KR101574173B1 - Hydrophobic organic or inorganic composite by polymer and silicate composite for intumescence fireproof coating - Google Patents

Abstract

A hydrophobic oil-and-inorganic composite fogging fire-retardant covering composition composed of a polymer and a silicate compound is disclosed. (A) 60 to 90% by weight of a 10% aqueous solution of PVA; (b) 5 to 20% by weight of an alkaline silicate; (c) 0.1 to 0.3% by weight of a nonionic surfactant; (d) 3 to 10% by weight of weak acid; And (e) 1.9 to 9.7% by weight of phenol, wherein the total amount of the components (a) to (e) is 100 parts by weight.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a hydrophobic oil-and-inorganic composite porosity resistant fire-retardant covering composition comprising a polymer and a silicate compound, and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a hydrophobic oil-based and inorganic composite fogging fire-retardant covering composition comprising a polymer and a silicate compound. More particularly, the present invention relates to a fire-retardant coating composition comprising a polyvinyl alcohol capable of forming a carbonized layer upon fire, Inorganic composite fogging fireproofing coating composition comprising a polymer and a silicate compound capable of exerting excellent heat resistance and heat insulation property by modifying it with a weak acid and phenol to produce a carbonized layer.

The fireproofing material protects buildings and the like from fire to provide a time to suppress the fire by blocking or delaying the approach of the high temperature heat or flame to the surface covering material of the building such as the steel or concrete wood, It is a covering material that provides time. A fire-resisting structure is a structure in which a main structural part of a building has a fire-proofing ability to withstand a high temperature for a certain period of time in a fire, and at the same time, can be reused by simple repair after a fire.

On the other hand, the low-carbon steel used for the structural steel structure has a critical temperature of about 540, and the strength is usually reduced to about 60% at the above critical temperature. Therefore, in order to minimize the damage of the steel structure due to the reduction of the strength of the steel frame and the damage caused by the fire, the steel frame is applied to the steel structure. Also, in case of concrete structures, it is necessary to maintain the original properties of the concrete structure after the fire suppression, and therefore fireproof coating is carried out.

In general, various basic performances are required for the fireproof fire-resistant cover material to exhibit the function of protecting the steel structure or the concrete structure in case of fire. First, in order to have sufficient heat insulation, the foaming should be smooth and the thickness of the foam coating should be higher than a certain level. When the foaming thickness is thin, sufficient heat insulating property can not be exhibited. Second, the density of the foam layer must be sufficiently high for effective insulation. Even if the thickness of the foam layer is thick, if the density of the foam layer is low, penetration of heat from the outside can not be effectively prevented. Third, uniform foaming should occur without cracking due to excessive foaming or shrinkage upon foaming. If cracks are generated in the foamed coating, the heat may flow into the steel or concrete through the cracked portion and the required fire resistance performance can not be exhibited. Most importantly, the steel or concrete of the building must have no change in film quality due to shrinkage expansion over a long period of time after construction.

On the other hand, as a general pseudo fire resistant coating composition, a composition comprising an organic polymer, an ammonium polyphosphate and a polyhydric alcohol is predominant. In this type of refractory covering composition, ammonia gas or halogen gas, which is poisonous gas, is generated as a by-product at the time of foaming when a fire occurs and the foam layer is made of a carbonized layer, so that the foam layer can easily break . That is, since the refractory performance is limited as described above, the products and applications thereof are limited.

In addition to these organic type fireproof coating materials, there are inorganic fireproof coating materials having a silicate as a main binder. This can solve the problems of the organic type fireproof coating material, but the thickness of the coating film is too thick as compared with the organic fireproof coating material, and cracks occur in the coating film during the drying shrinkage after the application, .

As a specific example, Korean Patent Laid-Open Publication No. 1989-0010138 discloses a technique for fouling fire resistant inorganic fire with liquid metal silicate as a main binder. However, such a composition has a very high pore resistance, but it has a limit in heat resistance of the metal silicate used, so that there is a problem that the foamed coating layer melts and flows down at a high temperature of about 600 or more.

Japanese Unexamined Patent Publication (Kokai) No. 5-86310 discloses a coating composition for a pseudo fire resistant coating material using ammonium polyphosphate as a foaming agent, melamine as a fireproofing agent, and modified epoxy as a binder. This type of coating material is a coating material in which the coating material composition receives heat and forms a carbon layer by chemical reaction at about 400 to protect the material from heat. This coating material is excellent in pore performance, but has the disadvantage that the foam layer easily breaks due to hot air because it forms a very weak carbonated layer as well as emits a large amount of ammonia gas when the coating film is foamed.

Korean Patent Laid-Open Publication No. 2005-0070809 also discloses a porcelain refractory coating composition containing a molar ratio controlling agent, a reinforcing agent, an extender pigment, an expandable graphite or an encapsulated foaming additive, and an additive in a silicate. Such a refractory coating composition is excellent in heat resistance by controlling the molar ratio of the silicate and using a reinforcing agent and an additive. However, in the above composition, the expandable graphite is used as the foaming aid for blocking the flame. Also, since the carbonized layer formed by the carbon dioxide is weak, the foam layer is easily broken by the hot air and the flame is infiltrated into the broken foam layers again have. In addition, the composition has a problem in that the carbon dioxide produced by pyrolysis is not retained in the foam layer and is released into the atmosphere, thereby deteriorating the capability of blocking flame propagation.

On the other hand, the general foaming / expansion / thermal insulation mechanism of the silicate fireproof covering material is as follows. That is, the silicate used as the binder has a water content of 40 to 70% by weight. When the water content of the silicate is 70 to 130 or more, the water is expanded and expanded to form various types of cells, do. However, the density of these cells is lowered by extender pigments and other fillers used together with the coating materials in manufacturing the coating materials, and the coated and expanded film is melted at a high temperature of 600 or more due to insufficient heat resistance. Therefore, in order to maintain excellent heat resistance performance at a high temperature for a long time, a thick coat layer of more than several thousand microns must be formed.

Korean Patent Publication No. 1989-0010138 Japanese Patent Application Laid-Open No. 5-86310 Korean Patent Publication No. 2005-0070809

An object of the present invention is to provide a method for preparing a polyvinyl alcohol (hereinafter referred to as "PVA") as a basic binder and crosslinking with an alkali silicate (hereinafter referred to as "SS") at a temperature of around 80 ° C. SS-compound forming a cross-link type foamable carbonization layer and a povidic layer, and a nonionic surfactant for stabilizing PVA-SS at room temperature, and to promote the carbonization layer formation of the PVA-SS compound By adding weak acid and phenol, it is possible to exert excellent fire resistance performance and heat insulation performance, and it is possible to effectively prevent the emission of carbon dioxide generated by pyrolysis and prevent the emission of atmospheric carbon dioxide Which is composed of a polymer and a silicate compound, so as to be able to block the flame-retardant coating material.

In order to accomplish the above object, the hydrophobic oil-and-mineral composite fugitive fireproofing coating composition composed of the polymer and the silicate compound according to the present invention,

(a) 60 to 90% by weight of a 10% aqueous solution of PVA; (b) 5 to 20% by weight of an alkaline silicate; (c) 0.1 to 0.3% by weight of a nonionic surfactant; (d) 3 to 10% by weight of weak acid; And (e) 1.9 to 9.7% by weight of phenol, based on 100 parts by weight of the total of components (a) to (e).

The alkali silicate is characterized by being selected from the group consisting of sodium silicate, potassium silicate and lithium silicate.

The weak acid may be selected from the group consisting of citric acid, tartaric acid and acetic acid.

A method of manufacturing a hydrophobic oil-and-inorganic composite fugitive fireproofing coating composition according to another embodiment of the present invention includes:

Mixing inorganic alkaline silicate with polyvinyl alcohol capable of generating a carbonized layer upon fire with a basic binder; Adding a nonionic surfactant to the mixture to cross-link the polyvinyl alcohol and the alkali silicate; Adding a weak acid to the cross-linked mixture to prevent cracking of the coating and to increase the strength of the foam layer; And adding phenol to the mixture to which the weak acid has been added to improve the refractory performance of the carbonized layer.

Wherein the PVA 10% aqueous solution contains 60 to 90% by weight, the alkali silicate 5 to 20% by weight, the nonionic surfactant 0.1 to 0.3% by weight, the weak acid 3 to 10% by weight, And a control unit.

 The hydrophobic organic and inorganic composite fogging fire retardant covering composition composed of the polymer of the present invention and a silicate compound is a composition comprising a carbonized layer formed by pyrolysis of PVA and phenol and a carbonized layer formed by decomposition and deformation of silica at a certain temperature or higher, The porosity is formed by the inorganic silicate compound, and thus the performance of heat shielding can be improved. Further, the composition of the present invention can improve the dry strength and heat resistance of the coating film and the strength of the porous pore layer by forming a complex oil and an inorganic compound of cross-linked PVA-SS. As a result, the hydrophobic oil-based and inorganic composite fogging fire-retardant covering composition composed of the polymer and the silicate compound of the present invention is excellent in heat resistance and heat insulation, and has excellent foaming efficiency and foam density. Therefore, the reinforcing bars, pillars, It is suitable as a fireproof covering material on pillars.

1 is a view showing a flame temperature by a general torch lamp,
2 is a diagram showing the results of the heat differential performance test according to the first embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, with reference to the accompanying drawings, a hydrophobic organic-inorganic composite fogging fire-retardant covering composition composed of a polymer and a silicate compound according to the present invention will be described in detail.

(A) 60 to 90% by weight of a 10% aqueous solution of PVA; (b) 5 to 20% by weight of an alkaline silicate; (c) 0.1 to 0.3% by weight of a nonionic surfactant; (d) 3 to 10% by weight of weak acid; And (e) 100 to 100 parts by weight of the total of the components (a) to (e) including 1.9 to 9.7% by weight of phenol. The hydrophobic organic / inorganic composite fire retardant covering composition comprising a polymer and a silicate compound to provide.

More specifically, the present invention relates to a process for preparing a polyvinyl alcohol, which comprises mixing a polyvinyl alcohol capable of forming a carbonized layer upon fire with an inorganic alkali silicate compound as a base binder, adding a nonionic surfactant to stabilize the compound, A hydrophobic oil-and-inorganic composite fugitive fireproofing coating composition composed of a polymer and a silicate compound exhibiting excellent heat resistance and heat insulation property can be obtained by modifying it with a weak acid and phenol to produce a carbonized layer.

In order for the hydrophobic oil-and-inorganic composite fogging fire-retardant covering composition composed of the polymer and the silicate compound to exhibit excellent fire resistance, the organic compound polyvinyl alcohol (PVA) and the inorganic compound alkali silicate (SS) The formation of the layer and the expansion of the pore must be done well. In the present invention, by controlling the composition ratio of PVA and SS and controlling the crosslinking by the surfactant, the formation of the carbonized layer and the expandability of the foam layer are improved, the foam density inside the foam layer by the carbonization is increased, The emission of carbon dioxide was prevented to increase the blocking performance of the flame propagation.

The above-mentioned PVA 10% aqueous solution employs general industrial PVA, and preferably has a molecular weight of 5000 or higher, but is not limited thereto.

The 10% PVA aqueous solution contains a carbon source. In the present invention, a large amount of carbon is converted into carbon dioxide by the initial combustion, and the cross-link type carbonized layer is formed by the temperature of the fire flame Which can be used as a fibrillated material having various types of pores in combination with the structure of an inorganic alkali silicate compound having a pore characteristic at a constant temperature.

The PVA 10% aqueous solution preferably contains 60 to 90% by weight, more preferably 70 to 80% by weight based on the total weight of the components (a) to (e). When the content of the PVA 10% aqueous solution is less than 60% by weight based on the total weight of the components (a) to (e), it is difficult to form the carbonized layer by complete combustion. When the content exceeds 90% The crosslinking with the alkali silicate does not proceed smoothly.

The alkali silicate, which is an inorganic silicate compound, is changed into a honeycomb structure by decomposition and deformation of silica at a temperature higher than a certain temperature to form a porous pore layer, thereby enhancing the performance of heat shielding.

The alkali silicate as the inorganic silicate compound is preferably included in an amount of 5 to 20% by weight based on the total weight of the components (a) to (e), and the content of the alkali silicate is in the range of When the amount is less than 5% by weight based on the total weight of the composition, formation of the formed povidone layer is insufficient. When the amount of the polyvinyl alcohol (PVA) is more than 20% by weight, generation of crosslinked products of polyvinyl alcohol (PVA) and alkali silicate (SS) .

The inorganic alkali silicate may be one or more selected from sodium silicate, potassium silicate and lithium silicate, but is not limited thereto.

In addition, the hydrophobic organic-inorganic composite fogging fire retardant covering composition composed of the polymer of the present invention and the silicate compound exerts a pore function of a carbonization layer of polyvinyl alcohol (PVA) and an alkali silicate (SS) In order to improve the cross-linking performance of SS, a non-ionic surfactant is used. By using such a nonionic surfactant, cross-linking of PVA-SS can be carried out smoothly.

In the present invention, it is preferable to use a weakly acidic substance as a reinforcing material. By using the reinforcing material, it is possible to prevent the coating film from being cracked due to water evaporation over a long period of time at room temperature after the coating layer of the crosslinked PVA-SS compound is applied to the building, to increase the strength of the foam layer in case of fire, An increase in heat resistance of the layer and prevention of cracks can be achieved. Further, in the case of a fire, carbon dioxide is discharged by pyrolysis due to temperature rise, and it is present in the pores of the inorganic fibrous material to block the oxygen source, thereby preventing continuous flame propagation.

The reinforcing material may be selected from the group consisting of citric acid, tartaric acid, and acetic acid, which are weakly acidic substances, but not limited thereto.

The reinforcing material is preferably 3 to 10% by weight, more preferably 6 to 8% by weight based on the total weight of the components (a) to (e). If the content of the reinforcing material is less than 3% by weight based on the total weight of the components (a) to (e), the effect as a reinforcing material is insignificant. If it exceeds 10% by weight, The acidity is deteriorated and the production efficiency can be lowered.

In the present invention, phenol is used as an additive to improve the refractory performance of the carbonized layer generated in the case of fire. The phenolic additive is a flame retardant and a heat resistant additive. When a fire occurs, it is dewatered at a temperature of 340 ° C or higher, and by performing a heat endothermic reaction, the heat transferred to the steel itself is exhausted to delay the temperature rise of the steel. In addition, the phenolic additive increases the strength of the pore layer by further strengthening the fibrous network structure in the pore layer expanded and expanded by the silicate compound, so that the pore layer is prevented from melting and flowing down even at a high temperature of 1,000 ° C or higher.

The phenol additive is preferably contained in an amount of 1.9 to 9.7% by weight, more preferably 3 to 6% by weight based on the total weight of the components (a) to (e). If the content of the phenol additive is less than 1.9 wt% based on the total weight of the components (a) to (e), the effect of the phenol additive is insufficient to achieve the purpose of use. If the content exceeds 9.7 wt% And the strength of the povidic layer due to the silicate compound is drastically strengthened in the event of a fire, resulting in an adverse effect on the foaming ratio of the coating film.

The hydrophobic organic and inorganic composite fire resistant coating composition composed of the polymer of the present invention and the silicate compound having the structure of the present invention is characterized in that polyvinyl alcohol which is a polymer in which an expansive carbonization layer is formed by a flame during a fire, A nonionic surface active agent for crosslinking PVA-SS, a porous fibrous compound capable of absorbing and storing weak acids and carbon dioxide for enhancing the dry strength (durability) of the povidic coating and exhibiting more effective functions in the event of a fire, And the reinforcing materials for strengthening the adhesion to the cover body are mixed at appropriate ratios, thereby effectively controlling the cracking and insufficient heat resistance of the carbonized layer and the pore layer, thereby maintaining the refractory performance for a long time even at a very hot high temperature.

Also, the hydrophobic oil-based and inorganic-composite fire-resistant coverings made of the polymer and the silicate compound obtained according to the present invention can be used as coating materials for general buildings, factory buildings, pillars and beams of dangerous goods storage and treatment facilities, and excellent fire resistance coating materials.

Hereinafter, examples and experimental examples of the present invention will be illustrated. The following Examples and Experimental Examples are provided only to aid understanding of the present invention, and thus the technical scope of the present invention is not limited thereto.

Example 1

10% by weight aqueous solution of PVA 10% by weight, 10% by weight of an inorganic alkali silicate compound which is converted into a pivalive membrane structure at a temperature of 500 ° C or higher and a silica content of 80% by weight or higher and mixed at a rotation speed of 200 rpm at 60 ° C for 10 minutes 0.2% by weight of a nonionic surfactant was added thereto, and the mixture was stirred at 80 ° C for 20 minutes at a rotation speed of 400 rpm. After 5.8% by weight of citric acid was added thereto, the mixture was further mixed at a rotation speed of 400 rpm for 10 minutes, Finally, phenol was added in an amount of 4.0% by weight, and the mixture was stirred at a rotational speed of 400 rpm for 20 minutes to prepare a refractory coating composition of the present invention.

The refractory coating composition prepared according to the above example was subjected to the fire resistance test as follows.

Experimental Example 1. Heating /

The purpose of this test is to test the fire resistance of the fireproof coating material by applying the fireproof coating material to the structural parts of beams and posts such as general buildings, factory buildings, and hazardous materials storage and treatment facilities. Specifically, a thermocouple was installed at uniform intervals on the steel plate and the plywood, and then the refractory covering material was painted and subjected to a heating test for 3 hours, so that the foamed coating of the refractory covering material was heat- As shown in Fig. At this time, a torch lamp was used as a heat source. The fire resistance performance is managed separately from the Korean industry standard (KS) by the heat capacity and the secondary performance. For the initial temperature (To), the average temperature should be within To + 140 ℃, It should not exceed 180 ℃. In the case of wood, there should be no flame propagation on the back.

Experimental Example 1-1: Heating performance test

The heat shielding performance of the refractory covering composition of Example 1 was tested on the iron plate, and the results are shown in Table 1 below. Specifically, 2 mm each of the refractory coating composition obtained in Example 1 was applied to a steel plate having a thickness of 1.6 mm, and the heat-insulating performance was tested.

As a result, as shown in the following Table 1, it was found that satisfies the heat performance of the standard for the refractory condition.

The flame temperature by a torch lamp which can be generally purchased in the market is as shown in Fig.

division Example 1 To 22.7 ° C Average temperature 139.3 DEG C Maximum temperature 186.7 DEG C

* To: measured at room temperature

EXPERIMENTAL EXAMPLE 2-2:

The results are shown in FIG. 2, after examining the iron-boron coating performance of the refractory coating composition of Example 1 against the plywood. Specifically, the refractory coating composition of the above example was applied to a plywood having a thickness of 12 mm by about 2 mm, thereby testing the iron-forming performance.

As a result, as shown in FIG. 1, the normal flame temperature of the torch lamp was in the range of 800 ° C on average, and the time to reach 800 ° C was within 15 minutes. However, in the case of the plywood to which the refractory coating composition of the embodiment was applied, as shown in FIG. 2, the temperature of the back surface of the plywood did not exceed 200 ° C. at maximum, and flame was not propagated to the wood even 1 hour after the flame was applied, Excellent.

From the above experimental results, it can be seen that the fireproof coating composition of the foamable carbonized layer structure according to the present invention is excellent in the ability to block the fire and prevent the temperature rise due to fire.

Claims (5)

(a) 60 to 90% by weight of a 10% aqueous solution of polyvinyl alcohol (PVA) which is a water-soluble polymer as a basic binder;
(b) 5 to 20% by weight of an alkali silicate, which is an inorganic silicate compound;
(c) 0.1 to 0.3% by weight of a nonionic surfactant;
(d) 3 to 10% by weight of weak acid as a reinforcing material; And
(e) 100 parts by weight of the total of components (a) to (e), including 1.9 to 9.7% by weight of phenol as an additive, to form a crosslinkable foamed carbonization layer and a foam layer by flame Wherein the hydrophobic oil-and-inorganic composite porphyritic fireproofing coating composition comprises The method according to claim 1,
Wherein the alkali silicate is at least one selected from sodium silicate, potassium silicate, and lithium silicate, wherein the alkali silicate is at least one selected from the group consisting of sodium silicate, potassium silicate, and lithium silicate. The method according to claim 1,
Wherein the weak acid is at least one selected from the group consisting of citric acid, tartaric acid and acetic acid. The hydrophobic organic / inorganic composite fugitive fire retardant coating composition according to claim 1, wherein the polymer and the silicate compound are selected from the group consisting of citric acid, tartaric acid and acetic acid. Mixing inorganic alkaline silicate with polyvinyl alcohol capable of generating a carbonized layer upon fire with a basic binder;
Adding a nonionic surfactant to the mixture to cross-link the polyvinyl alcohol and the alkali silicate;
Adding a weak acid to the cross-linked mixture to prevent cracking of the coating and to increase the strength of the foam layer; And
And a step of adding phenol to the mixture to which the weak acid is added in order to improve the refractory performance of the carbonized layer, thereby forming a crosslinked foamable carbonization layer and a pore layer by a flame during a fire. A method for manufacturing a fireproof fireproofing coating composition. 5. The method of claim 4,
Wherein the PVA 10% aqueous solution contains 60 to 90% by weight, the alkali silicate 5 to 20% by weight, the nonionic surfactant 0.1 to 0.3% by weight, the weak acid 3 to 10% by weight, Wherein the hydrophobic oil-and-inorganic composite porphyritic fire-retardant covering material composition comprises a water-insoluble polymer.

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