JP2018159065A - Process saving foaming fireproof coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process saving foaming fireproof coating material that has less time and labor required for the application until a coating attains a desired film thickness, does not impair the appearance of a structure at ordinary times and is suitable for suppressing the collapse and deformation of the structure in the case of fire.SOLUTION: The process saving foaming fireproof coating material includes (A) a binder component including (a1) a crosslinkable polymer and (a2) a plasticizer, (B) a foaming agent and (C) a carbonizing agent in which the masses of the component (A), the component (B) and the component (C) satisfy the relationship represented by formula (1) (omitted); and the ratio of the plasticizer (a2) to a nonvolatile content of the binder component (A) is 50 mass% or less, and is used for applying at a nonvolatile component concentration of the coating material of 75% or more. An application method, a fireproof coating method and a fireproof structure with a protective coating film using the foaming fireproof coating material are provided.SELECTED DRAWING: None

Description

  The present invention relates to a foam refractory paint that foams and expands in the event of a fire to form a thermal barrier and protect the building from collapse.

  Non-combustible building materials are used as the steel material that constitutes the framework of a building, but the strength is significantly reduced under intense heating conditions in the event of a fire, leading to the collapse of the entire building. For this reason, it is protected by spraying a fire-resistant coating material that is made into a paste form by mixing aggregate such as rock wool with cement-based inorganic binder and kneading with water, and prevents a sudden drop in strength. It is widely done.

  However, this rock wool fireproof covering material requires a thickness of 25 mm or more to the steel frame. For this reason, the rockwool fireproof coating material is not only limited in terms of construction method, but also has an uneven coating surface, and is not suitable for a site that requires an aesthetic appearance utilizing the form of the steel frame itself.

  Therefore, various fire-resistant fire-resistant paints in which an organic binder is mixed with a foaming agent, a carbon generating material, and the like have been proposed as fire-resistant coating materials suitable for parts requiring aesthetic appearance.

  The coating film formed using foamed fire-resistant paint protects the steel surface from external stimuli such as water as a protective coating film under normal conditions (when there is no fire), and decomposes due to high heat and generates noncombustible gas during a fire. To form a foamed layer. It is considered that this porous foam layer becomes a heat insulating layer, and the temperature rise of the steel frame is suppressed.

  As a foam fire-resistant paint, the present applicant in Patent Document 1 uses a bromine-containing phosphate ester and / or a condensate thereof as a flame retardant in a composition containing a resin, a foaming agent, a carbon supply agent, and an inorganic powder. Proposed foam fireproof paint. According to such a coating material, when the coating film is foamed by high heat, the carbonized layer can be well retained in the foamed layer, and the heat insulation can be maintained.

  However, the fire-resistant foam 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 under normal temperature drying conditions is not sufficient.

  By the way, in order for the foamed layer formed by the heat at the time of a fire to reach the level which suppresses the temperature rise of a steel frame, it is necessary to make the film thickness of the protective coating film by the foam fireproof paint applied to a steel frame thick. For this reason, in the paint having poor curability as described in Patent Document 1, the same paint must be repeatedly applied in multiple times, and repeated for each application, and repeated coating must be performed. In some cases, it takes about 2 weeks, for example, and improvement is required.

  On the other hand, various foam-type refractory paints using a cross-linked resin as a coating film forming component have been 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 this document, the epoxy / amine cross-linked coating film protects the structure under normal conditions, and in the event of a fire, a hard foam layer is obtained by the polysiloxane chain contained in the composition. Even in a severe rank fire called, the temperature rise of the structure can be suppressed by the heat insulation by the foam layer.

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

  However, the compositions described in Patent Documents 2 and 3 have a problem that they are easily cracked because the foamed layer is hard. Since the compositions described in these patent documents are intended for use in oil, gas, and chemical plant facilities where jet fire is assumed, the purpose is to improve the thermal insulation of the foam layer rather than the normal appearance. Therefore, painting workability is not sufficient.

  Patent Document 4 discloses a composition containing a silane-terminated polyether or a silane-terminated polyurethane in combination with a plasticizer as an expandable coating that can be cured in a short time and has good fire resistance. However, although the composition described in Patent Document 4 can provide a foam layer having excellent fire resistance in the event of a fire, when a coating film is provided on the edge portion of a steel frame, the foam on the edge portion is formed depending on the shape of the steel material. Cracks may occur in the layer and peel off.

  In this way, it is necessary to develop a foam fire-resistant paint that can easily form a protective coating film that does not impair the form of the structure in normal times, and can provide a dense and strong foam layer on the edge as well as the flat surface during heating expansion. It is said that.

Japanese Patent Laid-Open No. 10-7947 International Publication No. 2010-054984 Pamphlet International Publication No. 2014-0199947 Pamphlet International Publication No. 2010-131037 Pamphlet

  The purpose of the present invention is to reduce the time and labor required for coating until reaching a desired film thickness, without impairing the aesthetics of the structure during normal times, and saving processes suitable for suppressing the collapse / deformation of the structure during a fire. It is to provide a mold-foam fireproof paint.

  As a result of intensive studies on the above-mentioned problems, the present inventors have found that the ratio of the plasticizer in the binder component and the total mass of the foaming agent and the carbonizing agent are high only when they are in a specific range with respect to the binder component. It has been found that a thick film can be applied even at a non-volatile concentration, and a protective coating film can be easily formed that changes to a high-strength foam layer that can protect the structure from a flame in the event of a fire.

That is, the present invention
A binder component (A) comprising a crosslinkable polymer (a1) and a plasticizer (a2), a foaming agent (B) and a carbonizing agent (C);
The mass of the component (A), the component (B), and the component (C) is expressed by the following formula (1).

(In formula (1), A _(M) , B _(M) , and C _(M) are the masses of component (A), component (B), and component (C), respectively.
The relationship represented by
The proportion of the plasticizer (a2) in the binder component (A) non-volatile content is 50% by mass or less.
A process-saving foam fireproof paint for application with a non-volatile content of paint of 75% or more,
Coating and drying the foam refractory paint,
A fireproof coating method for a structure, in which the foamed fireproof paint is applied and dried to form a protective coating, and
A fireproof structure provided with a protective coating using the foamed fireproof paint,
About.

  According to the foam fire-resistant paint of the present invention, a thick coating film can be easily obtained without repeating many coating operations, so that a desired thick film protective coating can be obtained without spending a great deal of labor and time. Can be formed.

  Such a protective coating film is excellent in quick drying property and internal curability even under normal temperature drying conditions, and is excellent in various physical properties such as water resistance. For this reason, the structure provided with the said protective coating film can maintain aesthetics over a long period of time.

  Moreover, the protective coating film formed with the foamed fire-resistant paint of the present invention expands under a fire situation and changes to a foamed layer, which is useful for suppressing deformation and collapse of the structure during a fire. In addition, even when a protective coating is provided on the edges and protrusions as well as the flat surface of the building material that constitutes the structure, there is an advantage that cracking or peeling of the foam layer hardly occurs in the process of expansion due to heating. is there.

  The process-saving foam fire-resistant paint of the present invention is a composition containing a binder component (A), a foaming agent (B), and a carbonizing agent (C).

<Binder component (A)>
In the present specification, the binder component (A) is an organic component that can be a coating film forming component of the inventive process-type foam fire-resistant paint, and contains the crosslinkable polymer (a1) and the plasticizer (a2) as essential components. And an amphoteric dispersant (a3), an organic viscosity modifier (a4), a polyether compound (a5) having a hydroxyl group, and / or other components optionally.

<Crosslinkable polymer (a1)>
In the present invention, the crosslinkable polymer (a1) is a resin that self-crosslinks with heat, catalyst, air (oxygen), moisture (water), electron beam, etc., or a reaction with a crosslinking agent and / or other crosslinkable resin. A resin that crosslinks. When the binder component (A) includes the crosslinkable polymer (a1) as a part of the component, the curability of the coating film formed from the paint of the present invention is improved, which contributes to process saving. .

  Examples of such crosslinkable resins include, for example, hydroxyl groups, carboxyl groups, acid anhydride groups, amino groups, imino groups, isocyanate groups, methylol groups, hydrolyzable silyl groups, aldehyde groups, mercapto groups, epoxy groups, Acrylic resin, fluorine resin, polyamide resin, acrylic urethane resin, polyester resin, alkyd resin, phenol resin, melamine resin, silicone resin, urethane resin, epoxy resin having at least one crosslinkable reactive group selected from unsaturated groups , Polyoxyalkylene resins, amino resins, urea resins, and the like; two or more modified resins; a mixture of two or more; and the like.

  The weight average molecular weight of the crosslinkable polymer (a1) is preferably 500 to 100,000, more preferably 1,000 to 70,000, from the viewpoints of curability at normal temperature and thermal expansion.

  In the present invention, the crosslinkable polymer (a1) is contained in the nonvolatile component of the binder component (A) in an amount of 20 to 85% by mass, preferably 30 to 75% by mass.

  In this specification, the non-volatile content means a residue excluding volatile components, and the residue may be solid or liquid at room temperature. The non-volatile content concentration (%) is a percentage of the amount of the remaining substance after drying with respect to the mass before drying. Examples of the drying condition of the sample when measuring the non-volatile mass include a method of heating 1 gram of the sample at 110 ° C. for 1 hour.

  In this specification, the weight average molecular weight of the crosslinkable polymer (a1) is a value obtained by converting the weight average molecular weight measured by GPC (gel permeation chromatography) method into polystyrene.

  In the present invention, from the viewpoint of curability and heat expandability, use of a polymer having a hydrolyzable silyl group represented by the following general formula (1) in the molecule, preferably at the molecular end, as the crosslinkable polymer (a1). Is suitable.

-SiR ¹ _3-a (R ² ) _a Formula (1)
(Wherein R ¹ is the same or different and represents a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrolyzable group, and a represents 1, 2 or 3).

Examples of the hydrocarbon group represented by R ¹ include chain hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group octyl group, nonyl group, decyl group and icosyl group ( These chain hydrocarbon groups may be linear or branched. The same shall apply hereinafter; and examples thereof include aromatic hydrocarbon groups such as phenyl groups, such as methyl groups, ethyl groups, propyl groups, butyl groups, and phenyl groups. Are more preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are particularly preferable. Examples of the hydrolyzable group represented by R ² include an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group; a phenoxy group and a 2- (butoxy) ethyl group, and an alkoxy group is preferred. A methoxy group or an ethoxy group is more preferable.

  In the formula (1), the main chain is bonded to the silicon atom via a bonding functional group described later. Examples of the skeleton constituting the main chain include polyoxyalkylene, vinyl polymers (for example, polyacrylates, polymethacrylates, etc.), saturated hydrocarbon polymers, unsaturated hydrocarbon polymers, polyesters, polycarbonates, polydimethylsiloxanes, and the like. One or more types of skeletons selected from Such a skeleton may be included alone in the main chain of the crosslinkable polymer (a1), or two or more thereof may be included.

  In the present invention, the main chain of the crosslinkable polymer (a1) preferably has a polyoxyalkylene skeleton from the viewpoint of the heat expansion property of the cured coating film formed from the paint of the present invention.

  Examples of polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Is particularly preferred.

  In the case where the crosslinkable polymer (a1) is a polymer having a hydrolyzable silyl group represented by the above formula (1), the bonding functional group via the hydrolyzable silyl group and the main chain is a main chain. It is generated by a chemical reaction when a hydrolyzable silyl group is introduced into the structure, and is a chemical structure portion other than the main chain and the hydrolyzable silyl group. Specific examples of the bonding functional group include, for example, alkylene groups such as methylene group, ethylene group and propylene group, phenylene group, urethane bond, urea bond, substituted urea bond, carbonate group and the like, and a plurality of these and other chemical structures A divalent chemical bond containing

  The crosslinkable polymer (a1) may be produced by a conventional method, or a commercially available product may be used.

  Examples of commercially available products when the crosslinkable polymer (a1) is a polymer represented by the general formula (1) include “Excester ES-S2410”, “Excester ES-S2420”, and “Excester ES-S3430”. , “Exstar ES-S3630” (trade name, manufactured by Asahi Glass Co., Ltd.), “S-203”, “S-303”, “EST-250”, “EST-280”, “SAT-200”, “SAT-” 350 "," SAT-400 "," SAX-520 "," SAX-580 "," SAT-720 "," SAT-145 "," SAT-770 "and" HS-2 " Kaneka), “DESMOSEAL S XP2458”, “DESMOSEAL S XP2836” and “DESMOSEAL S XP2749” "LTP", "STP-E10" (trade name, manufactured by Wacker), "SPUR + prepolymer 1015LM" and "SPUR + prepolymer 1050MM" (above, trade name, manufactured by Momentive), etc. Or in combination of two or more.

<Plasticizer (a2)>
In the present invention, the binder component (A) contains the crosslinkable polymer (a1) in combination with the plasticizer (a2). By including the plasticizer (a2) in the binder component (A), not only the strength of the foamed layer generated upon heating is maintained, but also the coating application workability is improved, and the foam fire-resistant paint coating process is saved. Useful.

  As the plasticizer (a2), known ones added for the purpose of enhancing the flexibility of the coating film in the paint field can be used without limitation. 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, 1,2,3,6-tetrahydrophthalic acid bis (2-ethylhexyl), dimethyl Adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, dioctyl adipate, dibutyl diglycol adipate, diisononyl cyclohexane dicarboxyl Fatty acid ester plasticizers such as cyclohexane dicarboxylates such as dimethylcyclohexane dicarboxylate, diethylcyclohexane dicarboxylate, and di-2-ethylhexylcyclohexane dicarboxylate; 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, hydro Ciphenyldiphenyl phosphate, resorcinol bisdiphenyl phosphate, triaryl isopropylated phosphate, compounds obtained by modifying these with various substituents, phosphate ester plasticizers such as these various condensation types, and the like. Or in combination of two or more.

  In the present invention, the content of the plasticizer (a2) is 50% by mass or less in the binder component (A) non-volatile matter from the viewpoint of crack resistance of the foam layer on the edge portion of the substrate. 10 to 45% of the range is preferable, and 20 to 40% of the range is more preferable.

  In particular, as the plasticizer (a2), a phosphate plasticizer, particularly an aromatic phosphate plasticizer having an aryl group as an organic group, is excellent in compatibility with the crosslinkable polymer (a1) and is uniformly cured. A film can be formed and a uniform foamed layer can be formed during heating, which is suitable.

  In the present invention, only the phosphoric ester plasticizer may be used as the plasticizer (a2), and the mass proportion of the phosphoric ester plasticizer is 50% by mass or more in the plasticizer (a2). Within the range is appropriate.

  On the other hand, from the viewpoint of crack resistance of the foam layer on the substrate edge portion, the plasticizer (a2) does not contain a fatty acid ester plasticizer or a fatty acid ester plasticizer occupies the plasticizer (a2). It is suitable that the ratio is within a range of 50% by mass or less.

<Amphoteric dispersant (a3)>
Further, the binder component (A) can contain a dispersant. As a dispersant, if it can stably disperse pigments, fibers and the like, which will be described later, in a liquid, nonionic dispersants, anionic dispersants, cationic dispersants, amphoteric dispersants, etc., known in the paint field Although a dispersing agent can be used, use of an amphoteric dispersing agent (a3) is suitable among them. Although the mechanism of action is not clear, by using the amphoteric dispersant (a3) as a dispersant, the coating application workability can be improved, the time required for coating can be reduced, and the foamed layer after heat expansion has sufficient fire resistance. Has the effect of exerting sex.

  The amphoteric dispersant (a3) is a dispersant containing both an anionic skeleton and a cationic skeleton. For example, the acid value is 5 to 300, preferably 20 to 200, and the amine value is 5 to 300, preferably 20 to. 200 dispersants can be mentioned.

  Here, the amine value represents the number of mg of KOH equivalent to HCl necessary for neutralizing 1 g of the nonvolatile content of the dispersant. The acid value represents the number of mg of KOH necessary for neutralizing 1 g of the nonvolatile content of the dispersant.

  Commercially available amphoteric dispersants (a3) include “Disperbyk-142” (amine value = 43, acid value = 46, manufactured by BYK (BYK)), “Disperbyk-145” (amine value = 71, acid value = 76, manufactured by Big Chemie (BYK)), “Disperbyk-2001” (amine value = 19, acid value = 29, manufactured by BYK Chemy (BYK)), “Disperbyk-2020” (amine value = 38, acid value = 35, Big Chemie (BYK)), “Disperbyk-9076” (amine value = 44, acid value = 38, Big Chemie (BYK) company), “Solsperse 24000” (amine value = 42, acid value = 25, Lubrizol ( For example).

  In the present invention, the amphoteric dispersant (a3) can be used alone or in admixture of two or more.

  When the amphoteric dispersant (a3) is used, the blending amount is 0.1 to 12% in the binder component (A) non-volatile content from the viewpoint of coating workability and the strength of the expanded foam layer after expansion, The range of 0.3 to 8% is particularly suitable.

<Organic viscosity modifier (a4)>
In the present invention, the binder component (A) suitably includes an organic viscosity modifier (a4). As the organic viscosity modifier (a4), known ones used in the paint field can be used without limitation, and specific examples thereof include, for example, an acrylic viscosity modifier, a polyethylene viscosity modifier, and an amide viscosity. Examples include regulators, polyether-based viscosity modifiers such as polyether and urethane-modified products thereof, and cellulose-based viscosity modifiers such as hydroxyethylcellulose, methylcellulose and modified products thereof, and these are used alone or in combination of two or more. can do. In particular, the amide viscosity modifier is suitable as the organic viscosity modifier (a4) because it can be applied in a short time while having a high non-volatile content, and the appearance after application is excellent.

  The amide-based viscosity modifier is a compound having a —NH—CO— bond in the molecule. 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. The thing which uses a mixture as an active ingredient is mentioned.

  Specific examples 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, methylol stearic acid Methylol amide such as amide, methylene bis stearic acid amide, ethylene bis lauric acid amide, saturated fatty acid bis amide such as ethylene bishydroxy stearic acid amide, unsaturated fatty acid bis amide such as methylene bis oleic acid amide, m-xylylene bis stearic acid amide Aromatic bisamide, fatty acid amide ethylene oxide adduct, fatty acid ester amide, fatty acid ethanol amide, N-butyl-N′-stearyl It can be exemplified substituted ureas such as iodine, etc., which can be used alone or in combination.

  As amide type viscosity modifiers available as commercial products, “DISPARLON 6900-20X”, “DISPARLON 6900-10X”, “DISPARLON A603-20X”, “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", "DISPARL PFA-231", F-9020 "," DISPARLON F-9030 "," DISPARLON F-9040 "," DISPA “LON F-9050”, “DISPARLON NS-5010”, “DISPALON NS5025”, “DISPARLON NS-5210”, “DISPARLON NS-5310” (above, trade name, manufactured by Enomoto Kasei Co., Ltd.), “Tarren 7200-20”, Talen series (trade name, Kyoei Chemical Co., Ltd.) such as “Tarene 7500-20”, “BYK-405” (trade name, BYK Chemie), “AS-AT-75F” (trade name, Ito) Oil refinery).

  When the foamed fireproof paint of the present invention contains the organic viscosity modifier (a4), the nonvolatile content is 0.05 to 5% by mass, particularly 0.1% in the binder component (A) nonvolatile content. The range of ˜3 mass% is appropriate.

<Polyether compound having a hydroxyl group (a5)>
In the present invention, the binder component (A) preferably contains a blend polymer in addition to the crosslinkable polymer (a1) from the viewpoint of thermal expansion of the composition of the present invention. The blend polymer in the present invention is a polymer other than the crosslinkable polymer (a1), and the resin type is not particularly limited. For example, acrylic resin, fluororesin, polyamide resin, acrylic urethane resin, polyester resin, alkyd resin, phenol Resins such as resins, melamine resins, silicone resins, urethane resins, epoxy resins, polyether resins, amino resins, urea resins; two or more modified resins; a mixture of two or more; Can do.

  In the present invention, the compatibility with the polymer (a1) is good, and the binder component (A) is a polyether compound having a hydroxyl group as a blend polymer from the viewpoints of coating film appearance in normal times and foamed layer uniformity. It is suitable to contain a5).

  The polyether compound (a5) having a hydroxyl group is a compound having at least one hydroxyl group at the molecular chain end or branched chain end of the polyether compound. Specifically, polyoxyethylene polyol, polyoxypropylene polyol Aliphatic polyether compounds such as polyoxyethylene / oxypropylene polyol, polyoxytetramethylene glycol; bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, resorcin ethylene oxide or propylene oxide adduct Group ring-containing polyether compounds; and the like, and may be used alone or in combination of two or more. Among these, a compound having a polyoxypropylene structure in the molecule is preferable, and polyoxypropylene polyol is more preferable.

  The number average molecular weight of the polyether compound (a5) having a hydroxyl group is preferably in the range of 500 to 10,000, and more preferably in the range of 2,000 to 6,000.

  When the foamed fireproof paint of the present invention contains a polyether compound (a5) having a hydroxyl group, the nonvolatile content thereof is 1 to 50% by mass, particularly 5 to 40% by mass in the binder component (A) nonvolatile content. % Is suitable.

  In addition to the components (a1), (a2), (a3) and (a4) described above, the binder component (A) is a coating film of an organic flame retardant, a crosslinking agent, a surfactant, a wetting agent, etc. Components that can be forming components can be included as needed.

  Among these, examples of the crosslinking agent include compounds having at least two functional groups capable of reacting with the crosslinking reactive group contained in the crosslinkable polymer (a1). Specific examples of the functional group include hydroxyl group, carboxyl group, acid anhydride group, epoxy group, amino group, imino group, isocyanate group, alkoxysilyl group, methylol group, aldehyde group, mercapto group, epoxy group, unsaturated group. Etc.

<Foaming agent (B)>
In the process-saving foam fire-resistant paint of the present invention, the foaming agent (B) is considered to be a component that causes the gas generated when the cured coating film is exposed to a flame to change the cured coating film into a foamed layer. It is done.

  As such a foaming agent (B), those known in the field of foam fire-resistant paint can be used without limitation, and specific examples thereof include, for example, ammonium polyphosphate (APP), monoammonium phosphate, phosphorus Diammonium acid, potassium phosphate (for example, potassium tripolyphosphate), sodium phosphate, para-toluenesulfonic acid, sodium sulfate, potassium sulfate and sodium sulfate, such as potassium sulfate and sodium sulfate; Melamine formaldehyde, methylolated melamine, hexamethoxymethyl melamine, melamine monophosphate, dimelamine phosphate, melamine biphosphate, melamine polyphosphate, melamine pyrophosphate, dimelamine phosphate and melamine cyanurate Melamine foaming agents such as hexamethoxymethylmelamine; urea foaming agents such as urea, dimethylurea, butylated urea, alkylated urea, benzoguanine, glycoluril type compounds, tris (alkoxycarbonylamino) triazine type compounds, and guanylurea Glycine or amine phosphate (for example, ammonium polyphosphate), azodicarbonamide, 4,4 oxybis (benzenesulfonyl hydrazide), p-toluene hydrazide, p-toluenesulfonyl semicarbazide, dinitrosopentamethylenetetramine, 5-phenyl Examples include tetrazole, diazoaminobenzene; expansive graphite, sulfamic acid and tungstanate salts, tris- (2-hydroxyethyl) isocyanurate, and the like. These may be used alone or in combination of two or more. It can be used in conjunction look.

  The blending amount of the foaming agent (B) is suitably in the range of 25 to 385 parts by mass, particularly 35 to 325 parts by mass, based on 100 parts by mass of the binder component (A) non-volatile content.

<Carbide (C)>
In the process-saving foam fireproof paint of the present invention, as the carbonizing agent (C), when the cured coating film is exposed to a flame and changed into a foamed layer, it reacts with a phosphoric acid component to form a carbonized layer, It is believed to enhance the thermal insulation of the layer and is a component used. Examples of the carbonizing agent (C) include pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, cellulose powder, hydrocarbon resin, chloroparaffin, and the like. These may be used alone or in combination of two or more. Can do.

  The amount of the carbonizing agent (C) is suitably in the range of 25 to 85 parts by mass, particularly 35 to 75 parts by mass, based on 100 parts by mass of the binder component (A) non-volatile content.

<Curing catalyst (D)>
The fire retardant paint of the present invention may contain a curing catalyst (E) capable of catalyzing a crosslinking reaction between the crosslinkable polymers (a1) or between the crosslinkable polymer (a1) and a crosslinking agent blended as necessary. it can.

  Examples of the curing catalyst (D) include radical catalysts such as peroxides and azo compounds, acid catalysts, basic catalysts, and organometallic catalysts.

Among these, as the organometallic catalyst, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec. Aluminum alkoxides such as butoxide and aluminum tri-tert-butoxide; tris (ethyl acetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, Isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, di Sopropoxypropionyl acetonato aluminum, oleyl acetoacetate aluminum diisopropylate, acetyl acetonato bis (propionyl acetonato) aluminum, aluminum monoacetyl acetonate bis (ethyl acetoacetate), monoethyl acetoacetate bis (acetyl acetonato) Aluminum, acetylacetonato aluminum di-sec-butyrate, methyl acetoacetate-sec-butyrate, di (methyl acetoacetate) aluminum mono-tert-butyrate, diisopropoxyethyl acetoacetate aluminum, monoacetylacetona bis ( Ethyl acetoacetate) aluminum acetylacetonate such as aluminum, aluminum chloride, aluminum perchlorate, aluminum phosphate Aluminum salts such as aluminum; Aluminum-based catalysts such as dioctyltin dilaurate, dioctyltin dineodecanoate, dioctyltin bis (2-ethylhexyl maleate), dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin distearate , Dioctyltin oxide or condensate of dibutyltin oxide and silicate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyl Tin bis (2-ethylhexyl maleate), dibutyl tin bis (oleyl maleate), stannous octoate, tin stearate, di-n-butyl tin laurate oxide, dibutyl tin bisisononyl-3-mercaptopropionate Dioctyl tin bisiso Nonyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, dibutyltin bisisooctylthiogluconate, dioctyltin bisisooctylthiogluconate, octylbutyltin bisiso Tin catalysts such as octylthiogluconate, tin dioctylate and tin distearate; titanium alkoxides such as titanium isopropoxide and titanium butoxide, titanium acetylacetonate, titanium-2-ethylhexanate, titanium diisopropoxybis ( Organic titanium compounds such as acetylacetonate); organic iron compounds such as iron (II) or (III) acetate, acetylacetonate, 2-ethylhexanate; manganese (II) acetate, manganese (II) acetylacetate, manganese (II) -2-Ethylhe Organic manganese compounds such as sanates; organic cobalt compounds such as cobalt (II) acetate, cobalt (II) acetyl acetate, cobalt (II) benzoylacetonate, cobalt (II) -2-ethylhexanate, cobalt naphthanate; zirconium ( IV) Organic zirconium compounds such as propoxide, zirconium (IV) acetate, zirconium (IV) acetyl acetate, zirconium (IV) -2-ethylhexanate; nickel (II) propoxide, nickel (II) stearate, nickel ( II) Organic nickel compounds such as acetate, nickel (II) acetyl acetate, nickel (II) -2-ethyl hexanate; bismuth (III) neodecanate, bismuth (III) acetate, bismuth (II) -2-ethyl hexanate, etc. The organic Organic compounds such as copper (II) acetyl acetate and copper (II) butyl phthalate; organic zinc compounds such as zinc (II) acetate, zinc (II) acetyl acetate and zinc (II) -2-ethylhexanate Organic barium compounds such as barium (II) acetate, barium (II) acetyl acetate, barium (II) -2-ethylhexanate and the like can be used, and these can be used alone or in combination of two or more thereof.
Further, when the curability of the paint of the present invention, particularly the deep curability, is insufficient, water may be further added to the compound (D).

  The amount of the curing catalyst (D) is suitably within the range of 0.01 to 5 parts by mass, particularly 0.03 to 3 parts by mass, based on 100 parts by mass of the non-volatile content of the binder component (A).

<Inorganic material (E)>
The fire-resistant foam paint of the present invention contains at least one inorganic material (E) selected from fibers, inorganic viscosity modifiers, and inorganic pigments from the viewpoint of crack resistance of the foam layer on the substrate edge. Is preferred. Examples of the fibers include metals such as copper or copper alloys, aluminum, iron, zinc, tin, titanium, nickel, magnesium, silicon, or the like, or fibers in the form of alloys or 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, wollastonite and other inorganic fibers; aramid fibers, cellulose fibers, acrylic fibers, polyester fibers, nylon fibers, phenolic resins Organic fibers such as fibers; carbon fibers such as flame-resistant fibers, pitch-based carbon fibers, PAN-based carbon fibers, activated carbon fibers; these two or more types of modified products can be used, and these can be used alone or in combination of two or more types Can be used in combination.

As the mineral fiber, those containing SiO ₂ , Al ₂ O ₃ , CaO, MgO, FeO, Na ₂ O, or the like, or those containing one or more of these compounds can be used. Of these, those containing Al element are suitable. As a commercial item of a mineral fiber, for example, LAPINUS FIBERS B. For example, V Roxul series.

  When mineral fibers are used as the fibers, the average fiber length is suitably 0.1 to 4 mm, preferably 0.3 to 1 mm. Here, the average fiber length means that 50 fibers are selected at random, 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 3 to 12 mm, preferably 4 to 10 mm.

  When the foamed fire-resistant paint of the present invention contains fibers, the content of the binder component (A) is non-volatile from the viewpoint of fire resistance of the foamed layer and cracking resistance of the foamed layer on the edge of the substrate. An amount in the range of 1 to 30 parts by mass, particularly 2 to 25 parts by mass, based on 100 parts by mass is appropriate.

  Examples of the inorganic viscosity modifier include bentonite, swellable silica, hydrophobic silica, montmorillonite, mica, kaolin, serpentine, talc, vermiculite, smectite (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite. , Including a steven site), and sepiolite. These can be used alone or in combination of two or more. Further, these may be any of natural products, synthetic products, processed products using organic substances, and the like.

  When the foamed fireproof paint of the present invention contains an inorganic viscosity modifier, the content thereof is 1 to 15 parts by weight, particularly 3 to 10 parts by weight, based on 100 parts by weight of the binder component (A) nonvolatile content. Within the range of the part is appropriate. The inorganic pigment is not particularly limited, but is an inorganic color pigment such as titanium oxide, carbon black, chrome lead, ocher, yellow iron oxide; talc, silica, calcium carbonate, mica, kaolin, barium sulfate, Examples include extender pigments such as zinc white (zinc oxide). These can be used alone or in combination of two or more.

  The blending amount of the inorganic coloring pigment is suitably in the range of 30 to 100 parts by mass, particularly 45 to 85 parts by mass, based on the binder component (A) non-volatile content of 100 parts by mass, from the viewpoint of the strength of the foam layer. It is.

  The amount of the extender pigment is 0.01 to 25 masses based on the binder component (A) non-volatile content of 100 mass parts from the viewpoint of the strength of the foam layer and the crack resistance of the foam layer on the edge portion of the substrate. Parts, particularly in the range of 0.1 to 18 parts by weight.

  When the foamed fireproof paint of the present invention contains an inorganic material (E), the content thereof is 30 to 140 parts by weight, particularly 45 to 120 parts by weight, based on 100 parts by weight of the binder component (A) non-volatile content. The range of is suitable.

  In addition to the above, the foamed fire-resistant paint of the present invention can contain paint additives such as flame retardants, pigments other than inorganic pigments, organic solvents, surface conditioners, and antifoaming agents. Among these, as the flame retardant, for example, a flame retardant known in the paint field such as boron flame retardant and inorganic flame retardant can be used without limitation.

  Examples of the boron-based flame retardant include boric acid, zinc borate, sodium borate, boron nitride, and the like. Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, magnesium carbonate, and the like. Or it can use in combination of 2 or more types.

  In the case of using the above flame retardant, the blending amount is suitably 0.01 to 10 parts by mass, particularly 1 to 8 parts by mass based on 100 parts by mass of the binder component (A) non-volatile content.

<Foaming fireproof paint>
The above-described process-free foam fire-resistant paint of the present invention has a non-volatile content concentration of 75% by mass or more and preferably 80% by mass or more when applied. When the non-volatile content at the time of application is less than 75%, thick coatability is insufficient, the time required for application becomes long, and even if it can be applied, sagging tends to occur in the coating film.

  And the process-saving foam fireproof paint of the present invention satisfies the above-mentioned condition of the nonvolatile content concentration, and the mass of the component (A), the component (B) and the component (C) is expressed by the following formula (1).

(In formula (1), A _(M) , B _(M) and C _(M) are the masses of component (A), component (B) and component (C), respectively.
It is characterized by becoming the relationship represented by.

  In the case where the relationship of the formula (1) is not satisfied, the fire resistance of the foam layer is low, and cracks and tears are generated in the foam layer generated on the substrate edge portion at the time of thermal expansion.

  As a paint form of the foamed fireproof paint of the present invention, it can be appropriately selected from a single-component system or a multi-component system depending on the type of material as long as it is within the scope of the present invention.

When the foamed fire-resistant paint of the present invention is a multi-component system, for example, the curing catalyst (D) may be in a form that exists as a separate component from the crosslinkable polymer (a1).
Specifically, the first component includes a crosslinkable polymer (a1), a plasticizer (a2), a foaming agent (B), and a carbonizing agent (C), and the second component includes a curing catalyst (D). Can be mentioned.
Or the form in which a 1st component contains a crosslinkable polymer (a1), a plasticizer (a2), and a foaming agent (B) and a 2nd component contains a curing catalyst (D) and a carbonizing agent (C) is mentioned.
By making the coating form as described above, the storage stability of each component is good, and even when a multi-component mixed coating apparatus that automatically mixes multiple components at a predetermined ratio is used, a protective coating in a good state is obtained. A film can be formed in a wide range.

<Coating method>
The present invention provides a fireproof coating method for a structure, including a step of applying a foamed fireproof paint on a substrate surface, a step of drying a coating film obtained by the step, and forming a protective coating film. It is.

  Base materials include not only metals such as steel frames, aluminum, and zinc iron plates, but also wallpaper, plywood, wood, inorganic boards, concrete, mortar, FRP, plastics, paper, cloth, fibers, synthetic resins, rubber, silicon, electric wires Cable etc. are mentioned. Examples of the structure include a ground structure, an offshore structure, and the like. Particularly suitable structures include buildings defined in Articles 21 and 27 of the Building Standard Law. Specific examples include buildings, schools, hospitals, hotels, movie theaters, stores, warehouses, airports, and the like.

  When applied to a steel frame of an existing structure, the foamed refractory paint of the present invention may be applied after applying a base coating such as rust removal and then applying an undercoat if necessary.

  The application method is not particularly limited, and can be easily applied by a general application method such as a brush, a trowel, a roller, or a spray, and it is possible to form not only a smooth application but also an uneven pattern with a thick film. It is. These coating methods are appropriately selected according to the purpose of use of the substrate. The non-volatile content concentration of the paint at the time of application is 75% by mass or more, and more preferably 80% by mass or more.

  As drying conditions, it can be sufficiently dried at room temperature, but if necessary, forced drying or heat drying may be performed.

  The dry average film thickness of the protective coating provided on the substrate surface is 0.5 to 10 mm, preferably 1 to 6 mm, or 1 to 10 mm, preferably 3 to 6 mm. It is appropriate from the viewpoint of workability.

  In this invention, the dry average film thickness of a protective coating film shall be calculated | required by measuring with an electromagnetic film thickness meter.

  The foamed refractory paint of the present invention can be applied once because of its excellent drying properties, but may be applied in multiple steps as necessary.

  Various intermediate coatings and top coatings can be applied to the formed protective coating surface as necessary.

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

<Manufacture of foam fireproof paint>
Examples 1-10 and Comparative Examples 1-4 Each component was mix | blended with the compounding quantity shown to the following table | surface, and the foam fireproof paint (X-1)-(X-14) was manufactured (In addition, the quantity shown to the following table | surface is the amount. In addition to xylene, which is a volatile component, the amount of non-volatile components is indicated). Specifically, the component described in the first component was put in a container and stirred and mixed using a planetary mixer until uniform. The component described in the second component was placed in a separate container and stirred and mixed using a planetary mixer. It put into another container so that the mass ratio of the 1st ingredient and the 2nd ingredient might become the ratio of Table 1, and it mixed by the electric hand mixer, and obtained each fireproof paint.

(Note) Polyether resin: Polyether resin having a polyoxypropylene skeleton in the main chain and a dimethoxymethylsilyl group at the end of the main chain, weight average molecular weight 20000
(Note) Leophos 65: trade name, manufactured by Ajinomoto Fine Chemicals, triaryl isopropylated phosphate,
(Note) Hexamol DINCH: trade name, manufactured by BASF, diisononylcyclohexane dicarboxylate,
(Note) DISPER-BYK145: trade name, manufactured by BYK, amphoteric dispersant, amine value = 71, acid value = 76,
(Note) Disparon NS5025: trade name, active ingredient 25%, manufactured by Enomoto Kasei Co., Ltd., oxidized polyolefin-modified fatty acid polyamide,
(Note) PP4000: trade name, manufactured by Sanyo Chemical Industries, polypropylene glycol, weight average molecular weight 4000,
(Note) Mineral fiber: Average fiber length 500 μm,
(Note) Carbon fiber: Average fiber length 6 mm.

<Evaluation test>
(*) Coating workability The coating workability when each foamed refractory paint is troweled to a dry film thickness of 5 mm on the entire surface of a steel material with a thermocouple attached in the shape of H shown in Fig. 1 is as follows. Evaluation was based on criteria.
◎: It is very easy to spread with a trowel.
○: Can be spread with a trowel
Δ: Difficult to spread with a trowel
X: It is extremely difficult to spread the coating with a trowel.

(*) Sagging property The surface of each specimen prepared for the above coating workability test was observed and evaluated according to the following criteria.
○: Sauce is not recognized at all,
Δ: Sagging is slightly observed,
X: Sagging is noticeable.

(*) Dryness to touch Until each test specimen prepared in the above coating workability evaluation is left to stand at 23 ° C. and 50% RH and the surface of the coating film is touched with a finger, no sticky feeling is lost. Time was measured. The shorter the time, the better.

(*) Fire resistance test Each test specimen after the evaluation of dryness to touch is placed in a furnace heated to a predetermined temperature with respect to the elapsed time so as to have a temperature rising curve determined by ISO 834 by a flame and used for a fire resistance test. did. The numerical values in the table are steel material temperatures 2 hours after the start of heating. In the table, the lower the temperature, the better the fire resistance. In this test, 500 ° C. or lower was regarded as acceptable.

(*) Fire resistance test (edge crack)
FIG. 2 shows the relationship between the elapsed time and the average furnace temperature. In FIG. 2, it follows the ISO834 curve until the elapsed time of 2 hours, but the furnace temperature gradually decreases after 2 hours of stopping the heating.
In the fire resistance test, the specimen is exposed to the environment in the furnace including not only the heating time of 2 hours but also the cooling time of 6 hours thereafter. Each test body was taken out of the furnace, the edge portion of the test body was visually observed, and the state of the foam layer was evaluated according to the following criteria.
A: No cracking or peeling is observed from the edge of the specimen.
○: Some shallow cracks that do not reach the steel material from the edge of the specimen are observed.
Δ: Cracks reaching the steel material from the edge of the specimen are observed,
X: The foam layer is peeled off from the edge of the test specimen.

(*) The average thickness of the foam layer of the lower flange part of each specimen after the foaming ratio fire resistance test was measured, and the expansion coefficient (times) based on the average thickness of the cured coating film before the fire resistance test was calculated. .

FIG. 1 is a schematic view showing an example of the shape of a steel material used in a fire resistance test. FIG. 2 is a diagram showing an example of the relationship between the elapsed time of the furnace used in the fire resistance test and the average temperature.

Claims (11)

A binder component (A) comprising a crosslinkable polymer (a1) and a plasticizer (a2);
Including a blowing agent (B), as well as a carbonizing agent (C),
The mass of the component (A), the component (B), and the component (C) is expressed by the following formula (1).
(In formula (1), A _(M) , B _(M) , and C _(M) are the masses of component (A), component (B), and component (C), respectively.
The relationship represented by
Binder component (A) A process-saving foam fire-resistant paint for application at a paint nonvolatile content concentration of 75% or more, wherein the proportion of the plasticizer (a2) in the nonvolatile content is 50% by mass or less.   The process-resistant foam fireproof paint according to claim 1, wherein the plasticizer (a2) does not contain a fatty acid ester plasticizer or the proportion of the fatty acid ester plasticizer in the plasticizer (a2) is 50% by mass or less.   The foamed fire resistant paint according to claim 1 or 2, wherein the binder component (A) contains an amphoteric dispersant (a3) having an acid value of 5 to 300 mgKOH / g and an amine value of 5 to 300 mgKOH / g.   The fire-resistant foam paint according to any one of claims 1 to 3, wherein the binder component (A) contains an organic viscosity modifier (a4).   The fire-resistant foam paint according to any one of claims 1 to 4, wherein the binder component (A) contains a polyether compound (a5) having a hydroxyl group as a blend polymer.   The foamed refractory paint according to any one of claims 1 to 5, further comprising a curing catalyst (D).   The foamed fire-resistant paint according to claim 6, wherein the curing catalyst (D) is a multi-component composition in a form in which the curing catalyst (D) is present as a separate component from the crosslinkable polymer (a1).   The foamed fireproof paint according to any one of claims 1 to 7, further comprising at least one inorganic material (E) selected from fibers, inorganic viscosity modifiers and inorganic pigments.   A coating method, wherein the foam refractory paint according to any one of claims 1 to 8 is applied to a substrate surface and dried.   A fireproof coating method for a structure, in which a foam fireproof paint according to any one of claims 1 to 8 is applied to a substrate surface and dried to form a protective coating film.   A fireproof structure provided with a protective coating using the foamed fireproof paint according to any one of claims 1 to 8.