KR0182660B1 - Aqueous intumescent coating composition for exposure protection and the agent thereof - Google Patents

Abstract

Disclosed is an aqueous anti-foam coating composition for internal / external coating having an anti-combustion performance and excellent salt water resistance, cold heat resistance, and bending characteristics, and a combustion prevention material formed by coating the coating material. 5-30% by weight of aqueous vinyl acetate-based resin, which is the coating film-forming resin, 5-20% by weight of carbonizing agent, 2-40% by weight of catalyst, 10-20% by weight of blowing agent, and 2-10% by weight of special refractory pigment %, Colored pigment 2-10% by weight additives 2-6% by weight. In the event of a fire, a porous ceramic forbidden layer is formed to provide excellent anti-combustion effect, and as it is an aqueous paint, it not only improves the hygiene environment of the operator, but also provides environmental friendliness to actively cope with the regulation of volatile organic substances.

Description

Aqueous Intumescent Combustion-Preventing Paint Composition and Combustion-Preventing Product Manufacutred by Using the Same

The present invention is a combustion of a flammable material produced by applying a paint technology capable of exhibiting high salt resistance, high heat resistance, and flexible bending characteristics using a water-soluble resin as a colorant, and an intumescent theory using a carbonizing agent, a catalyst, and a blowing agent. It relates to a water-based forbidden combustion prevention coating composition excellent in the prevention effect and a combustion prevention material produced using the same.

Forbidden means that the combustion prevention material foams and expands by gas generation step by step as the temperature rises due to the flame, and exerts its performance as a heat insulating material.

If a fire occurs in a cable for electric or communication cables mainly made of thermoplastic resin, it is necessary to prepare for it because there is a risk of fire spreading and large communication breakage through the cable. For this purpose, a method of imparting flame retardancy to an electric or telecommunication cable material is used, but since it has a limit in imparting flame retardancy by adding a chemical flame retardant to the material composition while satisfying an essential function as an electric or telecommunication cable material, an electric or telecommunication cable is used. In some cases, a coating to prevent combustion must be applied.

In connection with the Forbi theory, the present applicant has invented a forbidden fire-resistant coating material and has applied for the name of the invention to the Korean Intellectual Property Office for the forbidden fire-resistant coating material composition and fire-resistant coating material prepared using the same. 95-61493; Inventors: Eom Dal, Profit Number). The coating composition disclosed above uses oil-based special thermoplastic acrylic resins such as vinyl toluene-acrylate copolymers, styrene-acrylate copolymers and halogen-modified acrylate copolymers as the plating agent which is the main agent for forming the film. When the oil-based paint as disclosed in the above patent application is used as the anti-combustion paint, it is mainly constructed in a closed or poorly ventilated working condition, so that it may not only provide another cause of fire, but also volatilize during construction. Organic solvents have fatal drawbacks that hinder worker health. In addition, in order to meet the international trend of tightening the regulation of Volatile Organic Compounds (VOCs), there is an increasing demand for water-based paints in which a large portion of the solvent is replaced by water.

The inventors of the present invention solve the above problems, while having an excellent anti-burning effect and excellent salt water resistance, cold resistance, and bending characteristics, and also safer in the hygienic environment or environmental pollution of the operator water-based forbidden combustion prevention paint composition In an effort to develop, the present invention has been completed by discovering that a special acryl resin, a carbonizing agent, a catalyst and a composition in which a blowing agent and a pigment are properly mixed can achieve the above object.

According to the present invention, 5-30% by weight of an ethylene vinyl acetate-based resin, which is a water-soluble resin, 5-20% by weight of a carbonization agent, a catalyst, 10-40% by weight, and a foaming agent of 5-20% by weight And 2-10% by weight of special thermally insulating pigments, 2-10% by weight of colored pigments and 2-6% by weight of additives.

In particular, the composition of the present invention achieves an optimal blending ratio so that the composition is excellent in the ratio of the pore effect (measured as the ratio of the thickness of the foamed film in the finished state to the thickness of the normal cured film before the pore is completely finished). In addition, the special heat-resistant pigment that can double the thermal insulation effect by maximizing the ceramic layer forming effect as well as the three-dimensional adhesion effect has a distinct advantage that it can simultaneously exhibit the general paint function for the interior and exterior and the special paint function for the combustion prevention material. Have

The above description of the Forbi principle is as follows. That is, the components forming the coating film are usually stable at an external temperature (-15 ° C.-40 ° C.), but the temperature inside the coating film continuously increases when exposed to a flame due to a fire or the like. When each component is polymerized through a chemical reaction by mutual heating. In addition, at the fire extinguishing temperature (about 250 ° C.), a combustion prevention layer is formed by forming a carbonaceous expansion film having a volume due to the thickness increase in the vertical direction of 50-100 times higher than the original dry coating while generating carbonized material and non-combustible gas. This insulating ceramic layer continues to maintain the effect of blocking heat conduction from the flame to the telecommunication cable. Therefore, dry film thickness may eventually become a management factor that has a significant effect on the combustion prevention performance.

The main components in producing an aqueous forbidden combustion prevention paint having such a performance will be described in detail.

First, as the resin used as a colorant, an aqueous ethylene-vinylacetate copolymer, an aqueous butyl acrylate copolymer, and an aqueous vinyl acetate-acrylate airborne Copolymers, aqueous vinylacetate-silane copolymers, water-soluble polyester resins, water-soluble alkyd resins, water-based epoxy resins, water-dispersible urethane resins, water-soluble acrylic resins and aqueous halogen-modified acrylates The water-soluble resin which is a copolymer is used individually or in mixture. It is preferable that the glass transition temperature of these resin is -50 degreeC-50 degreeC. If the composition of the aqueous resin is 5% by weight or less based on the total weight of the entire composition, it is not preferable because it is impossible to form a continuous coating film, and if it is 30% by weight or more, it is not preferable because it significantly lowers the nasal effect. Therefore, the content of the aqueous resin is used in 5 to 30% by weight, preferably 6 to 15% by weight.

Chemicals used as carbonizing agents include sorbitol, pentaerithritol, dipentaerythritol, tripentaerithritol, tripentaerithritol, methylol melamine, and lysosinol. Resorcinol), linseed oil, Trihydroxyethyl isocyurate, and alkyd resin, and the like, and these may be used alone or in combination. Carbonization is a suitable material for carbonizing in flames to form a non-combustible carbide ceramic layer. If the composition of the carbonizing agent is less than 5% by weight based on the total weight of the entire composition, it is not preferable because the chemical reaction product with the catalyst component is insufficient, and if it is more than 20% by weight, it is not preferable because it significantly lowers the poby effect. Therefore, the carbonizing agent is used in an amount of 5 to 20% by weight, preferably 6 to 15% by weight.

One of the components, the catalyst for promoting reaction, forms a molecular layer by chemical reaction with a carbonizing agent. Suitable chemicals include inorganic acids, ammonium polyphosphate, amine / amide phosphate, amine sulfate, melamine phosphate, dimelamine phosphate, melamine piers Phosphate (Melamine pyrophosphate) and tricresyl phosphate (Tricresyl phosphate) and the like. These catalysts can be used alone or in combination. If the composition of the catalyst is less than 10% by weight based on the total weight of the total composition, the chemical reaction product with the carbonization component is insufficient, and if it is more than 40% by weight, it is not preferable because it significantly lowers the poby effect. Therefore, the content of the catalyst is used in 10 to 40% by weight, preferably 15 to 25% by weight.

Another major component, the blowing agent, plays a direct role in generating the gases necessary to expand the polymer layer. Such blowing agents include melamine, guanidine, urea, glycine, glycandi, icyandiamide, chlorinated paraffin, neutralized phosphoric acid ester ), Dioctylphthalate, diazealate, diisophenylphthalate, tetrachlorophthalic polymer, and the like. In particular, when the neutralized phosphate ester compound or diisophenyl phthalate is used as the blowing agent, not only the blowing agent effect but also the flame retardancy and plasticity are imparted, and the coating film is excellent in preventing cracking. In addition, since it does not contain a halogen component, it has an excellent advantage that it does not emit any harmful gas during foam formation. These blowing agents can be used alone or in combination. If the composition of the blowing agent is 5% by weight or less based on the total weight of the total composition, the generated gas pressure is so low that it is insufficient to expand the polymer layer. If the composition is 20% by weight or more, the generated gas pressure is too high. It is not desirable because it will break the layer. Therefore, the content of blowing agent is used in 5 to 20% by weight, preferably 6 to 15% by weight.

In addition, as a special heat-insulating pigment that contributes to the physical adhesion inside the coating film and the effect of forming the ceramic layer, ceramic pigments, porous silicon-based pigments, glass filaments, metal oxides, and calcite stones have excellent effects. If the composition of the special heat insulating pigment is 2% by weight or less based on the total weight of the total composition is not preferable to exhibit a special heat insulating effect, it is not preferable, if more than 10% by weight will significantly reduce the nasal effect. Therefore, the content of the special insulating pigment is used in 2 to 10% by weight, preferably 2 to 6% by weight.

In addition, its function, which is a substance added during paint production, contains 2 to 10% by weight of the colored pigment required for the general water-soluble paint, based on the total weight of the total composition. If the content of the colored pigment is 2% by weight or less, the coloring power is insufficient, and it is not preferable. In addition, in order to give an optimum paint state and coating performance in an iso amount, an appropriate ratio, and additives such as an extender pigment, a surface leveling agent, a dispersant, an antifoaming agent, a plasticizer, and a detersive agent, the composition of the water-soluble resin is used to reduce the total weight of the whole composition. 2 to 6 weight% is contained as a reference.

Therefore, the four types of components for imparting refractory functions such as a colorant, a carbonizing agent, a catalyst and a foaming agent, and an aqueous ratio are prepared by combining a special insulating pigment and an additive for imparting a general paint function after the composition ratio is optimally adjusted. The anti-combustion paint can be used as an anti-combustion paint for telecommunication cables.

An advantage of the present invention is that melting due to flow above the melting point temperature inherent in the porous forbidden layer is possible because the special thermally insulating pigments containing ceramic components can be blended into the paint in the proper proportions to take full advantage of the physical properties of the pigments. By controlling the flow phenomena, it is possible to achieve continuous combustion prevention effect in a horizontal state with respect to the material surface. In addition, the pigment component not only enhances the adhesion effect between the compositions in three dimensions and maintains the coating film structure intact, but also significantly delays the penetration of oxygen into the interior of the fossa layer by forming a ceramic layer over the fossa layer. Eventually, it will contribute to increasing the combustion prevention effect for a longer time.

Accordingly, the present invention also provides 5-30% by weight of an aqueous resin, 5-20% by weight of a carbonizing agent, 10-40% by weight of a catalyst, 5-20% by weight of a blowing agent, 2-10% by weight of a special heat insulating pigment, and coloring as a colorant. Provided is a combustion prevention material having an abrasion property which is formed by coating an aqueous-based forbidden combustion prevention paint composition comprising 2-10% by weight of a pigment and 2-6% by weight of an additive, and inducing a heat insulating ceramic layer upon heating. do. Preferably, the composition is formed by coating the cable for telecommunication to have a dry coating thickness of 0.5-2.0 mm.

The anti-combustion effect and the coating film properties of the water-based forbidden combustion preventing paint prepared by the inventive technique of the present invention will be described in more detail with reference to the following examples, and the scope of the present invention is not limited to these examples. . In the following examples, the content means parts by weight.

Example 1

17.4 parts of water, 1.4 parts of Triton X-100 (manufactured by Union Carbide) as a dispersant, 3.7 parts of ethylene glycol (Ethylene Glycol) as a cryoprotectant, and a deformer HDW (Defoamer HDW, manufactured by Hongsan Chemical) as an antifoaming agent 0.2 part and 8 parts of alcoholic plasticizers are added, and it stirs at low speed to a uniform state. When the homogeneous state is reached, 19.6 parts of ammonium polyphosphate, 7.9 parts of dipentaerythritol, 5.3 parts of chlorinated paraffin (50% of chlorine content), 7.8 parts of melamine, and titanium oxide (TiO ₂₎ as color pigments ) 4.6 parts, 1.6 parts of porous ceramic pigments are added as a special heat-insulating pigment, and it is dispersed rapidly. Add 0.2 parts of Skyside PG-520 (Skycide PG-520, manufactured by SunKyung Industries) and 22.3 parts of ethylene vinyl acetate resin (60 wt% solids) as a preservative, and stir at low speed to a uniform state and adjust the viscosity to 90-110 KU. A water based forbidden combustion prevention paint is produced.

Example 2

Instead of using 22.3 parts of ethylene vinyl acetate-based resin (60 wt% solids), 7.9 parts of dipentaerythrite, except that 22.0 parts of styrene acrylate emulsion resin (60 wt% solids) and 13.5 parts of pentaerythritol are used. In the same manner as in Example 1, an aqueous forbidden combustion prevention paint was prepared.

Example 3

Except for using 19.6 parts of ammonium polyphosphate, 5.3 parts of chlorinated paraffin (50% chlorine content) and 7.8 parts of melamine, 21.8 parts of melamine pyrophosphate, 2.0 parts of neutralized phosphate ester compound, and 5.9 parts of melamine were used. In the same manner as in 1, an aqueous forbidden combustion prevention paint is prepared.

Example 4

Instead of using 4.6 parts of titanium oxide (TiO ₂ ) and 1.6 parts of porous ceramic pigments, except that 2.8 parts of titanium oxide (TiO ₂ ) and 3.4 parts of silica # 325 (Silica # 325, manufactured by Kyungin Chemical Co., Ltd.) are used. In the same manner as in Example 1, an aqueous forbidden combustion prevention paint was prepared.

Experimental Example 1

The composition prepared in Examples 1-4 of the present invention was measured for the performance of the dried coating film on the test communication cable so that the dry coating film thickness was 1.0 mm.

Oxygen Index Test

It is a method of testing the combustibility of rubber, plastic, fiber, etc. as a polymer material. Oxygen index refers to the minimum oxygen concentration required for a material to continue combustion under certain test conditions, expressed in volume percent of oxygen. In the test, a stand-alone test piece (length 115.0 × width 6.0 × thickness 3.5 mm) was subjected to the combustion test using a prescribed combustion device and evaluated for the lowest concentration of oxygen supplied, according to the method specified in KSM 3032.

[Flame retardancy test]

It is a method of testing the flame retardancy and self-extinguishing of rubber, plastic, fiber, etc. as a polymer material. The test is carried out by burning test of the self-supporting test piece (length 125.0 × width 13.0 × thickness 1.0mm) and the coated cable using the specified combustion device in accordance with the method specified in UL-94 and IEEE383, and the residual flame time secondary ignition and combustion. The length and self-extinguishing performance were evaluated and classified according to the prescribed grade.

[Flexibility test]

A method of testing the flexural properties of sheathed cables. Based on the hemispherical sample holder having a diameter of 20 times the cable diameter, the test body was slowly bent 180 degrees, and the bending test with 1 cycle of 180 degrees bend was conducted on the contrary, so that the inner surface of the hemispherical test body became the outer surface. Cracking, peeling, swelling, etc.) was visually evaluated.

[Expansion Test]

It is a method of testing the thermal expansion characteristics of the anti-combustion paint. The self-supporting test piece (length 50.0 * width 50.0 * thickness 1.0mm) was hold | maintained in 300 degreeC high temperature tank for 30 minutes, and the volume change rate before and behind a test was evaluated.

[Cold test]

It is a method to test the cold heat characteristics of the anti-combustion paint. After the self-supporting test piece (length 50.0 × width 50.0 × thickness 1.0mm) was subjected to two cycles of one cycle of leaving at -15 ° C for 24 hours at 80 ° C for 24 hours, the presence or absence of abnormality (splitting, peeling, swelling) And the like) were visually evaluated.

[Salt Spray Test]

It is a method to test the corrosion resistance of the anti-combustion paint. After the coated cable was left to soak for 10 days in a test tank kept at 3% saline at 40 ° C, the presence or absence of abnormalities (cracking, peeling, swelling, etc.) of the coating coating layer was visually evaluated.

The test results are shown in Table 1 below.

Evaluation order: Excellent-Good-Normal (No abnormal level)-Poor

Normal flammable plastics have an oxygen index of 5-30%. As can be seen from the above test results, when coating the telecommunication cable using the composition according to the present invention, the oxygen index is increased to be combustible in the atmosphere by increasing the combustibility of the cable which is 30% or less before coating to 45% or more. do.

In addition, flame retardancy is V-0 grade or more (not easily burned and burned out, even if burned, and the characteristics of self-extinguishing when the fire is removed), afterflame time is less than 5 seconds, secondary residual smoke Alternatively, the residual time is less than 10 seconds, and the combustion exhibits a level of flame retardancy in which no secondary combustion expanding material is generated.

In particular, in the case of using the neutralized phosphate ester compound as the blowing agent, as in Example 3, since the plasticizing effect is excellent and the flexibility is excellent, and since there is no halogen component, no harmful gas is emitted during the foam formation process. In addition, it can be seen that it exhibits excellent combustion prevention effect and flame retardant effect.

Claims (7)

As a colorant, an aqueous ethylene-vinylacetate copolymer, an aqueous butyl acrylate copolymer, an aqueous vinylacetate-acrylate copolymer, an aqueous vinylacetate-silane ( Aqueous system using vinylacetate-silane copolymer, water-soluble polyester resin, water-soluble alkyd resin, water-based epoxy resin, water-dispersible urethane resin, water-soluble acrylic resin, and aqueous halogen-modified acrylate copolymer alone or in combination. 5-30 wt% resin, 5-20 wt% carbonizing agent, 10-40 wt% catalyst, 5-20 wt% blowing agent, ceramic pigments, porous silicon pigments, glass filaments, metal oxides and calcite stones 2-10 weight% of special heat-insulating pigment, 2-10 weight% of coloring pigment, and 2-6 weight% of additives which are used alone or in combination. Coating composition. The method of claim 1, wherein the carbonizing agent is sorbitol (Sorbitol), pentaerythritol (Pentaerithritol), dipentaerythritol (Dipentaerithritol), tripenterithritol (Tripentaerithritol), methylol melamine (Methylol melamine), lyso Synol (Resorcinol), Linseed oil (Linseed oil), Trihydroxyethyl Isocyurate (Trihydroxyethyl Isocyurate) and Alkyd resin (Alkyd resin) composition comprising the use of a single or mixed. The method of claim 1, wherein the catalyst is an inorganic acid, ammonium polyphosphate (Ammonium polyphosphate), amine / amide phosphate (Aminc / Amide phosphate), amine sulfate (Amine sulfate), melamine phosphate (Melamine phosphate), Dimelamine phosphate (Dimelamine phosphate) ), Melamine pyrophosphate (Melamine pyrophosphate) and tricresyl phosphate (Tricresyl phosphate) composition, characterized in that using alone or in combination. According to claim 1, Melamine, Guanidine, Urea, Glycine, Dicyandiamide, Chlorinated paraffin, Neutralized phosphate ester compound as the blowing agent (Neutralized phosphoric acid ester), dioctylphthalate, Diazealate, Diisophenylphthalate and Tetrachlorophthalic polymers, the composition comprising a single or mixed use. The composition according to claim 4, wherein a neutralized phosphate ester compound, dioctylphthalate, diazitrate or diisophenyl phthalate is used as the blowing agent. As a colorant, an aqueous ethylene-vinylacetate copolymer, an aqueous butyl acrylate copolymer, an aqueous vinylacetate-acrylate copolymer, an aqueous vinylacetate-silane ( Aqueous system using vinylacetate-silane copolymer, water-soluble polyester resin, water-soluble alkyd resin, water-based epoxy resin, water-dispersible urethane resin, water-soluble acrylic resin, and aqueous halogen-modified acrylate copolymer alone or in combination. 5-30% by weight of resin, 5-20% by carbonizing agent, 10-40% by weight of catalyst, 5-20% by weight of blowing agent, ceramic pigments, porous silicon pigments, glass filaments, metal oxides and calcite stones Aqueous anti-corrosive combustion prevention method comprising 2-10% by weight of special heat-insulating pigments used alone or mixed, 2-10% by weight of colored pigments, and 2-6% by weight of additives. It is formed by coating the composition, preventing re-combustion with Poby property capable of eliciting an insulating ceramic layer when heated. The combustion preventing material according to claim 6, wherein the composition is coated on a telecommunication cable so as to have a dry coating thickness of 0.5-2.0 mm.