JP2019077865A - Foam fireproof coating material - Google Patents

Abstract

To provide a foam fireproof coating material which has good coating workability, is excellent in curability, and is suitable for protection of a structure in firing.SOLUTION: A foam fireproof coating material contains a crosslinkable resin composition (A), a foaming agent (B) and a carbonizing agent (C), in which the crosslinkable resin composition (A) contains a tertiary amino group-containing compound (A1), an epoxy group-containing compound (A2) and an organosilicate compound and/or its condensate (A3). A coating method using the foam fireproof coating material, a method for fireproof-covering a structure and a fireproof structure are also disclosed.SELECTED DRAWING: None

Description

  BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a foamed refractory paint that foams and expands in the event of a fire to form a heat insulating layer.

  Although incombustible building materials are used as the material of the steel frame that composes the framework of the building, the strength is significantly reduced under intense heating conditions when a fire occurs, leading to the collapse of the entire building. For this reason, aggregate such as rock wool is mixed with cement type inorganic binder, and it is protected by spraying a fireproof covering material which is mixed with water and made into paste form on the surface of the steel frame, and the rapid strength of the steel frame It is widely practiced to prevent the decline.

  However, this rock wool refractory coating material requires a thickness of 25 mm or more to the steel frame. For this reason, the rock wool refractory coating is not only restricted in terms of the method of construction, but it is not suitable for a part requiring a great appearance utilizing the form of the steel frame itself, since the coating surface is extremely uneven.

  Then, various foamy fireproof paints which mixed a foaming agent, a carbon generation material, etc. with an organic binder are proposed as a fireproof coating material suitable for a part which appearance is required.

  The coating film formed using the foamed fire-resistant paint protects the steel surface from external stimuli such as water as a protective coating film at normal time (when not fire), and decomposes due to high heat and generates incombustible gas at the time of fire And foam to form a foam layer. It is believed that this porous foam layer serves as a heat insulating layer to suppress the temperature rise and the rapid decrease in strength of the steel frame.

  The applicant of the present application is a paint containing a resin, a foaming agent, a carbon supply agent, an inorganic powder and a flame retardant as a foamed fireproof paint, wherein a bromine-containing phosphate ester and / or a condensate thereof is used as a flame retardant. We proposed a foamy fire-resistant paint characterized by According to such a paint, when the coating film is foamed due to high heat, it is possible to maintain the carbonized layer well in the foam layer to maintain the heat insulation.

  However, the foamed fire-resistant paint described in Patent Document 1 uses a non-crosslinked resin such as an acrylic resin as a coating film-forming component, and has a problem that the curability at normal temperature is not sufficient.

  By the way, in order for the foamed layer formed by the heat at the time of fire to reach a level that suppresses the temperature rise of the steel frame, it is necessary to increase the film thickness of the protective coating film made of the foamed refractory paint applied to the steel frame. For this reason, in a paint having poor curability as described in Patent Document 1, the same paint is divided into multiple coats, and it is necessary to carry out a coat recoating such that drying is repeated for each coat. In some cases, for example, about two weeks may be required for the total time required for the coating process, it is necessary to improve the painting workability.

  On the other hand, various foamable fire-resistant paints which use a crosslinkable resin as a film-forming component are also proposed.

  Patent Document 2 discloses a thermally expandable coating composition containing a resin containing a polysiloxane chain, an epoxy resin, an amine curing agent, a foaming agent, and a char-forming additive. According to the composition described in the document, a cross-linked coating of epoxy and amine protects the structure on a regular basis, and in the event of a fire, a rigid foam layer is obtained by means of the polysiloxane chains contained in the composition. For this reason, even in a fire of a severe rank called jet fire, it is possible to suppress the temperature rise of the structure by the heat insulating property by the foam layer.

  Patent Document 3 describes that a heat-resistant composition containing a polysulfide, an epoxy resin, an amine group- or amide group-containing compound, a phosphonate, a fiber and a polysiloxane is excellent in jet fire resistance and smoke resistance. There is.

However, the compositions described in Patent Documents 2 and 3 are intended to be applied to petroleum, gas, chemical plant facilities where jet fire is assumed, and for the purpose of improving the heat insulation of the foam layer rather than the normal coating appearance. It is designed. For this reason, the coating workability is not sufficient, and there is a problem that the foam layer is hard and therefore easily broken.
Japanese Patent Application Laid-Open No. 10-7947 International Publication No. 2010-054984 Pamphlet International Publication 2014-019947 Pamphlet

  The object of the present invention is to provide a foamed fireproof paint, a coating method, a fireproof coating method for a structure, and a fireproof structure having good paintability, excellent curability, and suitable for protection of a structure in case of fire. is there.

  As a result of intensive studies on the above-described problems, the present inventors have found that a crosslinkable resin composition containing a specific resin composition can be sufficiently applied to a foamed fire-resistant paint, and particularly foams that protect a structure from fire by heating during a fire. It has been found that a protective coating which can be converted into a layer can be easily formed.

Item 1. A foamable fire-resistant paint comprising a crosslinkable resin composition (A), a foaming agent (B) and a carbonization agent (C), wherein the crosslinkable resin composition (A) comprises a tertiary amino group-containing compound (A1), an epoxy Foamed fire-resistant paint comprising a group-containing compound (A2) and an organosilicate compound and / or a condensate thereof (A3).
Item 3. The foamed refractory paint according to Item 1, wherein the second-order amino group-containing compound (A1) is a third-order amino group-containing acrylic resin.
Item 3. Item 3. The foamed refractory paint according to Item 1 or 2, wherein the epoxy group-containing compound (A2) is a compound having an ether bond.
Item 4. Based on 100 parts by mass of the crosslinkable resin composition (A),
The blend ratio of the tertiary amino group-containing compound (A1), the epoxy group-containing compound (A2), and the organosilicate compound (A3) is
30 to 98 parts by mass of tertiary amino group-containing compound (A1) 1 to 50 parts by mass of epoxy group-containing compound (A2) 1 to 50 parts by mass of organosilicate and / or its condensate (A3) 4. A foamed refractory paint according to any one of Items 1 to 3.
Item 5. 5. The foamed refractory paint according to any one of Items 1 to 4, further comprising a plasticizer (D).
Item 6. The foamed refractory paint according to any one of Items 1 to 5, further comprising an organic viscosity modifier (E).
Item 7. 7. The foamed refractory paint according to any one of items 1 to 6, further comprising at least one inorganic material (F) selected from a fiber, an inorganic viscosity modifier and an inorganic pigment.
Item 8. 8. The foamed refractory paint according to any one of Items 1 to 7, further comprising a curing catalyst (G).
Item 9. Item 9. The foamed refractory paint according to any one of Items 1 to 8, further comprising a dispersant (H).
Item 10. 10. A coating method of coating and drying the foamed refractory paint according to any one of Items 1 to 9 on a substrate surface.
Item 11. The fireproof coating method of the structure which applies and dries the foaming refractory paint of any one of claim 1-9 on a substrate surface, and forms a protective coating film.
Item 12. 10. A fireproof structure provided with a protective coating using the foamed fireproof paint according to any one of Items 1 to 9.

  According to the foamed refractory paint of the present invention, coating workability is good. Therefore, the protective coating can be easily formed by coating.

  Such a protective coating film is excellent in curability at normal temperature. For this reason, the structure provided with the said protective coating film can maintain the aesthetics over a long period of time.

  In addition, the protective coating formed by the foamed fire-resistant paint of the present invention is transformed into a dense and strong foamed layer by expanding under the condition of fire. Therefore, the temperature rise of the structure base is suppressed, which helps to suppress the deformation and collapse of the structure at the time of fire.

  The foamed refractory paint of the present invention is a composition containing a crosslinkable resin composition (A), a foaming agent (B) and a carbonizing agent (C).

<Crosslinkable Resin Composition (A)>
The crosslinkable resin composition (A) which can be a film-forming component of the foamed fire-resistant paint of the present invention comprises a tertiary amino group-containing compound (A1), an epoxy group-containing compound (A2), and an organosilicate compound and / or condensation thereof The thing (A3) is included.
Hereinafter, (meth) acryloyl group means acryloyl group and methacryloyl group, or acryloyl group or methacryloyl group, and "(meth) acrylic acid" means acrylic acid and methacrylic acid, or acrylic acid or methacrylic acid. .

Tertiary amino group-containing compound (A1)
In the present invention, the tertiary amino group-containing compound (A1) may be a compound having a tertiary amino group in the molecule, for example, an amino group-containing polymerizable unsaturated monomer and a copolymerizable unsaturated monomer. An amino group-containing acrylic resin having other polymerizable polymerizable unsaturated monomer as a copolymerization component can be suitably used. Preferably, at least a portion of one or both of the amino group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer copolymerizable with the polymerizable unsaturated monomer contains an acryloyl group. More preferably, at least a portion of both the amino group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer copolymerizable with the polymerizable unsaturated monomer contain an acryloyl group.

The method for producing the tertiary amino group-containing compound (A1) is not particularly limited, and may be produced by a conventional method such as radical polymerization using an azo compound or a peroxide as an initiator, or a commercially available product, etc. It is also possible to use
In the present specification, the polymerizable unsaturated monomer means a compound having a radically polymerizable unsaturated group. As a radically polymerizable unsaturated group, a vinyl group, a (meth) acryloyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, a vinyl ether group etc. are mentioned, for example.

  Examples of the amino group-containing polymerizable unsaturated monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N- t-butylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide and the like can be mentioned, and these may be used alone or in combination of two or more kinds .

  In the present invention, in view of coating workability, curability of a protective coating, and the state of a foam layer, among all the monomers used for producing an amino group-containing acrylic resin, a co-polymer of the above amino group-containing polymerizable unsaturated monomer. The polymerization ratio is preferably in the range of 0.2 to 25% by mass, preferably 0.5 to 20% by mass.

  On the other hand, as other polymerizable unsaturated monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl ( Meta) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl ) Acrylates, t-Butylcyclohexyl (meth) acrylates, cyclododecyl (meth) acrylates, isobornyl (meth) acrylates, adamantyl (meth) acrylates, alkyl or cycloalkyl (meth) acrylates such as tricyclodecanyl (meth) acrylate, etc. Alkyl (meth) acrylates having an alkyl group; aromatic ring-containing polymerizable unsaturated monomers such as benzyl (meth) acrylate, styrene, α-methylstyrene and vinyltoluene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl A monoester of (meth) acrylic acid such as (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; E) ε-caprolactone modified product of monoester of acrylic acid and dihydric alcohol having 2 to 8 carbon atoms, N-hydroxymethyl (meth) acrylamide, allyl alcohol, polyoxyethylene chain having hydroxyl group terminal Hydroxyl group-containing polymerizable unsaturated monomers such as (meth) acrylates; (meth) acrylic acid dimethylaminoethyl methyl chloride salt, (meth) acrylic acid dimethylaminoethyl benzyl chloride salt, (meth) acrylic acid diethylaminoethyl methyl chloride salt, (Meth) acrylic acid diethylaminoethyl benzyl chloride salt, (meth) acrylic acid aminopropyldimethylammonium methyl chloride salt, (meth) acrylic acid aminopropyldimethylammonium benzyl chloride salt, (meth) acrylic acid amino acid Ropyl diethyl ammonium methyl chloride salt, aminopropyl diethyl ammonium benzyl chloride salt of (meth) acrylate, trimethyl ammonium methyl sulfate salt of (meth) acrylic acid, triethyl ammonium methyl sulfate salt of (meth) acrylic acid, aminopropyl (meth) acrylate Quaternary such as dimethylammonium methylsulfate, aminopropyldimethylammoniumethylsulfate (meth) acrylate, trimethylaminoethyl (meth) acrylate p-toluenesulfonate, aminopropyldimethylethylammoniumethylsulfate (meth) acrylate and the like Ammonium group-containing polymerizable unsaturated monomer; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyether) Polymerizable unsaturated monomers having an alkoxysilyl group such as tox) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, etc .; perfluorobutylethyl (meth) acrylate, peroxy Perfluoroalkyl (meth) acrylates such as fluorooctylethyl (meth) acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefins; polymerizable unsaturated monomers having a photopolymerizable functional group such as a maleimide group; Vinyl compounds such as N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc. Carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like Mer; nitrogen-containing polymerizable unsaturated monomer such as (meth) acrylonitrile, (meth) acrylamide, etc .; N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylate, methoxypropyl (meth) ) Alkoxy group-containing polymerization such as alkoxyalkyl (meth) acrylates such as acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, and polyalkylene glycol monoalkoxy (meth) acrylates such as polyethylene glycol monomethoxy (meth) acrylate Unsaturated monomer; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, 4 to 7 carbon atoms And carbonyl group-containing polymerizable unsaturated monomers such as vinyl methyl ketones (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like, which may be used alone or in combination of two or more. .

  In the present invention, the weight-average molecular weight of the above-mentioned tertiary amino group-containing compound (A1) is in the range of 1000 to 150000, preferably 5000 to 50000, compatibility with each component contained in the composition, It is suitable from the point of fire resistance, the state of a foaming layer, etc.

  In the present specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (manufactured by Tosoh Corp. "HLC 8120 GPC") with reference to the weight average molecular weight of polystyrene. The columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, and “TSKgel G-2000H × L” (all manufactured by Tosoh Corp., trade names) It was carried out under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI using four.

Epoxy group-containing compound (A2)
In the present invention, examples of the epoxy group-containing compound (A2) include compounds having at least two epoxy groups in the molecule. Specific examples thereof include ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol-epichlorohydrin type epoxy resin, glycerine-epichlorohydrin. Phosphorus adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A Type diglycidyl ether, dihydroxyanthracene type epoxy resin, polyethylene glycol diglycidyl ether Polypropylene glycol diglycidyl ether, polyoxyethylene polyoxypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, diphenyl sulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, bisphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full Orange glycidyl ether, biscresol orange glycidyl ether, bisphenoxyethanol orange glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidyl aniline, N, N-diglycidyl toluidine And the like, as well as any combination thereof.

  In particular, the epoxy group-containing compound (A2) is preferably a compound having an ether bond, particularly a polyether structure, in the molecule. By this, the expansion ratio at the time of heating of the protective coating film formed from the composition of the present invention becomes appropriate, and there is an effect that a strong and dense foam layer can be obtained.

  As the epoxy group-containing compound having such an ether bond, for example, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyoxyethylene polyoxypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether and the like, and any of them Combinations of

Organosilicate compound and / or condensate thereof (A3)
In the present invention, examples of the compound (A3) include organosilicates represented by the following formula and / or condensates thereof.
(R ¹ O) ₄ Si
Wherein R ¹ is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

  Specific examples of the compound (A3) include, for example, tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra-t- One or two or more tetraalkyl silicates such as butyl silicate, and one or two or more partial hydrolytic condensates selected from the silicates can be mentioned.

In the present invention, the compounding amounts of the tertiary amino group-containing compound (A1), the epoxy group-containing compound (A2), and the organosilicate compound (A3) are the above-mentioned crosslinkable resin compositions (C) A) Based on 100 parts by mass,
30 to 98 parts by mass, in particular 45 to 85 parts by mass of the tertiary amino group-containing compound (A1) 1 to 50 parts by mass, in particular 5 to 30 parts by mass of the epoxy group-containing compound (A2) The substance (A3) is preferably in the range of 1 to 50 parts by mass, in particular 5 to 30 parts by mass.

  In addition, the content of the crosslinkable resin composition (A) in the non-volatile component of the foamed refractory coating is 3 to 40% by mass, preferably 5 to 30% by mass from the viewpoint of fire resistance and coating workability. preferable.

In the present specification, the non-volatile content means the residue excluding volatile components, and the residue may be solid or liquid at normal temperature.
The amount of non-volatiles should be determined from the heating residue when the mixture, composition, etc. containing volatile components such as water and organic solvents are dried in a hot air dryer at 105 ° C for 3 hours to volatilize the volatile components. Can.

<Bubbling agent (B)>
In the foamed refractory paint of the present invention, the foaming agent (B) is considered to be a component that decomposes when the cured coating film is exposed to a flame, and the generated gas changes the cured coating film into a foam layer.

  As the foaming agent (B), those known in the field of foamed fire-resistant paints can be used without limitation, and specific examples thereof include, for example, ammonium polyphosphate (APP), monoammonium phosphate, diammonium phosphate , Phosphates or sulfates of sodium, potassium or ammonium such as potassium phosphate (eg, potassium tripolyphosphate), sodium phosphate, ammonium sulfate, potassium sulfate and sodium sulfate; melamine; melamine formaldehyde; methylolated melamine, hexamethoxy Methylmelamine, melamine monophosphate, dimelamine phosphate, melamine biphosphate, melamine polyphosphate, melamine pyrophosphate, dimelamine phosphate and melamine cyanurate, hexamethoxymethylmelamine, etc. Umine derivatives; urea; dimethylurea, butylated urea, alkylated urea, benzogamine, glycoluril type compounds, tris (alkoxycarbonylamino) triazine type compounds, and urea derivatives such as guanylurea; glycine, amine phosphate (eg, polyphosphate) Ammonium), azodicarbonamide, 4,4 oxybis (benzenesulfonyl hydrazide), p-toluenehydrazide, p-toluenesulfonyl semicarbazide, dinitrosopentamethylenetetramine, 5-phenyltetrazole, diazoaminobenzene, expandable graphite, sulfamic acid And tungstannate salts, tris- (2-hydroxyethyl) isocyanurate and the like, and these can be used alone or in combination of two or more.

  As a compounding quantity of the said foaming agent (B), the inside of the range of 100-1000 mass parts, especially 150-800 mass parts is preferable on the basis of 100 mass parts of said crosslinkable resin compositions (A).

<Carburizing agent (C)>
The carbonizing agent (C) in the foamed fire-resistant paint of the present invention reacts with the foaming agent (B) to form a carbonized layer when the cured coating film is exposed to a flame and converted to a foamed layer, It is a component considered to enhance heat insulation. Examples of the carbonizing agent (C) include pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, cellulose powder, hydrocarbon resin, chloroparaffin and the like, which may be used alone or in combination of two or more. Can.

  The compounding amount of the carbonizing agent (C) is preferably 20 to 300 parts by mass, particularly preferably 40 to 250 parts by mass, based on 100 parts by mass of the crosslinkable resin composition (A).

<Plasticizer (D)>
The foamed refractory paint of the present invention can contain a plasticizer (D). By including the plasticizer (D), not only the strength of the foam layer formed during heating is maintained, but also the coating workability of the paint is improved, and the process of the foamed fireproof paint coating process is saved.

  As the plasticizer (D), known ones added for the purpose of enhancing the flexibility of a coating film in the field of paints can be used without limitation, and specifically, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- Heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, dioctyl isophthalate, bis (2-ethylhexyl) 1,2,3,6-tetrahydrophthalate, dimethyl Adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di 2-ethylhexyl adipate, diisononyl adipate, dioctyl adipate, dibutyl diglycol adipate, diisononyl cyclohexane dicarboxylate Fatty acid ester plasticizers such as cyclohexanedicarboxylate, such as dimethylcyclohexanedicarboxylate, diethylcyclohexanedicarboxylate, and di-2-ethylhexylcyclohexanedicarboxylate; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate , Tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, Isodecyl diphenyl phosphate, hydroxide Phenyl diphenyl phosphate, resorcinol bis diphenyl phosphate, triaryl isopropylated compounds of phosphoric acid, compounds obtained by modifying them with various substituents, various condensation type phosphoric acid ester plasticizers, etc. are mentioned, and these can be used alone or It can be used in combination of species or more.

  In particular, as the plasticizer (D), a phosphoric acid ester-based plasticizer, particularly an aromatic phosphoric acid ester-based plasticizer having an aryl group as an organic group is excellent in compatibility with the crosslinkable resin composition (A) and uniform. A cured coating film can be formed, and a uniform foamed layer can be formed when heated, which is suitable.

  The content of the plasticizer (D) is preferably in the range of 1 to 300 parts by mass, particularly 35 to 250 parts by mass, based on 100 parts by mass of the crosslinkable resin composition (A).

<Organic-based viscosity modifier (E)>
The foamed fire-resistant paint of the present invention preferably contains an organic viscosity modifier (E) from the viewpoint of coating workability such as sag resistance. As the organic viscosity modifier (E), known materials used in the paint field can be used without limitation, and specific examples thereof include, for example, acrylic viscosity modifiers, polyethylene viscosity modifiers, polyamide based viscosity Modifiers, polyether type viscosity modifiers such as polyether and urethane modified products thereof, cellulose type viscosity modifiers such as hydroxyethyl cellulose, methylcellulose and modified products thereof, etc., and these may be used alone or in combination of two or more can do. In particular, an amide based viscosity modifier is suitable as the organic viscosity modifier (E) from the viewpoint that the foamable fire resistant coating can be coated in a thick film in a short time and the appearance after painting is excellent.

  The amide-based viscosity modifier is a compound having an —NH—CO— bond in the molecule, and is, for example, a reaction product of a fatty acid and an aliphatic amine and / or an alicyclic amine, an oligomer, or a modified product thereof What contains a mixture as an active ingredient is mentioned.

  Specific examples thereof include saturated fatty acid monoamides such as lauric acid amide and stearic acid amide, unsaturated fatty acid monoamides such as oleic acid amide, substituted amides such as N-lauryl lauric acid amide and N-stearyl stearic acid amide, and methylol stearic acid Amyl and other methylol amides, methylenebisstearic acid amides, ethylenebislauric acid amides, saturated fatty acid bisamides such as ethylenebishydroxystearic acid amides, unsaturated fatty acid bisamides such as methylenebis oleic acid amides, m-xylylene bisstearic acid amides Aromatic bisamides such as ethylene oxide adduct of fatty acid amide, fatty acid ester amide, fatty acid ethanolamide, N-butyl-N'-stearyl It can be exemplified substituted ureas such as iodine, etc., which can be used alone or in combination.

  As an amide system viscosity regulator which can be obtained as a commercial item, "DISPARLON 6900-20X", "DISPARLON 6900-10X", "DISPARLON 603-20X", "DISPARLON A603-10X", "DISPARLON A670-20M", " DISPARLON 6810-20X, DISPARLON 6850-20X, DISPARLON 6820-20M, DISPARLON 6820-10M, DISPARLON FS-6010, DISPARLON PFA-131, DISPARLON PFA-231, DISPARLON F-9020 "," DISPARLON F-9030 "," DISPARLON F-9040 "," DISPAR ON F-9050 "," DISPARLON NS-5010 "," DISPALON NS5025 "," DISPARLON NS-5210 "," DISPARLON NS-5310 "(trade names, manufactured by Kushimoto Chemical Co., Ltd.)," Tarlen 7200-20 ", Taren series such as "Tarlen 7500-20" (trade name, Kyoei Chemical Co., Ltd.), "BYK-405" (trade name, BYK Chem.), "AS-AT-75F" (trade name, Ito) Oil company, etc. can be mentioned.

  When the foamed refractory paint of the present invention contains an organic viscosity modifier (E), the content of the nonvolatile content of the organic viscosity modifier (E) is based on 100 parts by mass of the crosslinkable resin composition (A). Preferably, it is in the range of 0.1 to 50 parts by mass, particularly preferably 0.5 to 25 parts by mass.

<Inorganic material (F)>
The foamed fire-resistant paint of the present invention preferably contains at least one inorganic material (F) selected from fibers, inorganic viscosity modifiers, and inorganic pigments from the viewpoint of fire resistance, the state of the foam layer, and the like.
As the fibers, metals such as copper or copper alloy, metals such as aluminum, iron, zinc, tin, titanium, nickel, magnesium, silicon alone or in the form of alloys, and metals such as fibers mainly composed of metals such as cast iron fibers Fibers; Ceramic fibers, biodegradable ceramic fibers, mineral fibers, glass fibers, potassium titanate fibers, silicate fibers, inorganic fibers such as wollastonite; aramid fibers, cellulose fibers, acrylic fibers, polyester fibers, nylon fibers, phenol resin Organic fibers such as fibers; flame-resistant fibers, pitch carbon fibers, PAN carbon fibers, carbon fibers such as activated carbon fibers; modified products of two or more of these can be used alone or two or more of them Can be used in combination.

As the above-mentioned mineral fiber, those containing SiO ₂ , Al ₂ O ₃ , CaO, MgO, FeO, Na ₂ O, etc. or those containing one or more of these compounds can be used, and it is preferable. Contains an Al element. As a commercial item of mineral fiber, for example, LAPINUS FIBERS B. V-made Roxul series etc. are mentioned.

  When mineral fibers are used as the fibers, the average fiber length is preferably in the range of 0.1 to 4 mm, more preferably 0.3 to 1 mm. Here, with the average fiber length, 50 fibers are randomly selected, the fiber length is measured with an optical microscope, and the average value is obtained.

  When carbon-based fibers are used as the fibers, the average fiber length is preferably in the range of 3 to 12 mm, more preferably 4 to 10 mm.

  When the foamed refractory paint of the present invention contains fibers, the content thereof is preferably 0. on the basis of 100 parts by mass of the crosslinkable resin composition (A) from the viewpoints of fire resistance and the state of the foamed layer. It is in the range of 1 to 100 parts by mass, particularly preferably 1 to 70 parts by mass.

  Further, as an inorganic viscosity modifier, for example, bentonite, swellable silica, hydrophobic silica, montmorillonite, serpentine, vermiculite, smectite (including montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, Steven site) And sepiolite, which may be used alone or in combination of two or more. Moreover, these may be any of natural products, synthetic products, and processed products by organic matter and the like.

  When the foamed refractory paint of the present invention contains an inorganic viscosity modifier, the content thereof is preferably 0.01 to 70 parts by mass, particularly preferably 100 parts by mass of the crosslinkable resin composition (A). Is in the range of 1 to 40 parts by mass.

  Inorganic pigments are not particularly limited, but inorganic coloring pigments such as titanium oxide, carbon black, yellow lead, yellow earth, yellow iron oxide, etc .; talc, calcium carbonate, mica, kaolin, barium sulfate, zinc flower And extender pigments such as (zinc oxide). These can be used alone or in combination of two or more.

  The compounding amount of the inorganic coloring pigment is preferably 10 to 300 parts by mass, particularly preferably 40 to 250 parts by mass, based on 100 parts by mass of the crosslinkable resin composition (A), from the viewpoint of the strength of the foam layer. It is inside.

  The compounding amount of the extender pigment is preferably 0.1 to 100 parts by mass, particularly preferably 100 parts by mass, based on 100 parts by mass of the crosslinkable resin composition (A), from the viewpoint of the strength of the foam layer and the state of the foam layer. It is in the range of 1 to 50 parts by mass.

  When the foamed refractory paint of the present invention contains an inorganic material (F), the content thereof is, based on 100 parts by mass of the crosslinkable resin composition (A), from the viewpoints of fire resistance and the state of the foamed layer. Preferably, it is in the range of 1 to 500 parts by mass, particularly preferably 50 to 400 parts by mass.

<Hardening catalyst (G)>
The foamed refractory paint of the present invention can contain a curing catalyst (G) from the viewpoint of curability at normal temperature. Examples of the curing catalyst (G) include aluminum compounds, tin compounds, titanium compounds, iron compounds, manganese compounds, cobalt compounds, zirconium compounds, nickel compounds, bismuth compounds, copper compounds, zinc compounds, barium compounds and the like. These can be used alone or in combination of two or more.
As an aluminum compound, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide, aluminum tri- Aluminum alkoxides such as -tert-butoxide; tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, isopropoxybis (ethyl) Acetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, diisopropyl Xypropionylacetonatoaluminum, oleylacetoacetate aluminum diisopropiolate, acetylacetonato bis (propionylacetonato) aluminum, aluminum monoacetylacetonate bis (ethylacetoacetate), monoethylacetoacetate bis (acetylacetonato) aluminum Acetoalkoxyaluminum diisopropylate, acetylacetonatoaluminum di-sec-butylate, methylacetoacetate-sec-butylate, di (methylacetoacetate) aluminum mono-tert-butylate, diisopropoxyethylacetoacetate aluminum, mono Aluminum acetylacetonate such as acetylacetona bis (ethylacetoacetate) aluminum, aluminum chloride Include one or more of the like; um, aluminum perchlorate, aluminum salts such as aluminum phosphate.
Examples of tin compounds include dioctyltin dilaurate, dioctyltin dineodecanoate, dioctyltin bis (2-ethylhexyl maleate), dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin distearate, dioctyltin oxide or dibutyl tin oxide. Condensate of tin oxide and silicate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (2-ethylhexyl maleate) G) dibutyltin bis (oleyl maleate), stannous octoate, tin stearate, di-n-butyltin laurate oxide, dibutyltin bisisononyl 3-mercaptopropionate, dioctyltin bisisononyl-3- Mercaptopropione Octylbutyltinbisisononyl-3-mercaptopropionate, dibutyltin bisisooctylthioglucolate, dioctyltin bisisooctylthioglucolate, octylbutyltin bisisooctylthioglucolate, dioctyl One or more selected from tin acid, tin distearate and the like can be mentioned.
As the titanium compound, one or more of titanium alkoxides such as titanium isopropoxide and titanium butoxide, titanium acetylacetonate, titanium 2-ethylhexanate, titanium diisopropoxy bis (acetylacetonate) and the like Can be mentioned.
As an iron compound, 1 type (s) or 2 or more types in the acetate of iron (II) or (III), acetylacetonate, 2-ethyl hexanate etc. are mentioned.
As a manganese compound, 1 type (s) or 2 or more types in manganese (II) acetate, manganese (II) acetyl acetate, manganese (II) 2-ethylhexanate etc. are mentioned.
As the cobalt compound, one or more of cobalt (II) acetate, cobalt (II) acetyl acetate, cobalt (II) benzoylacetonate, cobalt (II) -2-ethylhexanate, cobalt naphthanate and the like Can be mentioned.
As a zirconium compound, 1 type (s) or 2 or more types in a zirconium (IV) propoxide, a zirconium (IV) acetate, a zirconium (IV) acetyl acetate, a zirconium (IV) 2-ethylhexanate etc. are mentioned.
Examples of nickel compounds include nickel (II) propoxide, nickel (II) stearate, nickel (II) acetate, nickel (II) acetyl acetate, nickel (II) 2-ethylhexanate, etc. There are more species.
As a bismuth compound, 1 type (s) or 2 or more types in bismuth (III) neodecanate, bismuth (III) acetate, bismuth (II) 2-ethylhexanate etc. are mentioned.
As a copper compound, 1 type (s) or 2 or more types in copper (II) acetyl acetate, copper (II) butyl phthalate, etc. are mentioned.
As a zinc compound, 1 type (s) or 2 or more types in zinc (II) acetate, zinc (II) acetyl acetate, zinc (II) 2-ethylhexanate etc. are mentioned.
As a barium compound, 1 type (s) or 2 or more types in barium (II) acetate, barium (II) acetyl acetate, barium (II) 2-ethylhexanate etc. are mentioned.

  The compounding amount of the curing catalyst (G) is preferably 0.01 to 50 parts by mass, particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the crosslinkable resin composition (A).

  Moreover, in the present invention, it is suitable from the viewpoint of room temperature curing that the curing catalyst (G) be used in combination with an aluminum compound and a tin compound. The use ratio of the aluminum compound and the tin compound in this case is in the range of 95/5 to 10/90, preferably 90/10 to 50/50, by mass ratio of aluminum compound / tin compound, more preferably aluminum compound. The ratio of the aluminum compound is higher than 50 in mass ratio of tin compound.

<Dispersing agent (H)>
In addition, the foamed refractory coating composition of the present invention can contain a dispersant. The mechanism of action is not clear, but the inclusion of the dispersant improves the coating workability of the paint, can reduce the time required for painting, and has the effect that the foamed layer after heat expansion exhibits sufficient fire resistance .

  As such a dispersing agent, if it is possible to stably disperse powder such as the above-mentioned pigment component and fiber in a liquid, nonionic dispersing agent, anionic dispersing agent, cationic dispersing agent, amphoteric dispersing agent, etc., paint field The known dispersants can be used, but the use of amphoteric dispersants is particularly suitable.

  The amphoteric dispersant is a dispersant containing both an anionic group and the cationic group, and examples thereof include dispersants having an acid value of 5 to 300 and an amine value of 5 to 300.

  Here, the amine value refers to the number of mg of KOH equivalent to HCl necessary to neutralize 1 g of dispersant non-volatiles. The acid value represents the number of mg of KOH necessary to neutralize 1 g of dispersant non-volatile matter.

  As a commercial item of the amphoteric dispersant, “Disperbyk-142” (amine number = 43, acid number = 46, manufactured by BYK Corporation), “Disperbyk-145” (amine number = 71, acid number = 76, BYK Chemie (BYK) product, "Disperbyk-2001" (amine value = 19, acid value = 29, BIC Chemie (BYK) company), "Disperbyk-2020" (amine value = 38, acid value = 35, BIC Chemie (BYK) ), "Disperbyk-9076" (amine number = 44, acid number = 38, BYK Chemie (BYK)), "Sorspurse 24000" (amine number = 42, acid number = 25, Lubrysol Co., Ltd.) And the like. These can be used alone or in combination of two or more.

  When using the said dispersing agent (H), As the compounding quantity, The viewpoint of coating workability and the intensity | strength of the foamed layer after expansion WHEREIN: Preferably based on 100 mass parts of crosslinkable resin compositions (A), it is preferably 0. It is in the range of 1 to 25 parts by mass, particularly preferably 0.3 to 15 parts by mass.

  In addition to the above, the foamable fire-resistant paint of the present invention can contain, if necessary, a paint additive such as a pigment other than an inorganic pigment, an organic solvent, a surface control agent, an antifoaming agent, and a flame retardant.

  Among these, as the flame retardant, for example, flame retardants known in the paint field such as boron flame retardants and inorganic flame retardants can be used without limitation.

  Examples of boron-based flame retardants include boric acid, zinc borate, sodium borate, and boron nitride. Examples of inorganic-based flame retardants include aluminum hydroxide, magnesium hydroxide, and magnesium carbonate. These flame retardants can be used alone or in combination of two or more.

  In the case of using the above flame retardant, the compounding amount thereof is preferably 0.1 to 100 parts by mass, particularly preferably 1 to 50 parts by mass, based on 100 parts by mass of the crosslinkable resin composition (A). It is.

As the paint form of the foamed refractory paint of the present invention, single-component paint or multi-component paint can be appropriately selected according to the type of the material as long as it is within the scope of the present invention.
The foamed refractory paint of the present invention can be used to provide a substrate or structure with fire resistance.
As the base material, not only metal such as steel frame, aluminum, zinc iron plate, etc. but also wallpaper, plywood, wood, inorganic board, concrete, mortar, FRP, plastics, paper, cloth, fiber, synthetic resin, rubber, silicon, electric wire It can also be used as a cable or the like. As structures, above-ground structures, marine structures and the like can be mentioned, and as particularly preferable structures, buildings and the like defined in Articles 21 and 27 of the Building Standard Act can be mentioned. Some of the specific examples include buildings, schools, hospitals, hotels, movie theaters, stores, warehouses, airports, and the like.

The foamed refractory paint of the present invention has good coating workability, and can reduce the time and labor required for coating until the desired film thickness is reached. Therefore, the protective coating can be easily formed by coating.
Moreover, such a protective coating film is excellent in curability at normal temperature. For this reason, the structure provided with the said protective coating film can maintain the aesthetics over a long period of time.
In addition, such a protective coating expands into a dense and strong foam layer by expanding under a fire condition. Therefore, the temperature rise of the structure base is suppressed, which helps to suppress the deformation and collapse of the structure at the time of fire. Furthermore, such a protective coating can protect a structure from the collapse by a flame.

<Coating method>
The present invention provides a method for fireproof coating of a structure, which comprises coating and drying the above-mentioned foamed refractory paint on the surface of a substrate to form a protective coating. The equipment and structures are as described above.

  In the case of applying to the steel frame of the existing structure, after subjecting to a surface treatment such as rust removal, if necessary, a primer coating may be applied and then the foamable fire resistant coating of the present invention may be applied.

  The coating method is not particularly limited, and can be easily applied by a general coating method such as brush, iron, roller, spray, etc., and it is possible to form not only smooth coating but also a thick and uneven pattern It is. These coating methods are suitably selected according to the use purpose of a base material.

  As drying conditions, although sufficient drying can be carried out by normal temperature drying, forced drying and heat drying may be performed as necessary.

  The dry average film thickness of the protective coating provided on the substrate surface is not particularly limited, but the range of 1 to 10 mm and 3 to 6 mm is preferable from the viewpoints of fire resistance and coating workability.

  In the present invention, the dry average film thickness of the protective coating film is obtained by calculating the non-volatile component in the coating amount and dividing by the coating area.

  The foamed refractory paint of the present invention can be applied once because it is excellent in drying property, but it may be applied in plural times if necessary.

The protective coating surface to be formed may be coated with various middle coats and top coats as required.
The present invention can also adopt the following configuration.
(1) A foamed refractory paint comprising a crosslinkable resin composition (A), a foaming agent (B) and a carbonizing agent (C),
A foamable fire-resistant paint, wherein the crosslinkable resin composition (A) contains a tertiary amino group-containing compound (A1), an epoxy group-containing compound (A2), and an organosilicate compound and / or a condensate thereof (A3).
(2) The foamed fire-resistant paint according to (1), wherein the tertiary amino group-containing compound (A1) is a tertiary amino group-containing acrylic resin.

(3) An amino group-containing compound wherein the tertiary amino group-containing compound (A1) comprises, as a copolymer component, an amino group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the polymerizable unsaturated monomer. An acrylic resin, wherein at least a part of one or both of the amino group-containing polymerizable unsaturated monomer and the other polymerizable unsaturated monomer copolymerizable with the polymerizable unsaturated monomer contains an acryloyl group (1) or The foamed refractory paint as described in (2).
(4) The monomer described in (2) or (3), wherein the proportion of the amino group-containing polymerizable unsaturated monomer in the monomer constituting the tertiary amino group-containing acrylic resin (A1) is 0.2 to 25% by mass. Foamed fireproof paint.

(5) The foamed refractory paint according to any one of (1) to (3), wherein the epoxy group-containing compound (A2) is a compound having an ether bond.
(6) The compound having an ether bond is polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyoxyethylene polyoxypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, or a combination thereof (5) Foamed fire-resistant paint as described in.
(7) The foamed fire-resistant paint according to any one of (1) to (6), wherein the compound (A3) is an organosilicate represented by the following formula and / or a condensate thereof.
(R ¹ O) ₄ Si
(Wherein R ¹ is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms)

(8) Based on 100 parts by mass of the crosslinkable resin composition (A),
The blend ratio of the tertiary amino group-containing compound (A1), the epoxy group-containing compound (A2), and the organosilicate compound (A3) is
30 to 98 parts by mass of tertiary amino group-containing compound (A1) 1 to 50 parts by mass of epoxy group-containing compound (A2) 1 to 50 parts by mass of organosilicate and / or its condensate (A3) And (1) to (7).
(9) The foamed refractory paint according to any one of (1) to (7), further comprising a plasticizer (D).
(10) The foamed refractory paint according to (9), wherein the plasticizer (D) contains a fatty acid ester plasticizer, a phosphoric acid ester plasticizer, or a combination thereof.

(11) The foamed refractory paint according to (9) or (10), wherein the content of the plasticizer (D) is 1 to 300 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A).
(12) The foamed refractory paint according to any one of (1) to (11), further comprising an organic viscosity modifier (E).
(13) The foamed refractory paint according to (12), wherein the organic viscosity modifier (E) contains an amide viscosity modifier.
(14) The content of the organic viscosity regulator (E) is, as the nonvolatile content, 0.1 to 50 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A) (12) or Foamed fire-resistant paint as described in (13).

(15) The foamed refractory paint according to any one of (1) to (14), further including at least one inorganic material (F) selected from a fiber, an inorganic viscosity modifier and an inorganic pigment.
(16) The inorganic material (F) contains a fiber, and the content thereof is in the range of 0.1 to 100 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A) (15) Foamed fire-resistant paint as described.
(17) The inorganic material (F) contains an inorganic viscosity modifier, and the content thereof is 0.01 to 70 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A). Foamed fire-resistant paint as described.
(18) The inorganic material (F) contains an inorganic coloring pigment, and the blending amount of the inorganic coloring pigment is 10 to 300 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A), described in (15) Foam fireproof paint.
(19) The inorganic material (F) contains an extender pigment, and the blending amount of the extender pigment is 0.1 to 100 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A), described in (15) Foam fireproof paint.

(20) The foamed fireproof as described in any one of (15) to (19), wherein the content of the inorganic material (F) is 1 to 500 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A) paint.
(21) The foamable fire-resistant paint according to any one of (1) to (20), further including a curing catalyst (G).
(22) The curing catalyst (G) is one or more of an aluminum compound, a tin compound, a titanium compound, an iron compound, a manganese compound, a cobalt compound, a zirconium compound, a nickel compound, a bismuth compound, a copper compound, a zinc compound and a barium compound The foamed refractory paint according to (21), which is two or more kinds.
(23) The amount of the curing catalyst (G) blended is 0.01 to 50 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A), (21) or (22) .

(24) The foamable fire-resistant paint according to any one of (1) to (23), further comprising a dispersant (H).
(25) The foamed refractory paint according to (24), wherein the dispersant (H) is an amphoteric dispersant.
(26) The foamed refractory paint according to (24) or (25), wherein the compounding amount of the dispersing agent (H) is 0.1 to 25 parts by mass based on 100 parts by mass of the crosslinkable resin composition (A).
(27) A coating method in which the foamed refractory paint according to any one of (1) to (26) is applied and dried on a substrate surface.

(28) A fireproof coating method for a structure, comprising coating and drying the foamed refractory paint according to any one of (1) to (26) on a substrate surface to form a protective coating film.
(29) The base material is not only metal such as steel frame, aluminum, zinc iron plate, etc. but also wallpaper, plywood, wood, mineral board, concrete, mortar, FRP, plastics, paper, cloth, fiber, synthetic resin, rubber, silicon, Or the method according to (27) or (28), which is a wire cable.
The fireproof structure provided with the protective coating film using the foaming refractory paint as described in any one of (30) (1)-(26).
(31) The fireproof structure according to (30), wherein the structure is a building, a school, a hospital, a hotel, a cinema, a store, a warehouse, an airport.

  Hereinafter, the present invention will be further described by way of examples. Here, "part" and "%" mean "mass part" and "mass%", respectively.

<Production of foamed fireproof paint>
Examples 1 to 6 and Comparative Examples 1 to 3
Each component was mix | blended so that it might become a composition shown to the following table, it stirred and mixed until it became uniform using a planetary mixer, and foaming fireproof coating composition (X-1)-(X-9) was manufactured. The numerical values in the table are displays of non-volatile components.

(Note 1) Acrylic resin (A1-1): isobutyl methacrylate / n-butyl methacrylate / n-butyl acrylate / N, N-dimethylaminoethyl methacrylate / hydroxyethyl acrylate (mass ratio) = 45/13/29/10 / 3 copolymer, amine equivalent 3100, weight average molecular weight 35000,
(Note 2) Acrylic resin (A4): isobutyl methacrylate / n-butyl methacrylate / n-butyl acrylate / hydroxyethyl acrylate (mass ratio) = 45/23/29/3 copolymer, weight average molecular weight 35,000,
(Note 3) Alkyl silicate: Low condensation product of tetramethoxysilane, average number of Si: 4, number average molecular weight 470,
(Note 4) Leofos 65: trade name, manufactured by Ajinomoto Fine Chemicals, triaryl isopropylated phosphate,
(Note 5) Disperon NS5025: trade name, active ingredient 25%, Kushimoto Chemical Co., Ltd., oxidized polyolefin-modified fatty acid polyamide,
(Note 6) Mineral fiber: Average fiber length 500 μm,
(Note 7) Carbon fiber: Average fiber length 6 mm,
(Note 8) “Prenact ALM”: trade name, manufactured by Ajinomoto Fine Techno Co., alkylacetoacetate aluminum diisopropylate,
(Note 9) DISPER-BYK 145: trade name, manufactured by BYK, amphoteric dispersant, amine value = 71, acid value = 76.

<Evaluation test>
(1) The foamed fire-resistant paint is applied to the entire surface of the sag resistant steel material so as to have a dry film thickness of 4 mm, and it is stood vertically for 1 hour under conditions of 23 ° C. and 50% RH. The presence or absence was evaluated based on the following criteria.
A: There is no evidence of dripping,
B: The sauce is very slight,
C: Slightly noticeable drip,
D: Sagging is noticeable.

(2) Each foamed fire-resistant paint was coated on the entire surface of a hardenable steel material so that the dry film thickness would be 4 mm, left at 23 ° C and 50% RH for 1 hour, and the coated film surface was touched with a finger Occasionally, the tackiness was evaluated according to the following criteria.
A: There is no feeling of stickiness,
B: There is a slight stickiness, but the coating leaves the hand immediately,
C: There is a feeling of stickiness clearly
D: The coating is broken.

(3) Time to reach 500 ° C. Each test body prepared in the above evaluation of curability is 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 ISO 834 by flame, It was formed and subjected to a fire resistance test. The values in the table are the time until the sample temperature reaches 500 ° C. In the table, the larger the value, the better, and "-" means that the test sample can not be measured because it was melted by heat during the test, and it means that it is defective.

(4) State of Foamed Layer The test body on which the foamed layer after the fire resistance test was formed was cut at the center, and the surface and cross section of the foamed layer were visually observed and visually evaluated according to the following criteria. In the table, "-" means that it can not be evaluated and is defective.
A: A dense and uniform foam layer was formed,
B: Very slight nonuniform parts and cavities are observed,
C: Defects that do not reach steel products are recognized
D: Dropping of the foam layer and defects reaching the steel material are observed.

Claims (12)

A foamed refractory paint comprising a crosslinkable resin composition (A), a foaming agent (B) and a carbonizing agent (C),
A foamable fire-resistant paint, wherein the crosslinkable resin composition (A) contains a tertiary amino group-containing compound (A1), an epoxy group-containing compound (A2), and an organosilicate compound and / or a condensate thereof (A3).   The foamed refractory paint according to claim 1, wherein the tertiary amino group-containing compound (A1) is a tertiary amino group-containing acrylic resin.   The foamed refractory paint according to claim 1 or 2, wherein the epoxy group-containing compound (A2) is a compound having an ether bond. Based on 100 parts by mass of the crosslinkable resin composition (A),
The blend ratio of the tertiary amino group-containing compound (A1), the epoxy group-containing compound (A2), and the organosilicate compound (A3) is
30 to 98 parts by mass of tertiary amino group-containing compound (A1) 1 to 50 parts by mass of epoxy group-containing compound (A2) 1 to 50 parts by mass of organosilicate and / or its condensate (A3) The foamed refractory paint according to any one of claims 1 to 3.   The foamed refractory paint according to any one of claims 1 to 4, further comprising a plasticizer (D).   The foamed fire-resistant paint according to any one of claims 1 to 5, further comprising an organic viscosity modifier (E).   The foamed fire-resistant paint according to any one of claims 1 to 6, further comprising at least one inorganic material (F) selected from fibers, inorganic viscosity modifiers and inorganic pigments.   The foamed refractory paint according to any one of claims 1 to 7, further comprising a curing catalyst (G).   The foamed refractory paint according to any one of claims 1 to 8, further comprising a dispersant (H).   A coating method of coating and drying the foamed refractory paint according to any one of claims 1 to 9 on a substrate surface.   The fireproofing coating method of a structure which applies and dries the foaming refractory paint of any one of Claims 1-9 on a base-material surface, and forms a protective coating film.   The fireproof structure provided with the protective coating using the foaming refractory paint of any one of Claims 1-9.