FI126518B - Fire-resistant coating material - Google Patents

Description

Fire-resistant coating material

BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a composite formed by an organic polymer and inorganic particles, and more particularly to a fire resistant coating material containing an organic / inorganic composite.

Description of Related Art Fire resistant or flame retardant materials may be used as architectural or decorative materials. The architectural materials disclosed in Taiwan Patents Nos. 583,078 and 397,885 consist essentially of a filler layer which functions as a fire-retardant layer consisting of inorganic materials such as perlite, MgCl 2, MgO, CaCO 3 or cement. In addition, a rigid, fire-resistant laminate can be obtained from flexible substrates of fibrous or nonwoven materials blended with flame retardants, blowing agents, and 50 to 80% by weight of inorganic materials.

Flame retardant coatings, which act as decorative materials and are disclosed in Taiwan Patents Nos. 442,549, 499,469, and 419,514, comprise a combination of foaming and expanding agents, carbonating agents, flame retardants, and adhesives that foam and expand when exposed. U.S. Patent No. 5,723,515 discloses a flame-retardant coating material comprising a fluid, expandable base material comprising blowing agents, a blowing agent, a carbonising agent, a binder, a solvent, and a pigment, which improves fracture and shrink resistance. The blend disclosed in U.S. Patent No. 5,218,027 is prepared from a composition of a copolymer or terpolymer, a low modulus polymer, and a synthetic hydrocarbon elastomer. The flame retardant additive comprises a Group I, Group II or Group III metal hydroxide, provided that at least 1% by weight of the composition is in the form of an organopolysiloxane. U.S. Patent No. 6,262,161 relates to filled copolymer compositions of ethylene and / or alpha-olefin / vinyl or vinylidene monomers having improved properties upon exposure to flame or ignition sources, and products made therefrom. Products can be in the form of film, sheet metal, multilayer structure, floor, wall or ceiling coverings, foams, fibers, electrical equipment or cable and cable installations.

EP 1384752 discloses an insulated electric cable comprising a combination of a micro-mixture and a modified micro-mixture, wherein the micro-mixture comprises polypropylene and the modified micro-mixture is made by bonding an organic acid group to the micro-mixture; polypropylene; and an ionic cross-linking filler which is magnesium hydroxide.

US 4,246,146 discloses a fire retardant protective coating produced by dissolving a water soluble polyisocyanate prepolymer in an aqueous slurry or solution of either fire retardant materials or thickeners. Aluminum trihydrate, Al (OH) 3, is used as a flame retardant or thickener.

US 4066578 discloses a polyurethane composition, in particular a cross-linked hydrophilic polyurethane foam system.

Conventional flame retardant polymer compositions are obtained by physical mixing of an organic polymer with an inorganic flame retardant, in which binders or surfactants are typically incorporated to improve dispersion of the inorganic flame retardant. However, since the organic polymer does not react with the inorganic component to form a well-structured composite by forming chemical bonds, conventional flame retardant compositions will readily melt, ignite, or produce flammable droplets when exposed to flame or ignition sources.

BRIEF SUMMARY OF THE INVENTION It is a general object of the invention to provide a fire-retardant coating material having excellent fire resistance and fire retardant properties.

To achieve the foregoing and other objects, the fire-retardant coating material of the invention comprises an organic / inorganic composite comprising an organic component having a first reactive, functional group, the organic component comprising a polymer, copolymer, monomer, oligomer or pre-polymer; inorganic particles having another reactive functional group; wherein the inorganic particles are chemically bonded to the organic component by reaction between the first and second reactive functional groups.

A detailed description will be given in the following embodiments with reference to the accompanying drawings.

Brief Description of the Drawings

The invention will be more fully understood by reading the following detailed description and examples with reference to the accompanying drawings, in which: Figure 1 is a schematic figure showing a flame test of the fire resistant coating of Example 1; Fig. 2 is a schematic diagram showing the temperature measurement of an A4 sheet of paper in Example 7; and Fig. 3 is a graph showing the temperature of the back side of an A4 sheet of paper as a function of the heating time comparing the fire-resistant coating material of Example 5 with a commercial fire-resistant coating material.

DETAILED DESCRIPTION OF THE INVENTION The following description is a preferred embodiment of the invention. This description is made for the purpose of illustrating the general principles of the invention and is not to be construed as limiting. The scope of the invention is best defined by the following claims.

The invention relates to a fire-resistant coating material comprising: an organic / inorganic composite comprising: 30 to 70% by weight of an organic component comprising polyurethane, or a polyolefin copolymer having a first functional group of isocyanate groups, 70 to 30% by weight of inorganic particles, is another reactive, hydroxyl functional group comprising a metal hydroxide Al (OH) 3 or Mg (OH) 2; wherein the inorganic particles are chemically bonded to the organic component by reaction between the first and second reactive functional groups; wherein the inorganic and organic components are sufficiently bonded to provide a flame-retardant coating material capable of withstanding flame temperatures from 1000 to 1200 ° C for more than 3 minutes.

Inorganic particles having reactive, functional groups initially or after surface modification may be well dispersed in and reacted with an organic component such as a polymer, monomer, oligomer, prepolymer or copolymer to improve its flame-retardant and mechanical properties. Because the well-structured composite is provided by the formation of chemical bonds, the carbon layer deposited on the surface is strong and able to retain its structural integrity without peeling or fracturing, which effectively prevents direct heat transfer to the interior. The organic / inorganic composite may be blended into a suitable continuous phase, depending on the type of organic component, to provide a fire-resistant coating material. In general, the organic / inorganic composite may comprise from 10 to 90% by weight of the organic component and from 90 to 10% by weight of the inorganic particles, according to the invention, the organic / inorganic composite comprises 30 to 70% by weight of the organic component and 70 to 30% by weight. % inorganic particles, and more preferably it comprises 40-60% by weight of the organic component and 60-40% by weight of inorganic particles.

The form of the fire-resistant coating material described herein is slurry. The organic component in the coating material may be a polymer, monomer, oligomer, prepolymer or copolymer, while the organic component in the solidified coating may be an oligomer, polymer or copolymer. For purposes of description, the term "polymer" refers to compounds having a number average molecular weight of 1,500 to more than 1,000,000 daltons, while an "oligomer" refers to compounds having a number average molecular weight of 200-1499 daltons.

In the organic / inorganic composite, the organic component and the inorganic particles are chemically bonded together by the corresponding reactive, functional group reactions. The reactive functional groups of the organic component and the inorganic particles may include, but are not limited to, -OH, -COOH, -NOO, -NH3, -NH2, -NH and epoxy groups. For example, an organic component having -COOH or -NCO groups (e.g., an organic acid or reactive polyurethane) may be used to react with inorganic particles having -OH groups (e.g., metal hydroxide). In addition, the organic component containing the epoxy groups can be used to react with inorganic particles having -NH 2 groups. Alternatively, the organic component having -OH groups (e.g. polyvinyl alcohol) may react with the inorganic particles having -COOH or -NCO groups, and the organic component having -NH 2 groups may react with the inorganic particles having have epoxy groups.

Suitable organic components include any monomers, oligomers, monopolymers, copolymers or prepolymers containing the aforementioned reactive functional groups. Reactive functional groups may be located on the backbone or side chain of the polymer. Preferred organic components are polyorganic acid, polyurethane, epoxy compound, polyolefin and polyamine. Polyorganic acid includes homopolymers or copolymers containing carboxylic or sulfonic acids such as poly (ethylene-coacrylic acid) and poly (acrylic acid-co-maleic acid). Representative examples of epoxy compounds include bis (3,4-epoxy-6-methylcyclohexylmethyl) diphenyl, vinylcyclohexene dioxide, diglycidyl-tetrahydrophthalate, poly-glycidyl hexamide, bis (2,3-epoxycyclopentyl ether resin, polyphenol-ethylethyl), and polyphenol-epinyl. (NH (CH 2) 5 CO) n), nylon 66 ((NH (CH 2) 6 -NH-CO (CH 2) 4 CO) n) and nylon 12 ((NH (CH 2) n CO) n). The polyimide contains a diamine such as 4,4-oxydianiline, 1,4-bis (4-aminophenoxy) benzene or 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and also includes a polyimide synthesized by diamine and dianhydride such as Polyolefins suitable for use include an olefinic monomer and the aforementioned reactive functional groups containing anhydrous phthalic anhydride, pyromellitic acid dianhydride or benzophenone tetracarboxylic acid dianhydride It should be noted that the organic component also includes the monomer, oligomer, copolymer and prepolymer of the typical polymers described above. Further, the organic components may be used singly or in a mixture of two or more.

Suitable inorganic particles for use herein are those which, initially or after surface modification, have corresponding functional groups capable of reacting with the functional groups of the organic component. Preferred inorganic particles include hydroxides, nitrides, oxides, carbides, metal salts and inorganic layered materials. Hydroxides include metal hydroxides such as Al (OH) 3 or Mg (OH) 2. Nitrides include, for example, BN and S13N4. Carbides include, for example, SiC. Metal salts include, for example, CaCO 3. Inorganic layered materials include, for example, clay, talc, and layered double hydroxide (LDH), where the clay may be smectite clay, vermiculite, halloocyte, sericite, saponite, monmorillonite, beidellite, nontronite, mica. The inorganic particles may also be used as a mixture of two or more. For example, clay containing reactive functional groups can be used in combination with metal hydroxide. Suitable inorganic particles include microparticulate particles and nanoparticulate particles. Nanoparticulate particles having diameters in the range of 1 to 100 nm are particularly preferred because the smaller the particle size, the larger the surface area per unit weight.

The organic component and the inorganic particles may be directly mixed for the reaction to form covalent or ionic bonds, or the reaction may be carried out in various solvents (e.g., water, ethanol or methyl ethyl ketone). The reaction temperature is usually from room temperature to about 150 ° C and the reaction time may vary from 10 minutes to a few days depending on the starting materials used. The slurry product from the reaction can be used directly as a fire-retardant coating, but solvent or water may be added thereto, depending on the coating material application methods. For example, in embodiments containing a polyorganic acid, water or alcohol (such as methanol or ethanol), the viscosity of the coating material may be reduced to facilitate spray coating or brush coating. In embodiments containing reactive polyurethane, a variety of solvents may be used, including, for example, hexane, ketone (e.g., acetone, methyl ethyl ketone), ester (e.g., butyl ester),?,? -Dimethylacetamide (DMAC), N-methylpyrrolidone. (NMP) or aromatic hydrocarbon solvents (e.g. benzene, xylene). Two or more types of solvent may be used together. Typically, a low boiling point solvent (boiling point 60-90 ° C) may be used in combination with a high boiling point solvent (boiling point 100-150 ° C) to reduce coating difficulties and improve coating quality.

To blend the aqueous coating material with the organic / inorganic composite, a pigment (depending on the desired color), water, thickener, antifoam and surfactant can be added to improve dispersibility. The thickening agent includes, for example, starch, clay and a cellulose thickener. Antifoam is typically a nonionic surfactant such as HCK-8112, ex. HCK Chemicals Corp. The surfactant used to improve the dispersibility may be an ionic or nonionic surfactant such as J678, ex. Johnson Polymer Corp., SINONATE 707SF, ex. Sino Chemical Corp., or Brij56, ex. Aldrich Chemical Corp. A pigment, a solvent, a resin, a smoothing agent, a curing agent, a silane or siloxane as a curing agent and other additives may be incorporated into the organic / inorganic composite to form a PU-based solvent-type coating material. Mostly the smoothing agent is a surfactant such as BYK-354, 333 and 306, ex. BYK-Chemie Corp. The hardener is most often an isocyanate such as toluene diisocyanate (TDI), methylene bisphenyl isocyanate (MDI) or hexamethylene diisocyanate (HDI). The most common curing aids are tetraethoxysilane (TEOS) and triethoxyvinylsilane (TEVS).

The fire-resistant coating material of the invention may be applied to the surfaces of flame retardants or flammable articles to improve fire resistance by any suitable method. It may be applied, for example, by brush coating, roller coating, blade coating or spray coating. Injection coating includes, for example, hot spray-bubble coating, air-spray coating, airless spray coating, air-mixed spray coating, high-volume low-pressure spray coating, low-volume medium-pressure injection coating.

When the organic / inorganic composite of the invention is burned or exposed to fire, the polymer forms a carbon layer and the inorganic particles radiate the absorbed heat. The inorganic particles also reinforce the mechanical properties of the structure by reaction between the inorganic and organic materials so that the formed carbon layer remains strong and its structural integrity is maintained without peeling or fracturing, which effectively prevents direct heat transfer to the coated article. The flame-retardant material is not only flame retardant, but also protects internal materials. As a result, the durability of fire resistance is significantly prolonged. According to the invention, the fire-resistant coating is capable of withstanding flame temperatures of 1000 to 1200 ° C for more than 3 minutes. Because the organic component and the inorganic particles are chemically bonded to each other (as compared to conventional physically mixed products), the fire-resistant composite of the invention does not melt, ignite, or produce flammable droplets when exposed to flame or ignition sources.

The fire resistant coating material according to the invention has a wide range of applications. For example, it is suitable as a fire-resistant material for coating interior structures and structural steel. In addition, it can be used as a coating material for cable sheaths, conductive sheaths or foaming materials. Fire-resistant coating material can also be used on surfaces of flammable objects in vehicles such as airplanes, ships, cars and trains. Thus, various additives may be incorporated by those of ordinary skill in the art depending upon the particular application. For example, a flame retardant such as melamine phosphates, red phosphorus, and a phosphorus based flame retardant may be present to improve fire protection. A silane (such as TEOS or TEVS) or siloxane may be present to enhance structural integrity and facilitate curing. Glass sand and fiberglass may be present to improve heat resistance and strengthen structural integrity. The amount of these additives is typically in the range of 0.1 to 20 parts by weight per 100 parts by weight of the organic / inorganic composite.

Example 1 10 g of poly (ethylene-coacrylic acid) was charged to the reactor, preheated to 80-120 ° C and then stirred at 300 rpm. 10.8 g deionized water and 10.8 g aqueous ammonia were added to the reactor to give a white emulsion after stirring for 10 minutes. Thereafter, 10 g of aluminum hydroxide powder was added to the reactor to give a white slurry after stirring for 10 minutes. As shown in Figure 1, a slurry of 2 mm thickness was applied to the surface of A4 sheet of paper 10 and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C. at 30 ° C, 30 minutes at 140 ° C, 30 minutes at 160 ° C, 30 minutes at 180 ° C, and finally cast at 200 ° C for 240 minutes.

A flame test was carried out on the surface of the sample layer 20 on a butane gas burner 30 using a flame temperature of 1000-1200 ° C (flame 40) for a period of 30 seconds to 3 minutes. The results of A4 paper sheet combustion are summarized in Table 1. No carbonization was observed on the A4 sheet after 30, 60 and 120 seconds of heating, but slight carbonation was observed after 180 seconds of heating.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the poly (ethylene-coacrylic acid) -COOH groups react with Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing.

Example 2 10 g of poly (ethylene-coacrylic acid) was charged to the reactor, preheated to 80-120 ° C and then stirred at 300 rpm. Thereafter, 10 g of aluminum hydroxide powder was added to the reactor to give a white slurry after stirring for 10 minutes. The slurry solidified to white lumps after cooling to room temperature. The white lumps were placed in a container and reheated to a white slurry at 100-120 ° C. The heated slurry was applied to an A4 sheet of paper and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, 140 ° C: at 30 ° C, 30 minutes at 160 ° C, 30 minutes at 180 ° C and finally cast at 200 ° C for 240 minutes.

A flame test was carried out on the surface of the sample layer on a butane gas burner using a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of A4 paper sheet combustion are summarized in Table 1. No carbonization was observed on the A4 sheet after 30, 60 and 120 seconds of heating, but slight carbonation was observed after 180 seconds of heating.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the poly (ethylene-coacrylic acid) -COOH groups react with the Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing.

Example 3 20 g of poly (acrylic acid-comalic acid) (50% solids content) was charged to the reactor, preheated to 80-90 ° C and then stirred at 300 rpm. 10 g of aqueous ammonia were added to the reactor and stirred for 10 minutes. Thereafter, 10 g of aluminum hydroxide powder was added to the reactor to give a yellow slurry after stirring for 10 minutes. The slurry was applied at a thickness of 2 mm onto a sheet of A4 paper and then placed in an oven, dried at 60 ° C for 60 minutes, 80 ° C for 60 minutes, 100 ° C for 60 minutes, 120 ° C for 30 minutes, At 140 ° C for 30 minutes, 160 ° C for 30 minutes, 180 ° C for 30 minutes and finally cast at 200 ° C for 240 minutes.

A flame test was carried out on the surface of the sample layer on a butane gas burner using a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of A4 paper sheet combustion are summarized in Table 1. No carbonization was observed on the A4 sheet after 30, 60 and 120 seconds of heating, but slight carbonation was observed after 180 seconds of heating.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the poly (acrylic acid-maleic acid) -COOH groups react with the Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing.

Example 4 50 g of reactive polyurethane containing 8% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 50 g of aluminum hydroxide powder was added to the reactor to give a white slurry after 5 minutes of agitation. The slurry was applied at a thickness of 2 mm onto a sheet of A4 paper and then dried at room temperature for 24 hours.

A flame test was carried out on the surface of the sample layer on a butane gas burner using a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The results of A4 paper sheet combustion are summarized in Table 1. No carbonization was observed on the A4 sheet after 30, 60 and 120 seconds of heating, but slight carbonation was observed after 180 seconds of heating.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the -NCO groups of the reactive polyurethane react with the -OH groups of Al (OH) 3 to form chemical bonds instead of physical mixing.

Example 5 50 g of reactive polyurethane containing 8% of reactive isocyanate groups were charged into the reactor and stirred at 300 rpm. Thereafter, 45 g of magnesium hydroxide powder and 5 g of modified nano-clay containing -OH groups (Closite 30B, ex. Southern Clay Prodct Corp.) were added to the reactor to give a white slurry after 5 minutes. The slurry was applied at a thickness of 2 mm onto a sheet of A4 paper and then dried at room temperature for 24 hours.

A flame test was carried out on the surface of the sample layer on a butane gas burner using a flame temperature of 1000-1200 ° C for 30 seconds to 3 minutes. The results of A4 paper sheet combustion are summarized in Table 1. No carbonization was observed on the A4 sheet after 30, 60 and 120 seconds of heating, but slight carbonation was observed after 180 seconds of heating.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e. the reactive polyurethane -NCO groups react with Mg (OH) 3 and nanosaven-OH groups to form chemical bonds instead of physical mixing.

Example 6 20 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (E4221, epoxy resin, ex. Union Carbide) was charged to the reactor and stirred at 300 rpm, followed by the addition of (8 g, equivalence ratio E4221 / MeHHPA). = 1 / 1.14) MeHHPA (hexahydro-4-methylphthalic anhydride) as curing agent and 0.1 g BDMA (N, N-dimethylbenzylamine) as catalyst. After stirring for 5 minutes, 48.1 g of aluminum hydroxide powder was added to the reactor to give a white slurry after 10 minutes of stirring. The slurry was applied at a thickness of 2 mm onto a sheet of A4 paper and then dried at room temperature for 24 hours.

A flame test was performed on the surface of the sample layer on a butane gas burner using a flame temperature of 1000-1200 ° C for a period of 30 seconds to 3 minutes. The A4 paper sheet burn results are summarized in Table 1. No carbonization was observed on the A4 sheet after 30 and 60 seconds of heating, while it became slightly charred after 120 seconds of heating and charred after 180 seconds of heating.

According to this example, the fire resistance time was more than 3 minutes due to the reinforced sample layer, i.e., the anhydride groups of the epoxy resin (derived from excess MeHHPA) reacted with Al (OH) 3 -OH groups to form chemical bonds instead of physical mixing. .

Example 7 Referring to Figure 2, a slurry of 2 mm thickness was applied to the surface of A4 sheet of paper 10 and dried at room temperature for 24 hours. The flame test was carried out on the surface of the sample layer 20 on a butane gas burner using a flame temperature of 1000-1200 ° C for 180 hours in which the bottom surface of A4 sheet of paper 10 was combined with a temperature detector 50 thermocouple 60 to monitor temperature rise. Commercial expandable, fire-resistant paint (FM900, ex. YUNG CHI PAINT & VARNISH MFG. CO., LTD) with a thickness of 2 mm was subjected to the same flame test. As shown in Figure 3, the temperature under the commercially expandable flame-retardant paint rose rapidly to 200 ° C after 60 seconds of heating. For comparison, the temperature under the sample layer of Example 5 rose to 200 ° C after heating for 180 seconds.

According to this example, the fire resistance time was significantly increased due to the reinforced sample layer, i.e., the -NCO groups of the reactive polyurethane react with Mg (OH) 3 and nanosaven-OH groups to form chemical bonds instead of physical mixing.

table 1

Although the invention has been described by way of example and with respect to a preferred embodiment, it is to be understood that the invention is not limited thereto. On the contrary, it is intended to cover various modifications and similar arrangements (which would be apparent to those skilled in the art). Accordingly, the broad scope of the appended claims should be construed to include all such modifications and corresponding arrangements.

Claims (10)

A fire-resistant coating material comprising: an organic / inorganic composite comprising: 30 to 70% by weight of an organic component comprising polyurethane or a polyolefin copolymer having a first functional group of isocyanate groups, 70 to 30% by weight of inorganic particles having is another reactive, hydroxyl functional group comprising a metal hydroxide Al (OH) 3 or Mg (OH) 2; wherein the inorganic particles are chemically bonded to the organic component by reaction between the first and second reactive functional groups; wherein the inorganic and organic components are sufficiently bonded to provide a flame-retardant coating material capable of withstanding flame temperatures from 1000 to 1200 ° C for more than 3 minutes. The fire-resistant coating material of claim 1, further comprising water or an organic solvent. The fire-resistant coating material of claim 1, further comprising water, pigment, thickener, antifoam, surfactant or combinations thereof. The fire resistant coating material of claim 1, further comprising an organic solvent, a pigment, a resin, a leveling agent, a curing agent, or combinations thereof. The fire-resistant coating material of claim 1, further comprising a flame retardant, silane, siloxane, glass sand or fiberglass. The fire-resistant coating material of claim 1, which is used for fire-resistant coating of interior structures. The fire resistant coating material according to claim 1, which is used for the fire resistant coating of structural steels. The fire-resistant coating material of claim 1, which is used for fire-resistant coating of conductive or cable sheaths. The flame retardant coating material of claim 1, which is used for the flame retardant coating of foamable materials. The fire-resistant coating material of claim 1, which is used for fire-resistant coating of fire-sensitive objects in vehicles. claim