Water-based foamed refractory coating composition

Abstract

To provide an aqueous foamable fireproof coating composition which is sufficiently excellent in fire resistance under fire and water resistance of a coating under normal conditions.SOLUTION: The aqueous foamable fireproof coating composition comprises a resin, a charring aid, a carbon source, a foaming agent, and water, where the carbon source comprises pentaerythritol phosphoric acid ester as part of components thereof. Also provided is a method of coating a substrate, the method comprising coating a substrate surface with the aqueous foamable fireproof coating composition. Further provided is a method of protecting a structure from heat and fire, the method comprising coating a substrate surface with the aqueous foamable fireproof coating composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an aqueous foaming refractory coating composition containing water as a diluent medium.

Background Art

[0002] Since iron rapidly loses its strength near 500°C, in the event of a fire, a steel-framed structure collapses, making evacuation and firefighting activities impossible. For this reason, in order to maintain the strength for a specified time even during a fire, it is obligatory by the Building Standards Law to apply a refractory coating with heat insulation properties to the steel frame of the structure. As this refractory coating material, there are rock wool refractory coatings and foaming refractory paints. Rock wool refractory coatings are inexpensive and widely distributed in the market, but in order to exhibit refractory performance, a thickness of 1 cm to several cm is required, and there is a problem that spraying work is difficult.

[0003] On the other hand, a foaming refractory paint is a coating material that expands the coating film due to the temperature rise during a fire and exhibits heat insulation properties. Unlike rock wool, the refractory coating using a foaming refractory paint is a thin film during normal times and does not damage the shape of the structure itself. During a fire, it expands and carbonizes, and a heat-insulating layer called char suppresses the temperature rise of iron and can delay the collapse of the structure.

[0004] As this foaming refractory paint, the applicant has proposed in Patent Document 1 a foaming refractory paint containing a hydrolyzable silyl group-containing resin, a plasticizer, a foaming agent, and a carbonizing agent. In this paint, thick coating is easy, and a protective coating film excellent in various physical properties such as quick drying property, internal curing property, and water resistance can be obtained, and in the situation of a fire, a foaming layer excellent in fire resistance can be formed.

[0005] However, the foaming refractory paint described in Patent Document 1 contains an organic solvent as a diluent medium, and there is a problem of odor when it is applied in hospitals, schools, etc. In addition, there are problems such as the inability to perform parallel work with electrical work due to the scattering of the organic solvent, and the demand for an aqueous foaming refractory paint using water as a diluent medium is increasing.

[0006] As an aqueous foaming fire-resistant paint, for example, Patent Document 2 discloses a paint composition containing an acrylic resin emulsion, a polyhydric alcohol, a foaming agent, a flame retardant dehydrating agent, and an alkali thickening type emulsion. Although this paint composition is excellent in painting workability and fire resistance, there is a problem that its application range is limited because the water resistance of the paint film is insufficient.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to propose an aqueous foaming fire-resistant paint composition that is sufficiently excellent in fire resistance during a fire and water resistance of the paint film during normal times.

Means for Solving the Problems

[0009] By the way, in order to generate char during a fire, a char formation assisting agent, a carbon source, and a foaming agent are blended in the foaming fire-resistant paint. The char generation mechanism by these components is not clear, but generally it is considered as follows. The temperature around the paint film becomes high due to the flame, and the char formation assisting agent contained in the paint film thermally decomposes to generate a Lewis acid. Then, the carbon source is decomposed by this Lewis acid to form a carbonized layer. On the other hand, the foaming agent contained in the paint film is decomposed by the high temperature to generate gas, and the carbonized layer expands by foaming the molten paint film forming components, thereby generating char.

[0010] The present inventor has intensively studied a method for improving the water resistance during normal times in an aqueous foaming fire-resistant paint composition. As a result, by using a specific compound as a carbon source used to generate char in the foamed refractory coating composition, a coating film excellent in water resistance during normal times has been successfully obtained without significantly reducing the fire resistance during a fire.

[0011] That is, the present invention is Item 1. An aqueous foamed refractory coating composition containing a resin, a char formation auxiliary agent, a carbon source, a foaming agent, and water, wherein the carbon source is many contains a polyhydric alcohol phosphate wherein the polyhydric alcohol phosphate ester is 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide, aqueous foamed refractory coating composition. Item 2. The aqueous foamed refractory coating composition according to Item 1, wherein the polyhydric alcohol source of the polyhydric alcohol phosphate is pentaerythritol. Item 3. The resin contains a carboxyl group, Item 1 or 2 aqueous foamed refractory coating composition described above. Item 4. The acid value of the resin is 3 to 100 mgKOH / g, according to any one of Items 1 to 3 aqueous foamed refractory coating composition described in any one of the above. Item 5. The resin is a copolymer emulsion of a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers, according to any one of Items 1 to 4 aqueous foamed refractory coating composition described in any one of the above. Item 6. The copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is in the range of 1 to 10% by mass in all polymerizable unsaturated monomers, Item 5 aqueous foamed refractory coating composition described above. Item 7. Further containing a crosslinking agent, according to any one of Items 1 to 6 aqueous foamed refractory coating composition described in any one of the above. Item 8. The crosslinking agent is a polyvalent metal compound, Item 7 aqueous foamed refractory coating composition described above. Item 9. A one-component coating composition, according to any one of Items 1 to 8The aqueous foaming refractory coating composition according to any one of claims 1 to 9. Item 10. A two-component coating composition, the aqueous foaming refractory coating composition according to any one of claims 1 to 9. Item 11. 8 A two-component coating composition that is mixed and used immediately before use, wherein the first component contains a resin, the second component contains a cross-linking agent, and the first component and / or the second component contains a carbon source, a char formation auxiliary agent, a foaming agent, and water. The aqueous foaming refractory coating composition according to claim 1. 0 Item 12. A method for coating a substrate, comprising coating the surface of the substrate with the aqueous foaming refractory coating composition according to any one of claims 1 to 11. 1 Item 13. A method for protecting a structure from heat and fire, comprising coating the surface of the substrate with the aqueous foaming refractory coating composition according to any one of claims 1 to 11. 1 Relating to.

Advantages of the Invention

[0012] According to the present invention, an aqueous foaming refractory coating composition capable of forming a coating film excellent in physical properties such as water resistance in normal times can be obtained. Further, the coating film formed by this aqueous foaming refractory coating composition is hardly deteriorated by rainwater or the like, and expands at high temperatures such as during a fire even after a long period has elapsed after coating, and exhibits excellent heat insulation properties, so that the collapse of the structure due to heat can be delayed.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] The aqueous foaming refractory coating composition of the present invention contains a resin, a char formation auxiliary agent, a carbon source, a foaming agent, and water.

[0015] <Resin> In the present invention, a resin that can be dissolved or dispersed in water is used. There is no particular limitation on the type of the resin, and when it is in the form of dispersed particles, it can be in a single-layer form or a multi-layer form such as a core-shell type.

[0016] As an example of the resin, any conventionally known resin having a coating film-forming ability can be used without particular limitation. Specific examples thereof include acrylic resin emulsion, acrylic-silicone resin emulsion, urethane resin emulsion, fluororesin emulsion, epoxy resin emulsion, polyester resin emulsion, alkyd resin emulsion, melamine resin emulsion, etc., but are not limited thereto. Further, these may be used alone or in combination of two or more.

[0017] Preferably, the resin contains a carboxyl group.

[0018] In the present invention, when the resin has a carboxyl group, the acid value of the resin is preferably in the range of 3 to 100 mgKOH / g, particularly 5 to 80 mgKOH / g. Here, the acid value is determined by a conventional method based on alkali neutralization titration, which is the number of mg of potassium hydroxide required to neutralize the acid groups contained in 1 g of the resin non-volatile matter.

[0019] Examples of the resin include copolymer emulsions of carboxyl group-containing polymerizable unsaturated monomers and other polymerizable unsaturated monomers.

[0020] Examples of the carboxyl group-containing polymerizable unsaturated monomers include (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, β-carboxyethyl acrylate, and combinations thereof.

[0021] When producing the copolymer emulsion, the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is preferably in the range of 1 to 20% by mass, particularly 3 to 10% by mass, in all the polymerizable unsaturated monomers.

[0022] Examples of other polymerizable unsaturated monomers include alkyl or cycloalkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name), cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate; (meth)acrylates having an isobornyl group such as isobornyl (meth)acrylate; (meth)acrylates having an adamantyl group such as adamantyl (meth)acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene; polymerizable unsaturated monomers having an alkoxysilyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane; perfluoroalkyl (meth)acrylates such as perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefin; monomers having a photopolymerizable functional group such as a maleimide group; nitrogen-containing polymerizable unsaturated monomers such as (meth)acrylonitrile, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, an adduct of glycidyl (meth)acrylate and amines; Monoesters of (meth)acrylic acid and dihydric alcohols having 2 to 8 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc., ε-caprolactone-modified products of monoesters of (meth)acrylic acid and dihydric alcohols having 2 to 8 carbon atoms, N-hydroxymethyl (meth)acrylamide, allyl alcohol, hydroxyl group-containing polymerizable unsaturated monomers such as (meth)acrylate having a polyoxyethylene chain with a hydroxyl group at the molecular end; Epoxy group-containing polymerizable unsaturated monomers such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, allyl glycidyl ether; (Meth)acrylate having a polyoxyethylene chain with an alkoxy group at the molecular end; Sulfonic acid group-containing polymerizable unsaturated monomers such as 2-acrylamido-2-methylpropanesulfonic acid, allyl sulfonic acid, sodium styrenesulfonate, sulfoethyl methacrylate, and its sodium salt or ammonium salt; Phosphate group-containing polymerizable unsaturated monomers such as 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate; Carbonyl group-containing polymerizable unsaturated monomers such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone); And combinations thereof.

[0023] As the other polymerizable unsaturated monomer, from the viewpoints of water resistance and fire resistance, it is preferable to use an alkyl or cycloalkyl (meth) acrylate and / or a vinyl aromatic compound.

[0024] The above copolymer emulsion can be obtained by adopting an ordinary method, but from the viewpoint of the water resistance of the formed coating film, the emulsion polymerization method is preferable. In emulsion polymerization, commonly used ionic or nonionic surfactants can be used.

[0025] Based on the total mass of the non-volatile components in the aqueous foaming fire-resistant coating composition, the resin can be present in the aqueous foaming fire-resistant coating composition in a range of 5 to 50% by mass, more preferably 10 to 35% by mass, in terms of the non-volatile content mass.

[0026] In the present invention, the mass of the non-volatile components in the aqueous foaming fire-resistant coating composition can be calculated by using an aqueous foaming fire-resistant coating composition with a known mass (for example, 0.3 g) as a sample, putting this sample into a pre-weighed aluminum dish, heating this sample in an oven at 105 °C for 30 minutes, measuring the mass of the dish again, and calculating from the mass before heating and the mass of the sample after heating (refer to ASTM D2697).

[0027] In this specification, unless otherwise specified, the value of mass% is calculated based on the total mass of the non-volatile components in the aqueous foaming fire-resistant coating composition. Incidentally, the non-volatile content means the residue excluding the volatile components, and the residue may be solid or liquid at normal temperature.

[0028] <Char formation auxiliary agent> The char formation assisting agent is for promoting the formation of char when the coating film formed by the aqueous foaming refractory coating composition is exposed to fire. Specifically, phosphorus-containing compounds such as ammonium phosphate, ammonium polyphosphate, and phosphoric acid are used. Among the phosphorus-containing compounds, ammonium phosphate compounds which are ammonium salts of phosphoric acid or polyphosphoric acid are preferred, and ammonium polyphosphate is more preferred. In the present invention, it is also possible to use other char formation assisting agents instead of or in addition to the phosphorus-containing compounds. For example, the combination of ammonium polyphosphate and tris-(2-hydroxyethyl)isocyanurate (THEIC) is an example thereof.

[0029] Based on the total mass of the non-volatile components in the aqueous foaming refractory coating composition, the above char formation assisting agent can be present in the aqueous foaming refractory coating composition in an amount of 10 to 70% by mass, more preferably 20 to 45% by mass.

[0030] <Carbon source> The aqueous foaming refractory coating composition contains a carbon source.

[0031] In the present invention, the carbon source includes polyhydric alcohol phosphate ester as a part of its components.

[0032] Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, cellulose powder, etc., and pentaerythritol is particularly preferred.

[0033] In the present invention, from the viewpoints of water resistance, fire resistance, and further durability, the use of 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide as the polyhydric alcohol phosphate ester is suitable.

[0034] 4-Hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide is a compound represented by the following general formula.

[0035] [Chemical]

[0036] In the present invention, the carbon source can preferably be present in the aqueous foaming refractory coating composition in an amount of 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the non-volatile components in the aqueous foaming refractory coating composition.

[0037] <Blowing agent> In the present invention, the aqueous foaming refractory coating composition contains a spumific. A spumific is one or more compounds that decompose to provide an expanding gas when exposed to heat (usually fire). The heat sufficient for the blowing agent to decompose and generate gas is usually about 90 °C or higher.

[0038] The temperature at which the blowing agent releases gas is desirably lower than the temperature at which the organic polymer softens and lower than the temperature at which char is formed. The aqueous foaming underground coating composition thus formed can form char after sufficient foaming and become a better heat insulator.

[0039] As foaming agents, melamine, melamine formaldehyde, methylolated melamine, hexamethoxymethyl melamine, melamine monophosphate, melamine diphosphate, melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, urea, nitro urea, dimethyl urea, dicyandiamide, guanylurea phosphate, glycine, amine phosphate, azodicarbonamide, 4,4'-oxybis(benzenesulfonyl hydrazide), p-toluene hydrazide, p-toluenesulfonyl semicarbazide, dinitrosopentamethylenetetramine, 5-phenyltetrazole, diazoaminobenzene, etc. can be used. When the above compounds are exposed to heat, they decompose and release nitrogen gas. In addition, ammonium borate, potassium carbonate, citric acid derivatives, etc., compounds that release carbon dioxide, water vapor and / or ammonia when exposed to heat, and expandable graphite can also be used as foaming agents. Preferred foaming agents can be melamine or its derivatives and are used alone or in combination.

[0040] Based on the total mass of the non-volatile components in the aqueous foaming refractory coating composition, the foaming agent can preferably be present in the range of 1 to 30% by mass, more preferably 5 to 25% by mass.

[0041] The aqueous foaming refractory coating composition of the present invention can further contain one or more of a crosslinking agent, a pigment, a plasticizer, and a film-forming aid.

[0042] <Crosslinking agent> In the present invention, the aqueous foaming refractory coating composition can optionally contain a crosslinking agent. In the present invention, polyvalent metal compounds are preferably used as the crosslinking agent. The polyvalent metal compound has a metal capable of forming a metal crosslink with a functional group contained in the resin. Metal crosslinking is a crosslinked structure that connects between resin molecules via a metal. The present inventor believes that such metal crosslinking decomposes at a lower temperature than a crosslinked structure formed by a covalent bond between non-metals, and thus forms a strong char without hindering the expansion of the coating film when exposed to a flame.

[0043] The polyvalent metal compound is a polyvalent metal compound containing a metal element capable of taking a divalent or higher, preferably divalent to tetravalent ionic valence. Examples include compounds containing metal elements such as Mg, Ca, Ba, Fe, Cu, Zn, Al, Ti, Si, Zr, and Mn. As the polyvalent metal compound, either an inorganic metal compound or an organometallic compound can be preferably used.

[0044] Examples of the inorganic metal compound include metal oxides, metal hydroxides, metal nitrates, metal sulfates, metal phosphates, etc. Among these, metal oxides are preferred.

[0045] Examples of the organometallic compound include metal organic salts, metal alkoxides, organometallic complexes, etc. Among these, the use of metal organic salts is preferred.

[0046] Examples of the organic acid constituting the metal organic salt include formic acid, acetic acid, propionic acid, butyric acid, zinc oxalate, valeric acid, α-methylbutyric acid, salicylic acid, stearic acid, lactic acid, etc.

[0047] Also, as a crosslinking agent, a compound having a functional group capable of reacting with the functional group contained in the resin can be used. Examples include polyoxazoline compounds, carbodiimide compounds, polyamines, hydrazine compounds, polyhydrazide compounds, polyisocyanate-based compounds, etc.

[0048] When the aqueous foaming refractory coating composition of the present invention uses a crosslinking agent, its amount can be present in the range of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the non-volatile content mass of the resin.

[0049] <Pigment> The aqueous foaming refractory coating composition of the present invention can optionally contain a pigment. The pigment excludes those which are the above-mentioned polyvalent metal compounds. As the coloring pigment, those known in the paint field can be used. For example, titanium dioxide (white pigment), carbon black, colored pigments such as iron oxide; filler pigments such as barite, talc, calcium carbonate, kaolin, clay, etc.; and fibers, etc. can be mentioned. The pigment can be present in the aqueous foaming refractory coating composition in the range of 1 to 40% by mass, preferably 5 to 30% by mass, based on the total mass of the non-volatile components in the aqueous foaming refractory coating composition.

[0050] <Plasticizer and / or film-forming aid> The aqueous foaming refractory coating composition of the present invention can optionally contain a plasticizer and / or a film-forming aid. The plasticizer is a compound that remains liquid at room temperature and remains in the coating film, and those known in the paint field can be used. Specific examples of the plasticizer include, for example, fatty acid ester-based plasticizers, phosphate ester-based plasticizers, epoxy-based plasticizers, etc.

[0051] On the one hand, a film-forming aid is a high-boiling organic solvent that is compatible with the resin. It remains in the coating film after water has evaporated, and gradually evaporates while promoting the fusion of resin particles. Specific examples of film-forming aids include glycol ether compounds such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monophenyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, etc.; ester compounds such as 2,2,4-trimethylpentanediol monoisobutyrate, 2,2,4-trimethylpentanediol diisobutyrate, etc.

[0052] When a plasticizer and a film-forming aid are contained, the content in that case is in the range of 0.1 to 15% by mass, preferably 0.5 to 10% by mass, based on the total mass of the non-volatile components in the aqueous foaming refractory coating composition.

[0053] <Aqueous foaming refractory coating composition> The aqueous foaming refractory coating composition of the present invention can optionally contain other components, such as pigment dispersants, catalysts, organic solvents, additives for changing the melt viscosity, rheology modifiers, curing agents, etc., but is not limited thereto.

[0054] The coating form of the aqueous foaming refractory coating composition of the present invention is not particularly limited. It can also be a one-component type. When the aqueous foaming refractory coating composition of the present invention contains a crosslinking agent, it is a two-component coating composition that is mixed and used immediately before use, where the first component (I) contains a resin, the second component (II) contains a crosslinking agent, and it is preferred that the first component and / or the second component contain a carbon source, a char formation aid, a foaming agent, and water.

[0055] <Coating method> The present invention further relates to a method for coating a substrate, which includes coating the above aqueous foaming refractory coating composition on the surface of the substrate.

[0056] The aqueous foaming refractory coating composition of the present invention can be cured and / or dried at ambient temperature, for example, -5°C to 40°C. Therefore, it is suitable for application to large structures where heat curing is not practical.

[0057] In the present invention, the thickness of the dry film of the layer of the aqueous foaming refractory coating composition can be appropriately selected according to the use. Typically, in the case of cellulose-based refractory applications (for example, applied to buildings such as office buildings), it is 100 μm to 8 mm, preferably 200 μm to 4 mm.

[0058] The present invention further relates to a method for protecting a structure from flame or heat, which includes coating the above aqueous foaming refractory coating composition on the surface of the substrate.

[0059] The aqueous foaming refractory coating composition of the present invention can be applied to various substrates.

[0060] Examples of the base material include not only metals such as steel frames, aluminum, and galvanized iron sheets, but also wallpaper, plywood, wood, inorganic boards, concrete, mortar, FRP, plastics, paper, cloth, fiber, synthetic resin, rubber, silicon, electric wire cables, etc. Examples of the structure include ground structures, marine structures, etc. Particularly preferred structures include buildings defined in Articles 21 and 27 of the Building Standards Law. Some specific examples thereof include buildings, schools, hospitals, hotels, movie theaters, stores, warehouses, airports, etc.

[0061] When applying the aqueous foaming fire-resistant coating composition of the present invention to the steel frame of an existing structure, after performing a base treatment such as rust removal, the aqueous foaming fire-resistant coating of the present invention can be applied after applying an undercoat paint as necessary. Further, a known topcoat painting may be performed after applying the aqueous foaming fire-resistant coating composition of the present invention.

[0062] The coating method is not particularly limited, and it can be easily applied by a general method such as a brush, a spatula, a roller, or a spray. It is possible not only to apply smoothly but also to form a pattern with unevenness in a thick film. These coating methods are appropriately selected according to the purpose of use of the base material.

Examples

[0063] Hereinafter, the present invention will be further described with reference to examples. Here, “parts” and “%” mean “parts by mass” and “mass %”, respectively.

[0064] Example 1 <Manufacture of one-component aqueous foaming fire-resistant coating composition> Example 1 The following components were placed in a container and stirred and mixed using a planetary mixer until uniform to obtain a one-component aqueous foaming fire-resistant coating composition (X-1).

[0065] [Composition of aqueous foaming fire-resistant coating composition (X-1)] Deionized water 20 parts Melamine 8.09 parts Pentaerythritol phosphate (Note 1) 8.09 parts 8 parts of titanium oxide 24.27 parts of ammonium polyphosphate 3 parts of rock wool fiber 17.26 parts of 50% acrylic resin emulsion (Note 2) 5.9 parts of 2,2,4 - trimethylpentanediol monoisobutyrate 0.2 part of thickener

[0066] (Note 1) Pentaerythritol phosphate: 4 - hydroxymethyl - 2,6,7 - trioxa - 1 - phosphabicyclo[2.2.2]octane 1 - oxide (Note 2) 50% acrylic resin emulsion: styrene / methacrylic acid / 2 - ethylhexyl acrylate / hydroxyethyl acrylate = 85 / 8 / 6.1 / 0.9, emulsion polymer, non - volatile content 50%, acid value 40 mgKOH / g

[0067] <Manufacture of two - component aqueous foaming refractory coating composition> Example 2 Using the aqueous foaming refractory coating composition (X - 1) obtained in Example 1 as the first component, 1.625 parts of 10% zinc acetate aqueous solution was added as the second component and stirred and mixed to produce an aqueous foaming refractory coating composition (X - 2).

[0068] Examples 3 - 4 and Comparative Example 1 Except that the formulation composition is as shown in Table 1, each aqueous foaming refractory coating composition (X - 3) - (X - 5) was produced in the same manner as in Example 1 or Example 2.

[0069]

Table 1

[0070] Test Example 1 For each of the aqueous foaming refractory coating compositions obtained in the above Examples and Comparative Examples, a simple fire - resistance test, durability, and blister - resistance were evaluated using a cone calorimeter.

[0071] (*) Simple fire - resistance test A 100×100×3.2 mm blast steel plate was coated with "ESCO NB Primer" (trade name, manufactured by Kansai Paint Co., Ltd., a modified epoxy resin rust preventive paint), and after drying, each aqueous foaming refractory paint composition was coated so that the dry film thickness was 1.0 mm, and a test panel was prepared by drying at 23°C for 3 days and at 50°C for 1 day. A thermocouple was attached to the back side of the test panel, and it was subjected to an ignition test using a cone calorimeter with a heating intensity of 50 kw / m 2 . The temperature of the thermocouple after 20 minutes was measured and evaluated according to the following criteria. 〇: The temperature of the thermocouple is 500°C or less, ×: The temperature of the thermocouple exceeds 500°C.

[0072] (*) Durability: The same test panel as that prepared in the above-mentioned simple fire resistance test was prepared, immersed in water at 20°C for 18 hours, cooled to -20°C for 3 hours, and heated to 50°C for 3 hours. One cycle was defined as one cycle, and this was repeated 10 times to deteriorate the coating film, and then it was similarly subjected to the simple fire resistance test. As a result, the deteriorated coating film had a higher temperature compared to the new coating film.

[0073] The numerical values in Table 1 are the temperature differences obtained by subtracting the temperature of the new coating film from the temperature of the deteriorated coating film with respect to the temperature of the back side of the test panel after 20 minutes in the cone calorimeter test. The smaller the numerical values in the table, the less the fire resistance decreases even when the coating film deteriorates, and it was judged that the durability was good. (*) Blister resistance Two pieces of 150×70×3.2 mm blast steel plates were coated with each aqueous refractory paint composition so that the dry film thickness was 2 mm and dried at 23°C for 7 days. One piece was left as it was, and on the other piece, "Cosmo Silicon" (trade name, manufactured by Kansai Paint Co., Ltd., an aqueous reaction-curing type acrylic silicon paint) was further coated so that the dry film thickness was 50 μm and dried at 23°C for 7 days to obtain test panels. Each test panel with or without the topcoat was immersed in water at 23°C for 3 weeks, dried at 50°C for 3 days, and the appearance was evaluated according to the following criteria. ◎: No change before and after immersion, 〇: Very slight blistering is observed, △: Swelling is clearly recognized. ×: Significant swelling is remarkably recognized.

[0074] Test Example 2 (*) Fire resistance test Example 5 A two-component water-based foaming fire-resistant coating composition (X-6) was produced with the following formulation. A steel material (size 300 mm × 300 mm × 4.5 mm) equipped with a thermocouple was prepared, and the water-based foaming fire-resistant coating composition (X-6) was applied thereto with a brush so that the dry film thickness became 3.3 mm, and dried at 23°C for 7 days to obtain a test piece. When this test piece was placed in a furnace heated to a predetermined temperature with respect to the elapsed time so as to have a temperature rising curve defined by ISO834 and subjected to a fire resistance test, the time until the temperature of the test piece reached 500°C was 89 minutes. The test piece after the fire resistance test of Example 5 was covered with char as shown in Fig. 1.

[0075] [Composition of water-based foaming fire-resistant coating composition (X-6)] First component 0.65 part of 25% zinc acetate aqueous solution 18 parts of deionized water 8.09 parts of melamine 8.09 parts of pentaerythritol phosphate (Note 1) 7.94 parts of titanium oxide 24.27 parts of ammonium polyphosphate 0.5 part of rock wool fiber Second component 17.26 parts of 50% acrylic resin emulsion (Note 2) 0.01 part of carbon black 5.9 parts of 2,2,4-trimethylpentanediol monoisobutyrate 0.1 part of thickener.

[0076] Comparative Example 2 The time to reach 500°C was measured in the same manner as in Example 5 except that the formulation was as follows, and it was 77 minutes. In Comparative Example 2, the time to reach 500°C was shorter than that in Example 5, and it was judged that the fire resistance was inferior. [Composition of Aqueous Foaming Fire-Resistant Coating Composition (X-7)] First Component 0.65 part of 25% zinc acetate aqueous solution 20 parts of deionized water 8.09 parts of melamine 8.09 parts of dipentaerythritol 7.94 parts of titanium oxide 24.27 parts of ammonium polyphosphate 0.5 part of rock wool fiber Second Component 17.26 parts of 50% acrylic resin emulsion (Note 2) 0.01 part of carbon black 5.9 parts of 2,2,4-trimethylpentanediol monoisobutyrate 0.1 part of thickener

Claims

1. An aqueous refractory coating composition comprising a resin, a char-forming auxiliary agent, a carbon source, a foaming agent and water, wherein the carbon source contains a polyhydric alcohol phosphate ester, and the polyhydric alcohol phosphate ester is 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide, the aqueous foaming refractory coating composition.

2. The aqueous foaming refractory coating composition according to claim 1, wherein the polyhydric alcohol source of the polyhydric alcohol phosphate ester is pentaerythritol.

3. The aqueous foaming refractory coating composition according to claim 1 or 2, wherein the resin contains a carboxyl group.

4. The aqueous foaming refractory coating composition according to any one of claims 1 to 3, wherein the acid value of the resin is 3 to 100 mgKOH / g.

5. The aqueous foaming refractory coating composition according to any one of claims 1 to 4, wherein the resin is a copolymer emulsion of a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers.

6. The aqueous foaming refractory coating composition according to claim 5, wherein the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is in the range of 1 to 10% by mass in all polymerizable unsaturated monomers.

7. The aqueous foaming refractory coating composition according to any one of claims 1 to 6, further comprising a crosslinking agent.

8. The aqueous foaming refractory coating composition according to claim 7, wherein the crosslinking agent is a polyvalent metal compound.

9. The aqueous foaming refractory coating composition according to any one of claims 1 to 8, which is a one-component coating composition.

10. The aqueous foaming refractory coating composition according to any one of claims 1 to 8, which is a two-component coating composition.

11. A two-component coating composition which is mixed and used immediately before use, wherein the first component (I) contains a resin, the second component (II) contains a crosslinking agent, and the first component and / or the second component contains a carbon source, a char-forming auxiliary agent, a foaming agent and water, the aqueous foaming refractory coating composition according to claim 10.

12. A method for coating a substrate, comprising coating the surface of the substrate with the aqueous foaming refractory coating composition according to any one of claims 1 to 11.

13. A method for protecting a structure from heat and fire, comprising coating the surface of the substrate with the aqueous foaming refractory coating composition according to any one of claims 1 to 11.

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