant treatment method using water glass, comprising the steps of: treating a substrate with water glass as a fire retardant by a spraying, dipping or application process; treating the above water glass-treated substrate with a treatment agent to chemically solidify the water glass and impart lipophiHcity to the water glass, the treatment agent including at least one modifier selected from alcohols, ketones and ethers capable of reacting with a silicate material to form a lipophilic group, and an acid capable of inducing a polymerization reaction of the silicate material; and drying the resulting substrate to evaporate water.
2. The fire retardant treatment method according to claim 1, further comprising the step of drying for removing water contained in the water glass after the treatment with water glass.
3. The fire retardant treatment method according to claim 1 or 2, wherein the addition of the treatment agent to the water glass is carried out by a spraying, dipping or application process.
4. The fire retardant treatment method according to claim 1 or 2, wherein the substrate is a non-woven fabric obtained from fiber or pulp, a paper, a knitted fabric, a woven fabric, a resin sheet, a panel made of resin or wood, or a board made of resin or wood.
5. The fire retardant treatment method according to claim 1 or 2, wherein the water glass is an aqueous solution of at least one silicate material selected from sodium silicate, potassium silicate and soda potassium silicate, and the silicate material is present in an amount of 0.5-80% by weight, based on the weight of the water glass.
6. The fire retardant treatment method according to claim 5, wherein the water glass contains 5-60% by weight of the silicate material, 94-39% by weight of water, 0.01-10% by weight of at least one functional additive and 0.1-10% by weight of water-insoluble suspended substances and impurities, and the functional additives is selected from quaternary ammonium salts, antibacterial agents such as chitosan, far-infrared emitting materials such as loess, silica, jade and silicon, heating materials such as ferrite and germanium, amon-emitting materials such as activated carbon or bamboo charcoal, deodorizing agents such as charcoal and activated carbon, fire" retardants such as antimony trioxide, phosphate compounds, boron, boric acid and aluminum oxides, and conductors such as conductive fillers and carbon fiber.
7. The fire retardant treatment method according to claim 1 or 2, wherein alcohol is selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclopropanol, cyclobutanol, phenol, benzyl alcohol, ethylene glycol, glycerol, sorbitol and polyvinyl alcohol.
8. The fire retardant treatment method according to claim 1 or 2, wherein the ketone is selected from acetone, methylethylketone, cyclohexanone, 2- methylcyclopentanone, methylvinylketone, acetophenone, benzophenone and dicyclopropylketone.
9. The fire retardant treatment method according to claim 1 or 2, wherein ether is selected from methylethylether, diethylether, diphenylether, 2- methoxypentane, trαH-?-2-methoxycyclohexanol, 1,3,5-trimethoxybenzene, 2- ethoxy-3-methylbutane, dicyclopropylether, ethylene oxide, tetrahydrofuran, tetrahydropyran and 1,4-dioxane.
10. The fire retardant treatment method according to claim 1 or 2, wherein the acid is selected from organic acids such as acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propionic acid, succinic acid, oxalic acid, ascorbic acid, gluconic acid, tartaric acid, maleic acid, citric acid, glutamic acid and toluenesulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.
11. The fire retardant treatment method according to claim 1 or 2, wherein the water glass is used in an amount of 2-300% by weight, based on the weight of the substrate.
12. The fire retardant treatment method according to claim 1 or 2, wherein the modifier is used in an amount of 1-50% by weight, based on the weight of water glass used.
13. The fire retardant treatment method according to claim 1 or 2, wherein the acid is used in an amount of 5-40% by weight, based on the total amount of the freatment agent so that the pH of the treatment agent is adjusted to 1-7.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2003/000102 WO2004062815A1 (en) | 2003-01-16 | 2003-01-16 | Fireproofing treatment method using water glass |
| AU2003203405A AU2003203405A1 (en) | 2003-01-16 | 2003-01-16 | Fireproofing treatment method using water glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2003/000102 WO2004062815A1 (en) | 2003-01-16 | 2003-01-16 | Fireproofing treatment method using water glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004062815A1 true WO2004062815A1 (en) | 2004-07-29 |
Family
ID=32709648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2003/000102 WO2004062815A1 (en) | 2003-01-16 | 2003-01-16 | Fireproofing treatment method using water glass |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU2003203405A1 (en) |
| WO (1) | WO2004062815A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011116450A1 (en) | 2010-03-26 | 2011-09-29 | Flamehalt Technologies, Inc. | Method for forming a fire resistant cellulose product, and associated apparatus |
| CN114716167A (en) * | 2022-05-17 | 2022-07-08 | 石家庄易辰防火保温材料有限公司 | Modified water glass for preparing heat-insulating fireproof material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3868258A (en) * | 1973-05-31 | 1975-02-25 | Idemitsu Kosar Kabushiki Kaish | Fireproofing composition and method |
| JPH02172847A (en) * | 1988-12-23 | 1990-07-04 | Shinto Paint Co Ltd | Expansion type fire proof protective composition |
| JPH10110121A (en) * | 1996-10-08 | 1998-04-28 | Kikusui Kagaku Kogyo Kk | Fire resistant coating material |
| US20010048984A1 (en) * | 2000-01-12 | 2001-12-06 | Legare David J. | Fire protection containers incorporating novel low free-water insulation materials |
| US20020110696A1 (en) * | 1996-03-15 | 2002-08-15 | K. M. Slimak | Process of using sodium silicate to create fire retardant products |
-
2003
- 2003-01-16 WO PCT/KR2003/000102 patent/WO2004062815A1/en not_active Application Discontinuation
- 2003-01-16 AU AU2003203405A patent/AU2003203405A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3868258A (en) * | 1973-05-31 | 1975-02-25 | Idemitsu Kosar Kabushiki Kaish | Fireproofing composition and method |
| JPH02172847A (en) * | 1988-12-23 | 1990-07-04 | Shinto Paint Co Ltd | Expansion type fire proof protective composition |
| US20020110696A1 (en) * | 1996-03-15 | 2002-08-15 | K. M. Slimak | Process of using sodium silicate to create fire retardant products |
| JPH10110121A (en) * | 1996-10-08 | 1998-04-28 | Kikusui Kagaku Kogyo Kk | Fire resistant coating material |
| US20010048984A1 (en) * | 2000-01-12 | 2001-12-06 | Legare David J. | Fire protection containers incorporating novel low free-water insulation materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011116450A1 (en) | 2010-03-26 | 2011-09-29 | Flamehalt Technologies, Inc. | Method for forming a fire resistant cellulose product, and associated apparatus |
| EP2550397A4 (en) * | 2010-03-26 | 2017-02-01 | Blmh Technologies Inc. | Method for forming a fire resistant cellulose product, and associated apparatus |
| CN114716167A (en) * | 2022-05-17 | 2022-07-08 | 石家庄易辰防火保温材料有限公司 | Modified water glass for preparing heat-insulating fireproof material |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003203405A1 (en) | 2004-08-10 |
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