KR20120011555A - Composite Contained by Modified Silicone Type Intumescent Fire-Resistant Coating Compositions - Google Patents

Abstract

PURPOSE: A modified silicon-based fire-resistant paint is provided to form a carbonation layer of high density, thereby having water resistance and heat resistance without separation. CONSTITUTION: A modified silicon-based fire-resistant paint comprises a binder, a carbonizing agent, a foaming agent, an acid catalyst, a reinforcing agent, and additives. The binder consists of a modified silicone-based resin. The foaming layer, which is foamed and expanded at high temperature, has excellent heat resistance and heat insulation. The modified silicon-based resin comprises a structure in which 2-3 epoxide functional groups are involved in polysilanol. The average molecular weight of the modified silicon-based resin is 250-1200. The length of the long axis of the reinforcing agent is 20-300 micron, and the thickness is 0.1-5 micron. The reinforcing agent is a plate type glass flake.

Description

Modified Silicone Type Refractory Coating Composition {Composite Contained by Modified Silicone Type Intumescent Fire-Resistant Coating Compositions}

The present invention is a refractory coating composition, comprising a binder, a carbonizing agent, a foaming agent, an acidic catalyst, a reinforcing agent and additives, the binder is a modified silicone-based resin, modified foam having an excellent heat resistance and thermal insulation foam expansion and expansion at high temperature It relates to a silicone-based foamed refractory coating composition.

Recently, as buildings are getting higher and larger, the use of steel structures is increasing. Steel frame material itself is a non-flammable material, but the heat conduction is fast, if the high temperature of 800 ~ 1000 ℃ occurs in the building, the strength of the steel material is sharply lowered, which can cause deformation or collapse of the structure. For this reason, according to the building law, the design and construction of buildings, which require that the fire resistance performance of the pillars and beams of the main structural parts to be maintained for more than two hours is increasing.

Accordingly, in order to secure structural safety of a building such as to provide a spare time for evacuation in the event of a fire in the building, and to prevent the spread of fire by maintaining the structure and performance for a certain time or more, a building of a certain size is important. It is mandatory to design the structural part as a fireproof structure. However, domestically, there are no fireproof paints corresponding thereto, and alternative materials such as gypsum, vermiculite, and concrete fireproof walls have been used despite various disadvantages.

The use of refractory paints is a method of imparting fire resistance to steel and reinforced concrete structures, which reduces the load burden of the structure due to its thin coating thickness and provides aesthetics to structures exposed to the outside. There is an advantage to reduce the cost of repair.

In particular, the foamed refractory paint has a dry coating thickness of several to several tens of millimeters when fired, but when exposed to heat, the dry coating carbonizes and foams at a rate of tens to hundreds of times to form a thick insulating layer and generate an inert gas. It maintains the firmness of the foamed coating to withstand the hot wind and flame shock transmitted to it and prevents collapse by delaying the time the structure reaches the critical temperature.

In general, the higher the foaming rate, the lower the rigidity. Thus, when these two elements are properly harmonized and heated, foaming is performed due to the flexibility of the coating film, while exhibiting thermal insulation performance. The design of this non-occurring paint is an important factor in the development of refractory paint technology. In addition, it is important to elicit a complex action of the above elements because the thermal function inherent can be exhibited when the function as the paint itself, such as appearance, storage, water resistance and workability, is satisfied.

However, to date, gypsum-based and vermiculite-spreading materials are mainly used as coating materials having fire resistance of 2 hours or more, and recently, aqueous inorganic and oil-based systems have been certified and applied to steel sites, but more than 2 hours There is no product on the fireproof paint for concrete with fire resistance.

However, the refractory spraying material is dust generated during the work, the appearance of the work is poor, the adhesion to the steel structure is poor, the peeling phenomenon occurs after construction, there is a problem in the air purification, maintenance and repair of the structure Is generated and its use is avoided.

Therefore, due to technical limitations, such as the fire resistance performance of more than 2 hours, despite the advantages of the refractory paints as described above, the refractory material is occupied the majority of the refractory coating material market to date.

In order to solve this problem, Korean Patent Registration No. 590502 discloses a composition having a fire resistance of 2 hours using an inorganic silicate-based resin, but when the inorganic resin is used, the water resistance is poor and the adhesion to the coating is poor. There is this.

In addition, Korean Patent Registration No. 784738 discloses a composition using oily styrene-modified acrylic, which has fast drying performance and excellent weather resistance, and has a fire resistance of 2 hours without desorption of the foamed carbonized layer. It is not suitable for human body and environment because it lacks adhesion and wear resistance and contains excessive amount of organic solvent.

All of the fireproof paints have a fire resistance of 2 hours for steel, can not be applied to reinforced concrete structures, and can not replace the fire-resistant material up to 3 hours has a disadvantage that it is difficult to use in high-rise building fireproof coating materials have.

Therefore, there is a high need for a technology of high-performance foaming refractory paint capable of simultaneously expressing environmentally friendly characteristics while having a thin coating thickness and fire resistance of 3 hours or more.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-described problems of the prior art and the technical problems required from the past.

The inventors of the present application, after repeated in-depth studies and various experiments, as described later, modified silicone foamed refractory paint composition comprising a binder, a carbonizing agent, a foaming agent, an acid catalyst, a reinforcing agent and an additive made of a modified silicone-based resin In the case of using, it was confirmed that the foamed and expanded foam layer at a high temperature had excellent heat resistance and heat insulation, and the present invention was completed.

Therefore, the modified silicone foamed refractory paint composition according to the present invention,

Including binders, carbonizing agents, blowing agents, acid catalysts, reinforcing agents and additives,

The binder is made of a modified silicone resin,

The foamed expanded foam layer at high temperature is characterized by having excellent heat resistance and heat insulation.

The modified silicone resin used as the binder is cured at room temperature to give excellent weather resistance, plasticity, plasticity, and gives a fluidity to the coating when exposed to high temperatures due to fire. In addition, when foaming gas is generated, it prevents external leakage of the foaming gas and effectively forms a foaming layer, thereby reducing the density of the carbonized layer and desorption with the coating.

The modified silicone foamed refractory paint composition according to the present invention does not flow down from the vertical surface even when coated with a thickness of 4 mm or more at a time, and the building according to the fire resistance test method of the building structural part specified in Korean Industrial Standard KS F2257. It provides a refractory coating composition suitable as a fireproof coating for 3 hours to the reinforcement beams, columns and reinforced concrete structures.

In the modified silicone foamed refractory coating composition according to the present invention, the modified silicone resin is preferably made of a structure in which the polysilanol includes two to three epoxide functional groups.

In addition, the modified silicone resin preferably has a weight average molecular weight in the range of 250 to 1200.

The modified silicone resin may be prepared by reacting epichlorohydrin with a polysilanol compound to adjust the molecular weight, preferably two or more epoxide functional groups, more preferably in the range of 2 to 3 and weight It is preferable that the average molecular weight is 250 to 1200.

The equivalent ratio of silanol and epichlorohydrin is related to the silanol molecular weight, and it is preferable that an epoxide functional group is added in the range of 2-3. If the epoxide functional group is less than 2, the crosslinking density with the curing agent may be lowered, and thus the chemical properties and the density of the carbonized layer may be lowered. If the epoxide functional group is more than 3, the network structure is formed to increase the viscosity and the desired molecular weight. Since the weight average molecular weight of silanol is 120-600 and the weight average molecular weight of modified silicone resin is 250-1200 in this invention.

When the molecular weight of the silanol and the modified silicone resin is less than the above value, the crosslink density with the curing agent is lowered because the epoxide functional group is less than two, resulting in problems of lowering the chemical resistance and the density of the carbonized layer. If high, the chemical structure of the designed silanol has a high risk of becoming highly viscous or gelated. Therefore, it is preferable that the said modified silicone resin contains the epoxide functional group in the range of 2-3 within the range of the said molecular weight.

The polysilanol may be obtained by condensing silanol obtained by hydrolyzing an alkoxy silicate.

The alkoxy silicate may be at least one compound selected from the group consisting of methoxy silicate, ethoxy silicate, normal butoxy silicate, isobutoxy silicate, propoxy silicate, isopropoxy silicate and the like.

The polysilanol may also be obtained by hydrolyzing a polyalkoxy siloxane.

The polyalkoxy siloxane is at least one selected from the group consisting of siloxanes such as polymethoxy siloxane, poly ethoxy siloxane, poly normal butoxy siloxane, poly isobutoxy siloxane, poly propoxy siloxane, poly isopropoxy siloxane and the like Compound.

The alkoxy silicate and the polyalkoxy siloxane are hydrolyzed using water to form poly silanol having a hydroxyl group as a functional group, wherein the molecular weight is determined by the repeating unit of the condensation reaction. Repeating the condensation reaction is preferably 1 to 5, wherein the molecular weight may be formed of polysilanol of 120 to 600.

When hydrolyzing the said polyalkoxy siloxane, it is preferable that the equivalence ratio of alkoxy and water is the range of 1: 1-1: 2.

When the equivalent ratio is less than 1: 1, that is, the content of alkoxy silicate or alkoxysiloxane is higher than water, hydrolysis occurs easily due to unreacted alkoxy functional groups remaining in the modified silicone resin desired by the present invention. Water resistance and alkali resistance fall remarkably.

When the equivalent ratio is greater than 1: 2, that is, the equivalent ratio of water is greater than twice the equivalent ratio of the alkoxy silicate or the alkoxysiloxane, the silanol having the desired molecular weight is synthesized because silanol forms a cyclic polymer by the internal condensation reaction. Is difficult and fluidity is lowered, which may cause gelation or poor storage stability as viscosity increases.

In the modified silicone foamed refractory paint composition according to the present invention, the carbonizing agent reacts with the foaming agent at a high temperature to form a carbonized layer exerting fire resistance.

As the material used as the carbonizing agent, one or more compounds selected from the group consisting of monopentaerythritol, dipentaerythritol, tripentaerythritol, starch, phenolformaldehyde resin, sugar and polyurethane resin may be used. It is not limited to the above materials.

As one preferred example, the carbonizing agent may be used at 5 to 15 parts by weight in the total coating composition. If the carbonizing agent is less than 5 parts by weight of the total coating composition, the compounding reaction with the blowing agent is weak, and the formation of the carbonized layer is insufficient.

In the modified silicone foamed refractory paint composition according to the present invention, the blowing agent is thermally decomposed at a high temperature to release an inert gas so that the refractory coating film foams the carbonized carbonized layer to maintain a heat insulating effect.

As the blowing agent, one or more nitrogen compounds selected from the group consisting of melamine, guanidine, urea, glycine and dicyanamide may be used, but are not limited thereto.

As one preferred example, the blowing agent may be used at 5 to 15 parts by weight in the total coating composition. If the blowing agent is less than 5 parts by weight of the total coating composition, the amount of gas generated is not sufficient, so it is not sufficient to foam the carbonized layer, and if it exceeds 15 parts by weight, the amount of gas is increased, so that the amount of gas before foaming the carbonized layer Due to the excessive jetting, it is difficult to form a uniform carbonized layer, and thus fire resistance cannot be expected.

In the modified silicone foamed refractory paint composition according to the present invention, the acid catalyst is thermally decomposed at high temperature to promote the reaction of the carbonizing agent while releasing gas to form a carbonized layer and at the same time affect the foaming of the carbonized layer.

Such acid catalysts include a group consisting of primary ammonium phosphate, secondary ammonium phosphate, ammonium phosphate, amine sulfate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, tricresyl phosphate, and trichloroalkyl phosphate. One or more compounds selected from may be used, but is not limited to the above materials.

As one preferred example, the acid catalyst may be used in an amount of 15 to 40 parts by weight in the total coating composition. When the acid catalyst is less than 15 parts by weight in the total coating composition, the reaction with the carbonizing agent and the blowing agent does not occur well, and the formation of the inorganic acid is insufficient. It is not preferable because it inhibits.

In the modified silicone foamed refractory paint composition according to the present invention, the reinforcing agent improves the strength and abrasion resistance of the coating film, and prevents cracking by reducing hardening shrinkage.

To this end, as one preferred example, glass flakes having low thermal conductivity and excellent high temperature stability may be used as reinforcing agents.

More preferably, the reinforcing agent may be a plate-shaped glass flake having a long axis of 20 to 300 µm and a thickness of 0.1 to 5 µm. Moreover, the average aspect ratio of the said plate-shaped glass flake is 30-300.

Since the plate-shaped glass flakes are arranged in parallel with the workpiece, diffusion and permeation of water and water vapor can be prevented.

As one preferable example, the plate-shaped glass flakes may be used at 5 to 10 parts by weight in the total coating composition. If the plate-shaped glass flakes are less than 5 parts by weight in the total coating composition, the above-mentioned functions cannot be properly exhibited. If the plate-shaped glass flakes are more than 10 parts by weight, the viscosity rises and workability becomes poor.

In the modified silicone foamed refractory coating composition according to the present invention, the additive may be amorphous fume silica and a hydrated magnesium silicate derivative as a flow inhibitor, but are not limited thereto.

When the modified silicone foamed refractory coating composition is coated at a thickness of 4 mm or more at a time, it is preferable that the modified silicone foamed refractory coating composition does not flow down from the vertical plane.

As one preferred example, the thixotropic agent and the flow inhibitor may be used in an amount of 1 to 8 parts by weight in the total coating composition, respectively. If the amount used is less than 1 part by weight, it is difficult to form a thick film of 4 mm or more in a single coating because it does not improve flow resistance and rheological properties in the vertical plane, and when it exceeds 8 parts by weight, the viscosity of the coating composition is excessively increased. It adversely affects the surface roughness and workability of the coating film.

As described above, the modified silicone foamed refractory paint composition according to the present invention forms a high-density carbonized layer at the time of forming the foamed carbonized layer to provide excellent water resistance and fire resistance without desorption of the foamed carbonized layer. It is useful to use for 3 hours fireproof coatings in concrete, pillar and reinforced concrete structures.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

<Manufacture example 1>

Into a four-necked flask equipped with a thermometer, a condenser, a water separator, a dropping funnel, and an agitator, 152.3 g of methoxysilicate and 72 g of water were substituted with nitrogen gas, and the temperature was raised to 80 ° C. while stirring. The silanol was synthesized with stirring for time. Thereafter, the temperature was raised to 120 ° C. to synthesize condensation silanol having a molecular weight of 330, and 0.1 g of tetrachlorotitanate catalyst and 370 g of epichlorohydrin were added thereto, and 463 g of 38% caustic soda at 75 ° C. was added thereto. After constant dropping over 3 hours, water and salt as reaction byproducts were removed to obtain 160 g of modified silicone resin having a molecular weight of 550.

<Manufacture example 2>

Into a four-necked flask equipped with a thermometer, a condenser, a water separator, a dropping funnel, and an agitator, 265 g of propoxysilicate and 72 g of water were substituted with nitrogen gas, and the temperature was raised to 80 ° C. while stirring. The silanol was synthesized with stirring for time. Thereafter, the temperature was raised to 120 ° C. to synthesize a silanol having a molecular weight of 410 by condensation reaction, and 0.1 g of tetrachloro titanate catalyst and 280 g of epichlorohydrin were added thereto, and 350 g of 38% caustic soda at 75 ° C. was added thereto. After constant dropping over 3 hours, water and salt as reaction byproducts were removed to obtain 170 g of a modified silicone resin having a molecular weight of 620.

<Manufacture example 3>

Into a four-necked flask equipped with a thermometer, a condenser, a water separator, a dropping funnel, and an agitator, 576 g of polymethoxysiloxane and 216 g of water were substituted with nitrogen gas, and the temperature was raised to 80 ° C. while stirring. Silanol was synthesized with stirring for 1 hour. Add 0.2 g of tetrachlorotitanate catalyst and 370 g of epichlorohydrin, and drop 463 g of 38% caustic soda at 75 ° C. over 3 hours to remove water and salt as reaction byproducts. 580 g of silicone resin was obtained.

&Lt; Preparation Example 4 &

Into a four-necked flask equipped with a thermometer, a condenser, a water separator, a dropping funnel, and a stirrer, 674 g of polyethoxysiloxane and 216 g of water were added, followed by substitution with nitrogen gas and raising the temperature to 80 ° C. while stirring. Silanol was synthesized with stirring for 1 hour. Add 0.2 g of tetrachlorotitanate catalyst and 231 g of epichlorohydrin, and drop 290 g of 38% caustic soda at 75 ° C. over 3 hours to remove water and salt as reaction byproducts. 520 g of silicone resin was obtained.

<Examples 1 to 4>

Each of the modified silicone resin compositions obtained in Preparation Examples 1-4 was used as a binder, monopentaerythritol as a carbonizing agent, melamine as a blowing agent, primary ammonium phosphate as an acid catalyst, and glass flakes as a reinforcing agent (Microglas RCF-015 from Nippon Glass Fiber). Amorphous fume silica (Tixogel MP250 from Sourthern clay products Inc.) as a thixotropic agent in additives, hydrated magnesium silicate derivative (Pangel B20 from Grupo Tolsa) as a flow inhibitor in additives and penalcamine (Cardolite lite from Cardolite Corp.) as a curing agent. -2001) to prepare a refractory coating composition (Examples 1-4). Table 1 shows the composition ratio of the components in parts by weight.

Comparative Example 1

Comparative Example 1 was a refractory coating composition was prepared in the same manner as in Example 1 except that a liquid bisphenol-A epoxy resin having an epoxy equivalent of 187 was used as the binder.

Comparative Example 2

Comparative Example 2 was a refractory coating composition was prepared in the same manner as in Example 1 except that the equivalent 171 liquid phenol novolac epoxy resin was used as the binder.

TABLE 1

Experimental Example 1: Fire Resistance Test

This fire resistance test is to check the fire performance after painting fire resistant paint on steel frame beams of general buildings, factory buildings, hazardous materials storage and treatment facilities, and structural structures such as columns and reinforced concrete, and KS F. The fire resistance performance for 3 hours specified in Annex 2 of 2257-6, 7 should be maintained for 3 hours with the average temperature of each specimen under 538 ℃ or below and the maximum allowable temperature of 649 ℃ below for 3 hours. It becomes fireproof paint.

12 thermocouples are installed on H-beam as prescribed in KS F 2257-6, 7 and then coated with fireproof paint and heated for 3 hours under standard heating conditions specified in KS F 2257-1. Evaluate the effect of effectively blocking the external temperature of the H-beam, which is the workpiece, and install 12 thermocouples on each specimen as specified in KS F 2257-6, 7 and measure the temperature of each part. The fire resistance performance results are shown in Table 3 below.

TABLE 2

Experimental Example 2: Water Resistance Test

Refractory paint is applied three times to a dry film thickness of 12 mm on a general steel plate, and dried at room temperature for about 1 month or longer, and the test specimen is completely immersed in a water bath containing fresh water, resulting in swelling, cracking, and peeling of the dry film. Table 3 shows the results of the water resistance test by measuring the time at which the coating defect occurs.

TABLE 3

As shown in Table 3, the high density foamed refractory coating composition including the modified silicone resin and the glass flakes according to Examples 1 to 4 of the present invention is compared with the coating compositions of Comparative Examples 1 to 2 without using the modified silicone resin. It can be seen that the three-hour fire resistance test, the density of the foamed carbonized layer, the strength and the crack portion of the carbonized layer is very good. In particular, it can be seen that the detachment phenomenon does not occur when the foamed carbonized layer of the dry coating layer is formed, and thus, the steel structure and the concrete structure are insulated for 3 hours.

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.

Claims (10)

As a fireproof coating composition,
Including binders, carbonizing agents, blowing agents, acid catalysts, reinforcing agents and additives,
The binder is made of a modified silicone resin,
A modified silicone foamed fire-resistant coating composition, characterized in that the foamed expanded foam layer at a high temperature has excellent heat resistance and heat insulation. The modified silicone foamed refractory coating composition according to claim 1, wherein the modified silicone resin has a structure in which polysilanol contains 2 to 3 epoxide functional groups. The modified silicone foamed refractory coating composition according to claim 1, wherein the modified silicone resin has a weight average molecular weight in the range of 250 to 1200. 3. The modified silicone foamed refractory coating composition according to claim 2, wherein the polysilanol is obtained by condensation reaction of a silanol obtained by hydrolysis of an alkoxy silicate. The modified silicone foamed refractory coating composition according to claim 2, wherein the polysilanol is obtained by hydrolyzing a polyalkoxy siloxane. 6. The modified silicone foamed refractory coating composition according to claim 5, wherein when hydrolyzing the polyalkoxy siloxane, the equivalent ratio of alkoxy to water is in the range of 1: 1 to 1: 2. According to claim 1, wherein the reinforcing agent is a modified silicone foamed refractory paint composition, characterized in that the plate-shaped glass flake (glass flake) having a long axis of 20 to 300 ㎛, thickness of 0.1 to 5 ㎛. 8. The modified silicone foamed refractory coating composition according to claim 7, wherein the plate-shaped glass flake has an average aspect ratio of 30 to 300. The modified silicone foamed refractory coating composition according to claim 1, wherein the additive uses a thixotropic agent and / or a flow preventing agent. The modified silicone foamed refractory coating composition according to claim 1, wherein the refractory coating composition does not flow down from the vertical surface when coated with a thickness of 4 mm or more at a time.