JP2011105855A - Water-based foamable fireproof coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based foamable fireproof coating composition capable of exhibiting excellent fire-extinguishing activity by the sufficient generation of chlorine gas, and excellent heat-insulation activity by the sufficient formation of carbonized layer, and also exhibiting excellent fireproof properties, excellent water permeation resistance, excellent water resistance and excellent weather resistance, to provide a method for forming a plural-layered coated film by using such the water-based foamable fireproof coating composition, and to provide a coated product having the plural-layered coated film obtained by such the method for forming the plural-layered coated film. <P>SOLUTION: The water-based foamable fireproof coating composition contains an organic-inorganic hybrid emulsion (1) containing an organic binder component and an inorganic binder component, and a foamable filler (2), wherein the foamable filler (2) contains a polyphosphoric acid salt (2-1) and an emulsion (2-2) of a chlorinated resin. The concentration of the chlorine element in the coated film provided by the coating composition is 1-20 mass%, and the mass proportion of the organic components in the coating composition is 5-30%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aqueous foam refractory paint composition. In detail, when a ceramic outer wall base material used for a housing outer wall is exposed to a flame, it is possible to quickly reduce the temperature rise of the outer wall base material by quickly forming a foam insulation layer, etc. The present invention relates to a water-based foam fire-resistant coating composition. Moreover, it is related with the coating material provided with the multilayer coating film obtained by such a multilayer coating-film formation method using such a water-based foam fireproof coating composition, and such a multilayer coating-film formation method.

  According to the Fire Department of the Ministry of Internal Affairs and Communications, arson and suspicion of arson have reached 30% of the cause of the fire of a house fire. It has become an important item.

  In recent years, exterior walls using ceramic building materials have a sealer layer + enamel layer + design coating layer (ink layer) + clear layer (+) in order to prolong the service life represented by improved weather resistance and diversify design variations. The coating is applied to form a multilayer coating film such as a functional layer (such as a low-contamination layer). With such multilayering, petroleum-based resins (sometimes referred to as organic matter) that become combustible materials in the event of a fire are often used, and there is no denying the tendency to burn easily.

  As a material for protecting a base material such as steel, concrete, wood, and synthetic resin from a fire, a foamable fireproof paint that forms a foamed layer by a temperature rise at the time of fire is known. The foamable refractory paint contains a component that decomposes as the temperature rises to generate a nonflammable gas and a component that carbonizes to form a porous carbonized layer. The fire extinguishing effect is expressed by the occurrence of fire, and the heat insulating effect is expressed by forming a porous carbonized layer by carbonization.

  Various proposals have been made on such foamable fireproof paints for the purpose of improving various physical properties such as fire resistance.

  For example, it has been proposed to define the melt mass flow rate at 125 ° C. and 190 ° C. of a dry film of a binder containing a hydroxyl group-containing synthetic resin emulsion (Patent Document 1). Further, it has been proposed to improve water resistance by reacting a urethane compound having a tertiary amino group and a polyalkylene oxide group with a hydroxyl group-containing synthetic resin emulsion to cause crosslinking (Patent Document 2). However, these have a problem that the remaining amount of the coating film component becomes insufficient due to the combustion of the synthetic resin by the flame, and it is difficult to form a sufficiently thick foam layer.

  Furthermore, a technique for mixing a synthetic resin component as an organic binder and a thermosetting inorganic binder has been proposed (Patent Document 3). However, there is a problem that the water resistance and freeze-thaw resistance are not sufficient due to the fact that the organic binder and the inorganic binder are simply mixed.

  On the other hand, it is known to use a foam filler as a technique for imparting fire resistance to a coating film. The foam filler may be blended with chlorinated paraffin or the like in order to develop a fire extinguishing action due to generation of chlorine gas and a heat insulating action due to formation of a carbonized layer. However, since chlorinated paraffin and the like have a hydrophobic property, when such a hydrophobic component is added to the aqueous coating material, it is separated in the coating material, making it difficult to obtain an emulsified state. For this reason, addition of such a foam filler to a water-based paint is difficult, and is limited to addition to a solvent-based paint. In addition, even if the chlorinated paraffin itself can be temporarily emulsified by forced stirring and added to the aqueous paint, the emulsion will be separated during long-term storage in the paint composition in which contaminants coexist. There's a problem.

JP 2008-13629 A JP 2008-88227 A Japanese Patent No. 3455378

  An object of the present invention is a water-based foam fire-resistant paint composition, which can exhibit an excellent fire extinguishing action due to sufficient generation of chlorine gas and an excellent heat insulating action due to the formation of a sufficient carbonized layer, as well as excellent fire resistance and excellent resistance. An object of the present invention is to provide a water-based foam fire-resistant coating composition that can exhibit water resistance, excellent water resistance, and excellent weather resistance. Moreover, it is providing the coating material provided with the multilayer coating film obtained by such a multilayer coating-film formation method using such a water-based foam fire-proof coating composition, and such a multilayer coating-film formation method.

The aqueous foam fire-resistant paint composition of the present invention comprises an organic-inorganic hybrid emulsion (1) containing an organic binder component and an inorganic binder component, and a foam filler (2), and the foam filler (2) is polyphosphoric acid. An aqueous foam fireproof coating composition comprising a salt (2-1) and an emulsion (2-2) of a chlorinated resin, wherein the chlorine element concentration in the coating film provided by the coating composition is 1 to 20 mass %, And the organic mass ratio in the coating composition is 5 to 30%. The binder component is a resin that forms a coating film, the organic binder indicates a coating film-forming organic resin component, more specifically the component (b) described later, and the inorganic binder is a coating film formation. This refers to the component (a) described later.
In preferable embodiment, solid content ratio (1) :( 2) of the said organic-inorganic hybrid emulsion (1) and the said foaming filler (2) is 1: 9-7: 3 by mass ratio.
In a preferred embodiment, the solid content ratio (2-1) :( 2-2) between the polyphosphate (2-1) and the chlorinated resin emulsion (2-2) is a mass ratio, 9: 1-3: 7.
In a preferred embodiment, the chlorinated resin has a number average molecular weight of 500 to 5,000.
In preferable embodiment, the density | concentration of the chlorine element in the coating film which the said coating composition provides is 2-18 mass%, and the organic mass ratio in the said coating composition is 5-20%.
In a preferred embodiment, the organic-inorganic hybrid emulsion (1) is a radical-polymerizable vinyl monomer (a) selected from organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane. An aqueous dispersion obtained by subjecting the mixture containing b) to hydrolysis, condensation reaction, and radical polymerization in an emulsified state.
In another embodiment of the present invention, a method for forming a multilayer coating film is provided. The method for forming a multilayer coating film of the present invention comprises forming a sealer layer using the water-based foam fire-resistant paint composition of the present invention, and at least a base enamel layer, a top enamel layer, and a clear layer in this order on the sealer layer. A multilayer coating film forming method for forming a multilayer film having a maximum heat generation rate in a cone calorimeter of 50 KW / m ² or less calculated by a measurement method based on the fact that continuous combustion is not exhibited The organic mass in a multilayer coating film is 5-75 g / m < ² >.
In another embodiment of the present invention, a painted article is provided. The coated product of the present invention includes a multilayer coating film obtained by the multilayer coating film forming method of the present invention on a substrate.

  According to the present invention, it is an aqueous foam fire-resistant paint composition, which can exhibit an excellent fire extinguishing action due to sufficient generation of chlorine gas and an excellent heat insulating action due to the formation of a sufficient carbonized layer, as well as excellent fire resistance, excellent It is possible to provide a water-based foam fire-resistant coating composition that can exhibit water resistance, excellent water resistance, and excellent weather resistance. Moreover, the coating material provided with the multilayer coating film obtained by such a multilayer coating-film formation method using such a water-based foam fire-proof coating composition and such a multilayer coating-film formation method can be provided.

≪A. Water-based foam fireproof coating composition >>
The aqueous foam fire-resistant paint composition of the present invention is an aqueous foam fire-resistant paint composition comprising an organic-inorganic hybrid emulsion (1) containing an organic binder component and an inorganic binder component and a foam filler (2), The foam filler (2) contains a polyphosphate (2-1) and an emulsion (2-2) of a chlorinated resin.

[Organic inorganic hybrid emulsion (1)]
The organic-inorganic hybrid emulsion (1) includes an organic binder component and an inorganic binder component. Preferably, the organic-inorganic hybrid emulsion (1) comprises at least one (a) selected from an organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane and a radical polymerizable vinyl monomer (b). It is a water-based emulsion obtained by hydrolyzing, condensing reaction, and radical polymerization of the containing mixture in an emulsified state.

The organosilane in the component (a) is preferably represented by the general formula (1).
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In General Formula (1), when two R ¹ are present, they are the same or different and each represents a monovalent organic group having 1 to 8 carbon atoms, and R ² is the same or different and has 1 to 5 carbon atoms. An alkyl group or a C1-C6 acyl group is shown, and n is an integer of 0-2.)

The organosilane hydrolyzate in component (a) need not have all the OR ² groups of general formula (1) contained in 2 to 4 of the organosilane hydrolyzed, for example, only one May be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.

  The organosilane condensate in the component (a) is one in which at least a part of silanol groups in the hydrolyzate of organosilane is condensed to form a Si—O—Si bond. That is, the condensate of organosilane does not need to have all the silanol groups of the hydrolyzate of organosilane condensed, such as those in which a small part of the silanol groups are condensed or the degree of condensation is different. It may be a mixture.

In the general formula (1), when two R ¹ are present, they are the same or different and represent a monovalent organic group having 1 to 8 carbon atoms. Examples of the monovalent organic group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl. Group, n-hexyl group, n-heptyl group, n-octyl group, alkyl group such as 2-ethylhexyl group; cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group; acetyl group, propionyl group, butyryl group, Acyl groups such as valeryl group, benzoyl group, trioyl group, caproyl group; vinyl group; allyl group; epoxy group; glycidyl group; (meth) acryloxy group; ureido group; amide group; fluoroacetamide group; Substituted derivatives of these groups; and the like.

  Examples of the substituent in the substituted derivative include a halogen group, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, and a ureido. Groups, ammonium bases and the like.

In General Formula (1), R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. Can be mentioned. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.

  Specific examples of the organosilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Run, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyl Trimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimeth Sisilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acrylicoxypropyltri Trialkoxysilanes such as ethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldi Ethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyl Diethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n- Heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. In addition to alkoxysilanes, methyltri Cetyl silane, dimethyl di acetyloxy silane.

  As the organosilane in the component (a), trialkoxysilanes and dialkoxysilanes are preferable. As trialkoxysilanes, methyltrimethoxysilane and methyltriethoxysilane are preferable. As the dialkoxysilanes, dimethyldimethoxysilane and dimethyldiethoxysilane are preferable.

  The component (a) is at least one selected from organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane. The component (a) is preferably a mixture of an organosilane and a condensate of organosilane (hereinafter also referred to as “polyorganosiloxane”). This is because when organosilane and polyorganosiloxane are co-condensed, a film excellent in properties such as hardness, chemical resistance, weather resistance, film formability, transparency, and crack resistance can be formed. In addition, the polymerization stability when the radically polymerizable vinyl monomer is polymerized after emulsification is remarkably improved, and the polymerization can be carried out at a high solid content, so that industrialization is easy.

  When the component (a) is a mixture of an organosilane and a polyorganosiloxane, dialkoxysilanes are preferred as the organosilane. This is because the use of dialkoxysilanes adds a linear component as a molecular chain and increases the flexibility of the resulting particles. Furthermore, when forming a coating film with the aqueous foam fire-resistant paint composition of this invention finally obtained using the obtained water-based emulsion, there exists an effect that the coating film excellent in transparency is obtained. As the dialkoxysilanes, dimethyldimethoxysilane and dimethyldiethoxysilane are particularly preferable.

  When the component (a) is a mixture of an organosilane and a polyorganosiloxane, the polyorganosiloxane may be a trialkoxysilane alone or a combination of trialkoxysilane and dialkoxysilane (trialkoxysilane: di A condensate of alkoxysilane = 40: 60 to 95: 5 (molar ratio)) is preferable. When dialkoxysilane is used in combination with trialkoxysilane, the resulting coating film is softened and alkali resistance can be improved.

  Polyorganosiloxane is used as a condensate of organosilane by previously hydrolyzing and condensing organosilane. When preparing the polyorganosiloxane, it is preferable to hydrolyze and condense the organosilane by adding an appropriate amount of water to the organosilane and, if necessary, an organic solvent. The amount of water used is preferably 1.2 to 3.0 mol, preferably 1.3 to 2.0 mol, per 1 mol of organosilane.

  As said organic solvent which can be added when preparing polyorganosiloxane, arbitrary suitable organic solvents can be employ | adopted if a polyorganosiloxane and the (b) component mentioned later can be mixed uniformly. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be mentioned. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, Examples include diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol. Examples of the aromatic hydrocarbons include benzene, toluene, xylene and the like. Examples of the ethers include tetrahydrofuran and dioxane. Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents may be used alone or in combination of two or more. In addition, when adding the said organic solvent when preparing polyorganosiloxane, you may remove this organic solvent from an aqueous dispersion before the condensation and polymerization reaction mentioned later.

  The weight average molecular weight Mw (polystyrene conversion) of the polyorganosiloxane is preferably 800 to 100,000, more preferably 1000 to 50,000.

  Commercially available products of polyorganosiloxane include, for example, MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resin manufactured by Toray Dow Corning, silicon resin manufactured by Toshiba Silicone, Shin-Etsu Chemical Examples thereof include a silicone resin manufactured by Kogyo Co., Ltd., a hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd., and a silicon oligomer manufactured by Nippon Unica Co., Ltd. These commercially available products may be used as they are or after being condensed.

When the component (a) is a mixture of an organosilane and a polyorganosiloxane, the content ratio thereof is preferably an organosilane (as a fully hydrolyzed condensate), preferably 95 to 5% by mass, more preferably Is 90 to 10% by mass, and polyorganosiloxane (in terms of complete hydrolysis condensate) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass (provided that organosilane + polyorganosilane = 100% by mass). When the content ratio of polyorganosiloxane (in terms of completely hydrolyzed condensate) is less than 5% by mass, the surface of the resulting coating film may be sticky or the coating film curability may be deteriorated. If the content ratio of polyorganosiloxane (in terms of completely hydrolyzed condensate) exceeds 95% by mass, the ratio of the organosilane component may be too small to emulsify the mixture containing the component (a), Moreover, there exists a possibility that the polymerization stability of (b) component may fall after emulsification, and there exists a possibility that the stability of the emulsion after emulsification may fall. Moreover, there exists a possibility that the film formability of the water-based foam fire-resistant paint composition of this invention finally obtained may fall. Here, the complete hydrolysis-condensation product refers to a product in which the R ² O— group of the organosilane is hydrolyzed to 100% to become a SiOH group, and further completely condensed to a siloxane structure.

  As the radically polymerizable vinyl monomer as the component (b), any appropriate radically polymerizable vinyl monomer can be adopted as long as it is a monomer having an unsaturated double bond capable of radical polymerization. Only 1 type may be used for such a radically polymerizable vinyl monomer, and it may use 2 or more types together. Examples of such radically polymerizable vinyl monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl methacrylate, and other (meth) acrylic Acid esters; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; ethylene glycol di (meth) acrylate Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyfunctionality such as pentaerythritol tetra (meth) acrylate ( (Meth) acrylic acid esters; fluorine atom-containing (meth) acrylates such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate Amino group-containing (meth) acrylic esters such as 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, and 3-aminopropyl (meth) acrylate; epoxy such as glycidyl (meth) acrylate (Meth) acrylic compounds such as group-containing (meth) acrylic acid esters;

  As the component (b), in addition to those listed above, for example, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene Aromatic vinyl monomers such as 2,4-dichlorostyrene, 2,6-dichlorostyrene and 1-vinylnaphthalene; polyfunctional monomers other than the above such as divinylbenzene; (meth) acrylamide, N-methylol (Meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) a Acid amide compounds such as rilamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; 4- (meth) acryloyloxy-2,2,6 , 6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, etc. Piperidine monomers; dicaprolactone; and the like.

  As the component (b), as the component (b) having a functional group, for example, unsaturated carboxylic acids other than the above such as crotonic acid, maleic acid, fumaric acid, itaconic acid; maleic anhydride, itaconic anhydride Unsaturated carboxylic acid anhydrides such as; hydroxyl group-containing vinyl monomers other than those such as N-methylol (meth) acrylamide and 2-hydroxyethyl vinyl ether; amino group-containing vinyl monomers such as 2-aminoethyl vinyl ether 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1, 1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine (meth) acrylimide, 1 Aminimide group-containing vinyl monomers such as 1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide; Epoxy group-containing vinyl monomers other than the above, such as allyl glycidyl ether Body; and the like.

  As said (b) component, a (meth) acryl compound is preferable. Among (meth) acrylic compounds, (meth) acrylic acid, (meth) acrylic acid esters, and hydroxyl group-containing (meth) acrylic acid esters are more preferable. More preferred are methyl methacrylate, butyl methacrylate, acrylic acid and 2-hydroxyethyl methacrylate.

  The content ratio of the component (A) and the component (b) is the total amount of the component (A) when the total amount of the component (A) and the component (B) is 100% by mass. Hydrolysis conversion condensate) is preferably 1 to 95% by mass, more preferably 10 to 90% by mass, and the total amount of component (b) is preferably 99 to 5% by mass, more preferably 90 to 10% by mass. is there. When the content rate of (b) component is less than 5 mass%, there exists a possibility that film-forming property and crack resistance may fall. When the content rate of (b) component exceeds 99 mass%, there exists a possibility that a weather resistance deterioration may become remarkable.

  The organic-inorganic hybrid emulsion (1) is obtained by subjecting a mixture containing the component (a) and the component (b) to hydrolysis, condensation reaction, and radical polymerization in an emulsified state. Preferably, the mixture containing the component (a) and the component (b) is emulsified in the presence of water and a surfactant and subjected to hydrolysis, condensation reaction, and radical polymerization. In this hydrolysis, condensation reaction, and radical polymerization, under the emulsified state, (co) condensation of component (a) (preferably a mixture of organosilane and polyorganosiloxane) and component (b) (radical polymerizability) The radical polymerization of the vinyl monomer) proceeds simultaneously. In addition, when (a) component is a mixture of organosilane and polyorganosiloxane, when said 2 types co-condense, said 2 types may each carry out a condensation reaction independently.

  The water that can be used in preparing the organic-inorganic hybrid emulsion (1) may be water present in a mixture containing the component (a) and the component (b), or Furthermore, water added together with the surfactant may be used. The amount of water used is preferably 80 to 1000 parts by mass, more preferably 100 to 500 parts by mass, with respect to 100 parts by mass of the total amount of component (a) (completely hydrolyzed condensate) and component (b). . If the usage-amount of the said water is less than 80 mass parts, there exists a possibility that emulsification may become difficult and stability of the emulsion after emulsification may fall. When the usage-amount of the said water exceeds 1000 mass parts, there exists a possibility that productivity may fall.

  Any appropriate surfactant can be adopted as the surfactant. For example, anionic surfactants such as alkyl sulfate ester salts, alkylaryl sulfate ester salts, alkyl phosphate ester salts and fatty acid salts; cationic surfactants such as alkylamine salts and alkyl quaternary amine salts; polyoxyethylene alkyl Nonionic surfactants such as ethers, polyoxyethylene alkylaryl ethers and block-type polyethers; amphoteric surfactants such as carboxylic acid types (for example, amino acid types and betainic acid types) and sulfonic acid types; . These surfactants may be used alone or in combination of two or more.

  The amount of the surfactant used is preferably 0.05 to 10% by mass, more preferably 0.1 to the total amount of the component (a) (in terms of complete hydrolysis condensate) and the component (b). 5% by mass. If the amount of the surfactant used is less than 0.05% by mass, it may not be sufficiently emulsified, and the stability of the reaction solution during hydrolysis, condensation reaction, and radical polymerization may be reduced. When the usage-amount of the said surfactant exceeds 10 mass%, there exists a possibility that foaming may become a problem.

  In the above hydrolysis, condensation reaction, and radical polymerization, a radical polymerization initiator can be used. Any appropriate radical polymerization initiator can be adopted as the radical polymerization initiator. For example, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic peroxide, 2,2′-azobis (2 Water-soluble initiators such as -N-benzylamidino) propane hydrochloride; benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxyoctoate, azobisisobutyro And oil soluble initiators such as nitriles; redox initiators used in combination with reducing agents such as acidic sodium sulfite, Rongalite, and ascorbic acid. The usage-amount of a radical polymerization initiator becomes like this. Preferably it is 0.05-10 mass% with respect to the radically polymerizable vinyl monomer which is (b) component, More preferably, it is 0.1-5 mass%.

  In the above hydrolysis, condensation reaction, and radical polymerization, it is preferable to make the aqueous system into a mini-emulsion by using mechanical means such as a high-pressure homogenizer, ultrasonic waves, a homomixer, or the like.

  As for the reaction conditions for the hydrolysis, condensation reaction and radical polymerization, the temperature is preferably 25 to 80 ° C., more preferably 40 to 70 ° C., the reaction time is preferably 0.5 to 15 hours, more preferably 1-8 hours.

  In the hydrolysis, condensation reaction, and radical polymerization, when the component (a) or the component (b) has an acidic group such as a carboxyl group or a carboxylic acid anhydride group, the hydrolysis, condensation reaction, and radical After the polymerization reaction, it is preferable to adjust the pH by adding at least one basic compound. This is because the hydrophilicity of the resulting emulsion can be increased and the dispersibility can be improved. Examples of the basic compound include amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, and dimethylaminoethanol; alkali metal hydroxides such as caustic potash and caustic soda; Is mentioned.

  In the hydrolysis, condensation reaction, and radical polymerization, when the component (a) or the component (b) has basicity such as an amino group or an amineimide group, the hydrolysis, condensation reaction, and radical polymerization reaction Later, it is preferred to adjust the pH by adding at least one acidic compound. This is because the hydrophilicity of the resulting emulsion can be increased and the dispersibility can be improved. Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid; formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, citric acid, adipic acid, (meth) acrylic acid, maleic acid, fumaric acid Organic acids such as itaconic acid; and the like.

  In the above hydrolysis, condensation reaction, and radical polymerization, when the component (a) or the component (b) has an acidic group and a basic group, after the reaction of the hydrolysis, condensation reaction, and radical polymerization, According to the ratio of these groups, it is preferable to adjust pH by adding at least one basic compound or acidic compound. This is because the hydrophilicity of the resulting emulsion can be increased and the dispersibility can be improved.

  The pH value of the emulsion during the pH adjustment is preferably 6 to 10, more preferably 7 to 8. When the pH value of the emulsion is below the lower limit of the above preferable value, the circulation stability in the coating line of the paint using the emulsion may be deteriorated. On the other hand, when the upper limit of the preferable value is exceeded, the water resistance of the coating film obtained using the emulsion may deteriorate, which is not preferable.

  In the hydrolysis, condensation reaction, and radical polymerization described above, any appropriate additive may be contained in the reaction solution. For example, silane coupling agents, curing accelerators, other resins, inorganic compounds, pigments, ceramics, metals, alloys, metal oxides, metal hydroxides, metal carbides, metal nitrides, metal sulfides, UV absorbers, Examples thereof include UV stabilizers, dyes, leveling agents, and other appropriate additives that can be used in other coating compositions.

  In the organic-inorganic hybrid emulsion (1), an organic-inorganic hybrid (organic-inorganic composite) is dispersed in an aqueous medium, and the dispersion state is preferably particulate or aqueous sol. In this case, the average particle diameter of the organic-inorganic hybrid (organic-inorganic composite) is preferably 0.01 to 100 μm, more preferably 0.05 to 10 μm. The average particle diameter is an average particle diameter measured by a laser light scattering method (manufactured by Otsuka Electronics Co., Ltd., product number: ELSZ-2).

  The solid content concentration of the organic-inorganic hybrid emulsion (1) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass. This solid content concentration is usually adjusted by the amount of water.

  The aqueous medium in the organic-inorganic hybrid emulsion (1) consists essentially of water, but in some cases, an organic solvent such as alcohol may be contained up to about several mass%. Moreover, when the organic-inorganic hybrid emulsion (1) contains an organic solvent used as necessary when preparing the component (a), the organic solvent can be removed from the emulsion. Furthermore, in the organic-inorganic hybrid emulsion (1), various organic solvents as described above used at the time of preparing the component (a) can be added as necessary.

  The organic-inorganic hybrid emulsion (1) may contain any other appropriate additive. As such an additive, various additives that can be used in ordinary fireproof paints can be adopted. For example, silane coupling agents, curing accelerators, other resins, inorganic compounds, pigments, fibers, thickeners, ceramics, metals, alloys, metal oxides, metal hydroxides, metal carbides, metal nitrides, metal sulfides Products, UV absorbers, UV stabilizers, antioxidants, catalysts, dyes, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, dispersions Agents, antifoaming agents, adsorbents, crosslinking agents, and other suitable additives that can be used in other coating compositions. Moreover, expansive substances, such as expansive graphite and unexpanded vermiculite, can also be mix | blended.

[Foamed filler (2)]
The foam filler (2) contains a polyphosphate (2-1) and an emulsion (2-2) of a chlorinated resin.

  Any appropriate polyphosphate can be adopted as the polyphosphate (2-1) as long as it is a salt of polyphosphoric acid. Preferably, it is ammonium polyphosphate. When the foaming filler (2) contains the polyphosphate (2-1), a phosphate glassy layer is formed by a temperature rise due to a fire or the like, and a fire extinguishing action, a fire resistance action, and a heat insulation action can be expressed.

  Arbitrary appropriate chlorinated resin can be employ | adopted as a chlorinated resin in the emulsion (2-2) of a chlorinated resin. Examples thereof include chlorinated paraffin, chlorinated polypropylene, chlorinated polyethylene, chlorinated polyolefin, and vinylidene chloride. These chlorinated resins may be used alone or in combination.

  The number average molecular weight of the chlorinated resin in the chlorinated resin emulsion (2-2) is preferably 500 to 50,000, more preferably 500 to 5,000. When the molecular weight of the chlorinated resin in the chlorinated resin emulsion (2-2) falls within these ranges, excellent storage stability of the paint can be obtained. Moreover, in the coating film, it can exhibit excellent fire extinguishing action due to sufficient generation of chlorine gas and excellent heat insulation effect due to sufficient carbonization layer formation, as well as excellent fire resistance, excellent water permeability resistance, excellent warm water resistance, excellent It is possible to provide the water-based foam fire-resistant paint composition of the present invention that can exhibit excellent weather resistance and excellent adhesion to the top coat film.

  The chlorine content of the chlorinated resin in the chlorinated resin emulsion (2-2) is preferably 40 to 75 mass%. When the chlorine content of the chlorinated resin in the chlorinated resin emulsion (2-2) falls within these ranges, excellent storage stability of the paint can be obtained. Moreover, in the coating film, it can exhibit excellent fire extinguishing action due to sufficient generation of chlorine gas and excellent heat insulation effect due to sufficient carbonization layer formation, as well as excellent fire resistance, excellent water permeability resistance, excellent warm water resistance, excellent It is possible to provide the water-based foam fire-resistant paint composition of the present invention that can exhibit excellent weather resistance and excellent adhesion to the top coat film.

  The emulsion (2-2) of chlorinated resin can be prepared by any appropriate method. For example, it can be prepared by mixing a chlorinated resin, water and an emulsifier, and employing any appropriate emulsification method such as mechanical emulsification method or phase inversion emulsification method alone or in combination. Examples of the mechanical emulsification method include a homomixer, a valve homogenizer, a colloid mill, and an ultrasonic method. Any appropriate emulsifier can be adopted as the emulsifier. For example, for example, anionic surfactants such as alkyl sulfate ester salts, alkylaryl sulfate ester salts, alkyl phosphate ester salts, and fatty acid salts; cationic surfactants such as alkylamine salts and alkyl quaternary amine salts; Nonionic surfactants such as ethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, block type polyethers; amphoteric surfactants such as carboxylic acid types (for example, amino acid types, betainic acid types) and sulfonic acid types; It is done.

  In the foam filler (2), the solid content ratio (2-1) :( 2-2) between the polyphosphate (2-1) and the chlorinated resin emulsion (2-2) is a mass ratio, Preferably it is 9: 1-3: 7, More preferably, it is 7: 3-5: 5. When the solid content ratio of the polyphosphate (2-1) and the chlorinated resin emulsion (2-2) falls within the above range, excellent storage stability of the paint can be obtained. Moreover, in the coating film, it can exhibit excellent fire extinguishing action due to sufficient generation of chlorine gas and excellent heat insulation effect due to sufficient carbonization layer formation, as well as excellent fire resistance, excellent water permeability resistance, excellent warm water resistance, excellent It is possible to provide the water-based foam fire-resistant paint composition of the present invention that can exhibit excellent weather resistance and excellent adhesion to the top coat film.

  The foam filler (2) may contain any appropriate additive in addition to the polyphosphate (2-1) and the chlorinated resin emulsion (2-2). As such an additive, various additives that can be used in ordinary fireproof paints can be adopted. For example, silane coupling agents, curing accelerators, other resins, inorganic compounds, pigments, fibers, thickeners, ceramics, metals, alloys, metal oxides, metal hydroxides, metal carbides, metal nitrides, metal sulfides Products, UV absorbers, UV stabilizers, antioxidants, catalysts, dyes, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, dispersions Agents, antifoaming agents, adsorbents, crosslinking agents, and other suitable additives that can be used in other coating compositions. Moreover, expansive substances, such as expansive graphite and unexpanded vermiculite, can also be mix | blended.

[Water-based foam fire-resistant paint composition]
The aqueous foam fire-resistant paint composition of the present invention is an aqueous foam fire-resistant paint composition containing the organic-inorganic hybrid emulsion (1) and the foam filler (2).

  In the aqueous foam fire-resistant paint composition of the present invention, the solid content ratio (1) :( 2) between the organic-inorganic hybrid emulsion (1) and the foam filler (2) is a mass ratio, preferably 1: 9-7. : 3, more preferably 3: 7 to 7: 3. When the solid content ratio (1) :( 2) between the organic-inorganic hybrid emulsion (1) and the foam filler (2) is within the above range, excellent fire extinguishing action due to generation of sufficient chlorine gas and sufficient carbonized layer It is possible to provide the water-based foamed fire-resistant coating composition of the present invention that can exhibit excellent heat insulation effect due to formation, and can exhibit excellent fire resistance, excellent water permeability, excellent warm water resistance, and excellent weather resistance. it can.

  The water-based foam fire-resistant paint composition of the present invention may contain a polyhydric alcohol. By containing a polyhydric alcohol, it helps to form a thick carbonized layer with excellent heat insulation. Any appropriate polyhydric alcohol can be adopted as the polyhydric alcohol. Examples include pentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol, trimethylolpropane, sorbitol, inositol, mannitol, glucose fructose, starch, cellulose and the like. When polyhydric alcohol is included, the content ratio of the polyhydric alcohol is preferably 5 to 1000 parts by mass, more preferably 10 to 500 parts by mass, with respect to 100 parts by mass of the solid content of the organic-inorganic hybrid emulsion (1). More preferably, it is 10-200 mass parts. When the content ratio of the polyhydric alcohol is within the above range, it is possible to more efficiently form a thick carbonized layer having excellent heat insulation.

  The aqueous foam refractory paint composition of the present invention may contain a film-forming aid. By including a film-forming aid, each component in the coating composition helps to form a stable coating film with excellent homogeneity that does not become unevenly distributed in the coating film. Any appropriate film-forming aid may be employed as the film-forming aid. For example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Examples include butyl ether, dipropylene glycol monobutyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and benzyl alcohol. It is done. When the film-forming auxiliary is included, the content of the film-forming auxiliary is preferably 0.001 to 50 parts by mass, more preferably 0.001 parts by mass with respect to 100 parts by mass of the solid content of the organic-inorganic hybrid emulsion (1). It is 01-40 mass parts, More preferably, it is 0.1-30 mass parts. If the content rate of the said film forming adjuvant is settled in the said range, the stable coating film can be formed more efficiently. Providing the coating film with homogeneity as described above also contributes to improving adhesion with the top coat film. If each component in the water-based foam fire-resistant paint composition of the present invention is unevenly distributed in the coating film, the properties of the surface of the paint film provided by the water-based foam fire-resistant paint composition are not uniform, and therefore the adhesion to the top coat film Tends to be unable to be secured, which is not preferable. This tendency becomes more prominent when the water-based foam fire-resistant coating composition is a lacquer containing no curing agent.

  The water-based foam fireproof coating composition of the present invention may contain a filler. Examples of fillers include silicates such as talc; carbonates such as calcium carbonate and sodium carbonate; metal oxides such as aluminum oxide, titanium dioxide, and zinc oxide; natural minerals such as clay, clay, shirasu, mica, and silica. And the like. When the filler is included, the content of the filler is preferably 1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and further preferably 100 parts by mass of the solid content of the organic-inorganic hybrid emulsion (1). Is 10 to 200 parts by mass. If the content rate of the said filler is settled in the said range, the stable coating film can be formed more efficiently.

  The aqueous foam fire-resistant paint composition of the present invention may contain a foaming agent. By including the foaming agent, it helps to develop the foaming action of the water-based foam fireproof coating composition of the present invention. Examples of the foaming agent include melamine and derivatives thereof, dicyandiamide and derivatives thereof, azobistetrazole and derivatives thereof, azodicarbonamide, urea, and thiourea. These foaming agents can be expected to have a fire-extinguishing effect by generating nitrogen gas. Further, since it is not as hydrophobic as the chlorinated resin, it is not necessary to add to the paint after emulsifying like the chlorinated resin. When the foaming agent is included, the content of the foaming agent is preferably 1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, and still more preferably, with respect to 100 parts by weight of the solid content of the organic-inorganic hybrid emulsion (1). Is 10 to 200 parts by mass. If the content rate of the said foaming agent is settled in the said range, the foaming effect | action of the water-based foam fire-proof coating composition of this invention can be expressed more effectively.

  The water-based foam fire-resistant coating composition of the present invention may contain any appropriate additive. As such an additive, various additives that can be used in ordinary fireproof paints can be adopted. For example, silane coupling agents, curing accelerators, other resins, inorganic compounds, pigments, fibers, thickeners, ceramics, metals, alloys, metal oxides, metal hydroxides, metal carbides, metal nitrides, metal sulfides Products, UV absorbers, UV stabilizers, antioxidants, catalysts, dyes, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, dispersions Agents, antifoaming agents, adsorbents, crosslinking agents, and other suitable additives that can be used in other coating compositions. Moreover, expansive substances, such as expansive graphite and unexpanded vermiculite, can also be mix | blended.

  The water-based foam fire-resistant paint composition of the present invention can be produced by uniformly mixing the above various components by a conventional method. Usually, a one-pack type may be used.

  The effect of the water-based foam fire-resistant coating composition of the present invention can be further exerted by applying and laminating to a base material (a material to be coated) to which fire resistance is to be imparted. Any appropriate base material can be adopted as such a base material. For example, ceramic building materials, concrete, steel materials, wooden members, resin-based members, and the like can be given. Such a substrate may be subjected to a rust prevention treatment or the like.

In the aqueous foam fire-resistant coating composition of the present invention, the chlorine element concentration in the applied coating film is 1 to 20% by mass, preferably 2 to 18% by mass, more preferably 3 to 18% by mass. The concentration of chlorine element in the coating film is obtained by measurement with a fluorescent X-ray analyzer. If the chlorine element concentration in the coating film is less than 1% by mass, there is a risk that chlorine gas exhibiting fire extinguishing properties will not be sufficiently generated when the coating film burns. When the chlorine element concentration in the coating film exceeds 20% by mass, the aqueous foam refractory coating composition of the present invention needs to contain a large amount of emulsion (2-2) of chlorinated resin. As a result, the storage stability of the resulting water-based foam fire-resistant coating composition of the present invention may be deteriorated, or the adhesion with the topcoat may be reduced. In addition, the said chlorine element density | concentration can be adjusted by adjusting the compounding quantity of the emulsion (2-2) of the chlorinated resin contained in the water-based foam fireproof coating composition of this invention.
The water-based foamed fireproof coating composition of the present invention has an organic mass ratio (%) (= 100 (%) − 500 ° C. ash content (%)) of preferably 5 to 30%, more preferably 5 to 20%. The organic mass ratio is an index of the organic content ratio. The lower the organic mass ratio, the lower the organic content ratio, and the smaller the organic substance that becomes a combustible material in the event of a fire, it means superior fire resistance. . If the organic mass ratio exceeds 30%, the fire resistance may be poor. On the other hand, when the organic mass fraction is less than 5% in the water-based foamed fire-resistant coating composition of the present invention, there is a possibility that the components necessary for exhibiting the effects of the present invention are insufficient. Further, the stability of the resulting water-based foam fire-resistant coating composition of the present invention may be lowered, the weather resistance of the coating film, or the adhesion of the base and / or the top coat may be deteriorated. In addition, the measuring method of 500 degreeC ash content (%) is mentioned later.

≪B. Method for forming multilayer coating film >>
The method for forming a multilayer coating film of the present invention comprises forming a sealer layer using the water-based foam fire-resistant paint composition of the present invention, and at least a base enamel layer, a top enamel layer, and a clear layer in this order on the sealer layer. A multilayer coating film forming method for forming a multilayer film having a maximum heat generation rate in a cone calorimeter of 50 KW / m ² or less calculated by a measurement method based on the fact that continuous combustion is not exhibited It is a multilayer coating-film formation method whose organic mass in a multilayer coating film is 5-75 g / m < ² >.

  In the multilayer coating film forming method of the present invention, a sealer layer is formed using the water-based foamed fireproof coating composition of the present invention, and at least a base enamel layer, a top enamel layer, and a clear layer are formed on the sealer layer. A multilayer having the layers in order is formed. By adding these top coat films, not only can the beauty be imparted to the article to be coated, but also the weather resistance can be greatly improved.

  The sealer layer is formed by coating the water-based foamed fire-resistant coating composition of the present invention on any appropriate substrate. As an application method, any appropriate application method such as a normal application method of a fireproof coating composition can be adopted. For example, a coating method such as spraying, rollering, brushing, trowel, spatula or the like is used to coat and apply once or several times. After coating, it may be dried at any appropriate temperature and time as required. At the time of painting, the water-based foamed fireproof coating composition of the present invention can be diluted with water or the like as necessary. What is necessary is just to set the thickness of the sealer layer finally formed suitably by a desired fireproof performance, an application site | part, etc. Preferably it is 0.01-10 mm, More preferably, it is 0.1-5 mm, More preferably, it is 0.2-3 mm.

  In the multilayer coating film forming method of the present invention, at least a base enamel layer is formed on the sealer layer in order to protect the fireproof sealer layer formed by using the water-based foamed fireproof coating composition of the present invention. A multilayer having a top enamel layer and a clear layer in this order is formed. Such a multi-layer can be formed by sequentially applying any appropriate water-based or solvent-type paint, which is usually used as a base enamel layer, a top enamel layer, and a clear layer. Any appropriate coating method can be adopted as a coating method of various paints for forming such a multilayer. For example, a coating method such as spraying, rollering, brushing, trowel, spatula or the like is used to coat and apply once or several times. After coating, it may be dried at any appropriate temperature and time as required. At the time of painting, the paint used with water or the like can be diluted as necessary. What is necessary is just to set the thickness of the multilayer finally formed suitably by a desired fireproof performance, an application site | part, etc. Preferably it is 0.01-30 mm, More preferably, it is 0.1-20 mm, More preferably, it is 0.2-10 mm.

In the multilayer coating film forming method of the present invention, the organic mass in the multilayer coating film to be formed (the sealer layer + the multilayer) is 5 to 75 g / m ² , preferably 25 to 65 g / m. ² . The organic mass can be satisfied by setting the blending ratio of the chlorinated resin emulsion (2-2) contained in the aqueous foam fire-resistant paint composition of the present application within the predetermined range. This organic mass is calculated by a measurement method based on the fact that the maximum heat generation rate in a corn calorimeter is 50 KW / m ² or less and does not indicate continuous combustion, and details will be described later. When the organic mass in the formed multilayer coating film falls within the above range, a multilayer coating film excellent in fire resistance can be obtained. When the organic mass in a multilayer coating film exceeds 75 g / m < ² >, there exists a possibility that this multilayer coating film may be inferior to fire resistance. Even if the fire resistance of the sealer layer formed using the water-based foam fire-resistant paint composition of the present invention is excellent, when the organic mass in the multilayer coating film exceeds 75 g / m ² , It means that it is inferior to fire resistance when evaluated as the whole multilayer coating film.

Multilayer coating film formed in the multilayer coating film forming method of the present invention, the total amount of heat generated at the heat generating resistance test conforming ISO5660Part1 is, preferably 8 MJ / ^{m 2} or less, more preferably 7.5 mJ / ^{m 2} Or less, more preferably 7.0 MJ / m ² or less, and particularly preferably 6.5 MJ / m ² or less. The lower limit of the total calorific value is preferably as low as possible, and the preferable lower limit is 0 MJ / m ² , but the realistic lower limit is 0.5 MJ / m ² . When the total calorific value of the multilayer coating film formed in the multilayer coating film forming method of the present invention exceeds 8 MJ / m ² , the fire extinguishing action, the heat insulating action, and the fire resistance may not be sufficient. By setting the organic mass ratio in the water-based foamed fireproof coating composition of the present invention and the chlorine element concentration in the coating film within the above-mentioned predetermined ranges, the total calorific value can be set within the above preferred range. Further, the blending ratio of the organic-inorganic hybrid emulsion (1) and the foaming filler (2) and / or the blending ratio of the chlorinated resin emulsion (2-2) contained in the aqueous foam fire-resistant paint composition of the present invention, By setting the above-mentioned predetermined range, the total calorific value can be set to the above preferable range.

  The multilayer coating film formed in the multilayer coating film forming method of the present invention makes the coating film itself difficult to burn by setting the organic mass ratio in the aforementioned desirable range, while the chlorine element contained in the coating film is In addition, it can exhibit excellent fire extinguishing action due to sufficient generation of chlorine gas and excellent heat insulation effect due to sufficient carbonized layer formation when the coating film burns, and also has excellent fire resistance, excellent water permeability resistance, and excellent warm water resistance Excellent weather resistance can be expressed.

In the multilayer coating film formed in the multilayer coating film forming method of the present invention, the maximum value of the heat generation rate in the exothermic test according to ISO 5660 Part 1 is preferably 80 KW / m ² or less, more preferably 70 KW / m ^2. or less, still more preferably not more than 60 KW / ^{m 2,} particularly preferably not more than 50 KW / ^{m 2,} and most preferably not more than 40 KW / ^{m 2.} The lower the lower limit of the heat generation rate, the better. The preferable lower limit is 1 KW / m ² . When the maximum value of the heat generation rate of the multilayer coating film formed in the multilayer coating film forming method of the present invention exceeds 80 KW / m ² , the fire extinguishing action, the heat insulating action, and the fire resistance may not be sufficient. By setting the organic mass ratio in the water-based foam fire-resistant paint composition of the present invention and the chlorine element concentration in the coating film to the above-mentioned predetermined ranges, the maximum value of the heat generation rate can be set to the above-mentioned preferable range. it can. Further, the blending ratio of the organic-inorganic hybrid emulsion (1) and the foaming filler (2) and / or the blending ratio of the chlorinated resin emulsion (2-2) contained in the aqueous foam fire-resistant paint composition of the present invention, By setting the above-mentioned predetermined range, the maximum value of the heat generation rate can be set to the above preferable range.

≪C. Painted items >>
The coated product of the present invention includes a multilayer coating film obtained by the multilayer coating film forming method of the present invention on a substrate.

  Any appropriate base material can be adopted as the base material. For example, ceramic building materials, concrete, steel materials, wooden members, resin-based members, and the like can be given. Such a substrate may be subjected to a rust prevention treatment or the like.

  The method for forming the multilayer coating film obtained by the multilayer coating film forming method of the present invention on the substrate is as described above.

  Since the coated product of the present invention is provided with the multilayer coating film obtained by the multilayer coating film forming method of the present invention, it has excellent fire extinguishing action due to sufficient generation of chlorine gas and excellent heat insulation effect due to sufficient carbonization layer formation. As well as excellent fire resistance, excellent water permeability, excellent warm water resistance, and excellent weather resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on mass. The unit of numerical values in the table is parts by mass unless otherwise specified. The meanings of the abbreviations in the table are as follows.

KR510: Methyl / phenyl-containing methoxysilane oligomer (manufactured by Shin-Etsu Silicone)
KBM22: Dimethyldimethoxysilane (manufactured by Shin-Etsu Silicone)
MMA: Methyl methacrylate St: Styrene CHMA: Cyclohexyl methacrylate 2-EHA: 2-ethylhexyl acrylate HEMA: Hydroxyethyl methacrylate AA: Acrylic acid APS: Ammonium persulfate Snowtex C: Colloidal silica (manufactured by Nissan Chemical Industries, Ltd.)
HALS: Light stabilizer Tinuvin 292 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
UVA: Ultraviolet absorber Tinuvin 1130 (manufactured by Ciba Specialty Chemicals)

<Measurement of ash content at 500 ° C>
Using a TG / DTA (Thermogravimetry / Differential Thermal Analysis) 320 thermal mass / differential thermal simultaneous measuring instrument (manufactured by Seiko Denshi Kogyo Co., Ltd.), the heating rate was 10 ° C./min, the inside of the tank was refluxed with nitrogen, 500 ° C. The heating residual amount at the time was calculated | required and 500 degreeC ash content was computed by the following formula.
500 ° C. Ash content (%) = (Remaining heating amount at 500 ° C. (g)) / (Initial dry mass (g))

<Calculation method of organic mass ratio>
The organic mass ratio was calculated by the following formula.
Organic mass ratio (%) = 100 (%) − 500 ° C. ash (%)

<Measurement of total calorific value>
An exothermic test conforming to ISO 5660 Part 1 was performed, and the total calorific value for 20 minutes after the start of heating was measured. Similar to the criteria for the exothermic test in conformity with ISO 5660 Part 1, the case where the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less passes (○), and the case where it exceeds 8 MJ / m ² is rejected (×). did.

<Measurement of heat generation rate>
An exothermic test conforming to ISO 5660 Part 1 was conducted, and the maximum exothermic rate was measured for 20 minutes after the start of heating. The case where the maximum heat generation rate in 20 minutes after the start of heating was 80 KW / m ² or less was determined to be acceptable (◯), and the case where it exceeded 80 KW / m ² was determined to be unacceptable (x).

<Evaluation of water resistance>
A φ75 mm funnel was affixed to the test plate to be evaluated, and the water permeation resistance was evaluated according to the funnel method of JIS K 5400. Evaluation was performed according to the following criteria.
○: Water reduction after 24 hours is 500 cc / m ² or less Δ: Water reduction after 24 hours exceeds 500 cc / m ² and 1000 cc / m ² or less ×: Water reduction after 24 hours exceeds 1000 cc / m ²

<Evaluation of hot water resistance>
The appearance when the test plate to be evaluated was immersed in warm water at 60 ° C. for 10 days was evaluated. Evaluation was performed according to the following criteria.
○: Blister is not seen △: Blister occurs only at the end ×: Blister occurs uniformly over the entire test plate surface

<Evaluation of weather resistance>
The test plate to be evaluated was irradiated for 4 hours and wetted for 4 hours using an i-super UV tester (manufactured by Iwasaki Electric Co., Ltd.). The color difference was evaluated by ΔE using a SM color computer color difference meter (SM-5, manufactured by Suga Test Instruments Co., Ltd.). The weather resistance was evaluated according to the following criteria.
○: Gloss retention is 80% or more and color difference ΔE is less than 3 Δ: Gloss retention is 50% or more, color difference ΔE is 3 or more and less than 6 ×: Gloss retention is less than 50% and color difference ΔE is 6 or more

[Production Examples 1 to 7]: Production of Organic-Inorganic Hybrid Emulsions (1) to (7) After mixing each component at a blending ratio (mass basis) described in Table 1 to make a uniform solution, a reactive emulsifier ( ADEKA rear soap SR-1025 (manufactured by ADEKA) was mixed and emulsified using an emulsifier (TK Robotics, manufactured by PRIMIX) while cooling with ice to obtain an emulsion.
In a separate reaction vessel, 100 parts by mass of deionized water was added, the internal temperature was set to 70 ° C., and the emulsion obtained above and 0.20 part by mass of a radical polymerization initiator (ammonium persulfate) were added dropwise over 2 hours. Aging was performed for 2 hours to complete the polymerization of the organic components.
Thereafter, the internal temperature of the reaction vessel was set to 85 ° C., and aging was further performed for 10 hours to perform hydrolysis and condensation reaction of the inorganic components.
As described above, organic-inorganic hybrid emulsions (1) to (7) were obtained.

[Production Example 8]: Production of emulsion (A) of chlorinated resin Chlorinated paraffin (chlorine content 70%, molecular weight 1156, Ajinomoto Fine Techno Co., Ltd.) 250 parts by mass, chlorinated paraffin (chlorine content 40%, After adjusting molecular weight 611, Ajinomoto Fine Techno Co., Ltd.) 250 parts by mass, emulsifier (Newcol 707SF, polyoxyethylene polycyclic phenyl ether sulfate ester, Kao Co., Ltd.) 200 parts by mass to 95 ° C. with stirring, After mixing and transferring 300 parts by mass of deionized water adjusted to 95 ° C., the mixture was stirred for 30 minutes. Thereafter, the mixture was emulsified using an emulsifier (manufactured by Sanwa Engineering Co., Ltd., high-pressure homogenizer H20) to obtain a chlorinated resin emulsion (A).
The 500 ° C. ash content of the chlorinated resin emulsion (A) was 25%.

[Production Example 9]: Preparation of emulsion (B) of chlorinated resin 400 parts by mass of chlorinated paraffin (chlorine content 70%, molecular weight 1156, manufactured by Ajinomoto Fine Techno Co.), chlorinated paraffin (chlorine content 40%, After adjusting the molecular weight 611, 100 parts by mass of Ajinomoto Fine Techno Co., Ltd., and 200 parts by mass of an emulsifier (Newcol 707SF, polyoxyethylene polycyclic phenyl ether sulfate, Kao Co., Ltd.) to 95 ° C. with stirring, After mixing and transferring 300 parts by mass of deionized water adjusted to 95 ° C., the mixture was stirred for 30 minutes. Thereafter, the mixture was emulsified using an emulsifier (manufactured by Sanwa Engineering Co., Ltd., high-pressure homogenizer H20) to obtain an emulsion (B) of a chlorinated resin.
The 500 ° C. ash content of the chlorinated resin emulsion (B) was 30%.

[Examples 1 to 5]: Production and evaluation of water-based foam fire-resistant paint compositions (1) to (5) The blending ratio (based on mass) shown in Table 2 (however, as a blend not listed in Table 2, (Thickeners, plasticizers, pH adjusters, preservatives, dispersants, antifoaming agents are mixed in appropriate amounts) After mixing each component uniformly, adjust the overheating residue to NV = 45%. Water-based foam fireproof paint compositions (1) to (5) were produced.
Table 2 shows the evaluation results of the obtained water-based foam fire-resistant paint compositions (1) to (5).

[Comparative Examples 1 to 4]: Manufacture and evaluation of water-based foam fire-resistant paint compositions (C1) to (C4) The blending ratio (based on mass) shown in Table 2 (however, as a blend not listed in Table 2, (Thickeners, plasticizers, pH adjusters, preservatives, dispersants, antifoaming agents are mixed in appropriate amounts) After mixing each component uniformly, adjust the overheating residue to NV = 45%. Water-based foam fire-resistant paint compositions (C1) to (C4) were produced.
Table 2 shows the evaluation results of the obtained water-based foam fire-resistant paint compositions (C1) to (C4).

[Production Example 10]: Preparation of base enamel For UDITE 339 base manufactured by Nippon Paint Co., Ltd. (beige color) (superheated residue NV = 47.0%, content of organic component in coating film solid content = 60. 0%) was the base enamel.

[Production Example 11]: Preparation of top enamel for AUDEITE 339 top manufactured by Nippon Paint Co., Ltd. (light beige) (superheated residue is NV = 47.0%, content of organic component in coating film solid content = 60 0.0%) was the top enamel.

[Production Examples 12 to 16]: Production of Clears (1) to (5) Composition ratios (mass basis) described in Table 3 (however, as a composition not described in Table 3, thickener, plasticizer, After mixing each component uniformly with an appropriate amount of pH adjuster, preservative, dispersant, and antifoaming agent), the superheat residue is adjusted to NV = 35%, and clear (1)-( 5) was produced.

[Example 6]: Production and evaluation of multilayer coating film (1) and coated product (1) Aqueous foam fire-resistant paint composition obtained in Example 1 on the surface of a wood cement ceramic building material (specific gravity 1.1) The product (1) was applied by air spraying under the coating conditions shown in Table 4 and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 4, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 4, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (4) obtained in Production Example 15 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 4, and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (1) provided with a multilayer coating film (1) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 16 shows the results of evaluation on the obtained coated product (1).

[Example 7]: Production and evaluation of multilayer coating film (2) and coated product (2) Aqueous foam fire-resistant paint composition obtained in Example 2 on the surface of a wood cement ceramic building material (specific gravity 1.1) The product (2) was applied by air spraying under the coating conditions shown in Table 5, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 5, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was coated with a sponge roll coater under the coating conditions shown in Table 5, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Then, on the top enamel layer, the clear (3) obtained in Production Example 14 was applied by air spraying under the coating conditions shown in Table 5, and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (2) provided with a multilayer coating film (2) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 16 shows the results of evaluation on the obtained coated product (2).

[Example 8]: Production and evaluation of multilayer coating film (3) and coated article (3) Aqueous foam fire-resistant paint composition obtained in Example 3 on the surface of a wood cement ceramic building material (specific gravity 1.1) The product (3) was applied by air spraying under the coating conditions shown in Table 6, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 6, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Further, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 6, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Then, on the top enamel layer, the clear (2) obtained in Production Example 13 was applied with air spray under the coating conditions shown in Table 6 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (3) provided with a multilayer coating film (3) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 16 shows the results of evaluation on the obtained coated product (3).

[Example 9]: Production and evaluation of multilayer coating film (4) and coated product (4) Aqueous foam fire-resistant paint composition obtained in Example 4 on the surface of a wood cement ceramic building material (specific gravity 1.1) The product (4) was applied by air spraying under the coating conditions described in Table 7, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions described in Table 7, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 7, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (1) obtained in Production Example 12 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 7 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (4) provided with the multilayer coating film (4) on the surface of the wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 16 shows the results of evaluation on the obtained coated product (4).

[Example 10]: Production and evaluation of multilayer coating film (5) and coated product (5) Aqueous foam fire-resistant paint composition obtained in Example 1 on the surface of a wood cement ceramic building material (specific gravity 1.1) The product (1) was applied by air spraying under the coating conditions shown in Table 8, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 8, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 8, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (1) obtained in Production Example 12 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 8, and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (5) provided with a multilayer coating film (5) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 16 shows the results of evaluation on the obtained coated product (5).

[Example 11]: Production and evaluation of multilayer coating film (6) and coated product (6) Aqueous foam fire-resistant paint composition obtained in Example 5 on the surface of a wood cement ceramic building material (specific gravity 1.1) The product (5) was applied by air spraying under the coating conditions shown in Table 9, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 9, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was coated with a sponge roll coater under the coating conditions shown in Table 9, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Then, on the top enamel layer, the clear (2) obtained in Production Example 13 was applied by air spraying under the coating conditions shown in Table 9 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (6) provided with the multilayer coating film (6) on the surface of the wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 16 shows the results of evaluation on the obtained coated product (6).

[Comparative Example 5]: Production and Evaluation of Multi-layer Coating Film (C1) and Painted Product (C1) Aqueous Foam Refractory Paint Composition Obtained in Comparative Example 3 on the Surface of Wood Cement Ceramic Building Material (Specific Gravity 1.1) The product (C3) was applied by air spraying under the coating conditions shown in Table 10, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 10, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Further, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 10, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (5) obtained in Production Example 16 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 10 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (C1) having a multilayer coating film (C1) on the surface of the wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 17 shows the results of evaluation on the obtained coated product (C1).

[Comparative Example 6]: Manufacture and Evaluation of Multilayer Coating Film (C2) and Painted Product (C2) Aqueous Foam Refractory Paint Composition Obtained in Comparative Example 3 on the Surface of Wood Cement-Based Ceramic Building Material (Specific Gravity 1.1) The product (C3) was applied by air spraying under the coating conditions shown in Table 11, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions described in Table 11, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 11, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (1) obtained in Production Example 12 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 11 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (C2) having a multilayer coating film (C2) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 17 shows the results of evaluation on the obtained coated product (C2).

[Comparative Example 7]: Production and Evaluation of Multi-layer Coating Film (C3) and Painted Product (C3) Aqueous Foam Refractory Paint Composition Obtained in Comparative Example 3 on the Surface of Wood Cement Ceramic Building Material (Specific Gravity 1.1) The product (C3) was applied by air spraying under the coating conditions described in Table 12, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions described in Table 12, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 12, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. A clear layer was not formed on the top enamel layer.
As described above, a coated product (C3) provided with a multilayer coating film (C3) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 17 shows the results of evaluation on the obtained coated product (C3).

[Comparative Example 8]: Manufacture and Evaluation of Multilayer Coating Film (C4) and Painted Product (C4) Aqueous Foam Refractory Paint Composition Obtained in Comparative Example 2 on the Surface of Wood Cement Ceramic Construction Material (Specific Gravity 1.1) The product (C2) was applied by air spraying under the coating conditions shown in Table 13, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 13, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was applied with a sponge roll coater under the coating conditions shown in Table 13, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (1) obtained in Production Example 12 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 13, and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated product (C4) provided with a multilayer coating film (C4) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 17 shows the results of evaluation on the obtained coated product (C4).

[Comparative Example 9]: Manufacture and Evaluation of Multilayer Coating Film (C5) and Painted Product (C5) Aqueous Foam Refractory Paint Composition Obtained in Comparative Example 1 on the Surface of Wood Cement Ceramic Building Material (Specific Gravity 1.1) The product (C1) was applied by air spraying under the coating conditions described in Table 14, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 14, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Further, on the base enamel layer, the top enamel obtained in Production Example 11 was coated with a sponge roll coater under the coating conditions shown in Table 14, and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (1) obtained in Production Example 12 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 14 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (C5) provided with a multilayer coating film (C5) on the surface of the wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 17 shows the results of evaluation on the obtained coated product (C5).

[Comparative Example 10]: Production and Evaluation of Multilayer Coating Film (C6) and Painted Product (C6) Aqueous Foam Refractory Paint Composition Obtained in Comparative Example 4 on the Surface of Wood Cement-Based Ceramics Building Material (Specific Gravity 1.1) The product (C4) was applied by air spraying under the coating conditions shown in Table 15, and dried at 100 ° C. for 5 minutes to form a sealer layer. Next, the base enamel obtained in Production Example 10 was applied on the sealer layer by air spraying under the coating conditions shown in Table 15, and dried at 100 ° C. for 5 minutes to form a base enamel layer. . Furthermore, on the base enamel layer, the top enamel obtained in Production Example 11 was coated with a sponge roll coater under the coating conditions shown in Table 15 and dried at 100 ° C. for 5 minutes to form a top enamel layer. did. Thereafter, the clear (3) obtained in Production Example 14 was applied on the top enamel layer by air spraying under the coating conditions shown in Table 15 and dried at 100 ° C. for 5 minutes to form a clear layer. did.
As described above, a coated article (C6) having a multilayer coating film (C6) on the surface of a wood cement ceramic building material (specific gravity 1.1) was obtained.
Table 17 shows the results of evaluation on the obtained coated product (C6).

Table 16 shows that for Examples 6 to 11 in which a multi-layer coating film was formed using the water-based foam fire-resistant paint composition of the present invention to construct a coated material, the total calorific value for 20 minutes after the start of heating even 8 MJ / ^{m 2} or less (ISO5660Part1 acceptance level criteria pyrogenic test compliant), and the maximum heat release rate are both at 80 kW / ^{m 2} or less at the start of heating after 20 minutes (acceptable level), the water penetration resistance The evaluation of each is ○ (water loss after 24 hours is 500 cc / m ² or less), and the evaluation of warm water resistance is ○ (no blisters are observed) or Δ (blisters are generated only at the edges). Yes, all of the weather resistance evaluation is ○ (gloss retention is 80% or more, color difference ΔE is less than 3), excellent fire extinguishing action due to sufficient generation of chlorine gas, and excellent heat insulation effect due to sufficient carbonization layer formation. Departure Together are made, good fire resistance, excellent water penetration resistance, excellent warm water resistance, it can be seen that can exhibit excellent weatherability.

On the other hand, when Table 17 is seen, about the comparative example 5 (equivalent to the conventional normal ceramics building material coating conditions), the total calorific value for 20 minutes after the start of heating greatly exceeds 8 MJ / m ² (heat generation according to ISO 5660 Part 1). The highest heat generation rate in 20 minutes after the start of heating greatly exceeds 80 KW / m ² (failed level), and the weather resistance evaluation is △ (gloss retention is 50% or more) The color difference ΔE was 3 or more and less than 6.

In Comparative Example 6 (corresponding to the case using Clear (1) obtained in Production Example 12 instead of Clear (5) in Comparative Example 5), the total calorific value for 20 minutes after the start of heating was 8 MJ / m ^2. (According to ISO 5660 Part 1 exothermic test criteria), the maximum heat generation rate in 20 minutes after the start of heating greatly exceeds 80 KW / m ² (fail level), and the weather resistance is evaluated. Δ (gloss retention is 50% or more, color difference ΔE is 3 or more and less than 6).

For Comparative Example 7 (corresponding to the case where there is no clear layer in Comparative Example 5), the total calorific value for 20 minutes after the start of heating exceeds 8 MJ / m ² (failed by the judgment standard of the exothermic test according to ISO 5660 Part 1) Level), the maximum heat generation rate in 20 minutes after the start of heating exceeds 80 KW / m ² (failed level), and the water permeability evaluation is △ (the amount of water reduction after 24 hours exceeds 500 cc / m ² and 1000 cc / M ² or less), the evaluation of hot water resistance is Δ (blisters are generated only at the edges), and the evaluation of weather resistance is × (gloss retention is less than 50%, color difference ΔE is 6 or more). .

For Comparative Example 8 (corresponding to a case in which a sealer layer was formed using the water-based foamed fire-resistant paint composition (C2) which is a colloidal silica blend sealer produced in Comparative Example 2), the water permeation resistance was evaluated as Δ (24 hours The subsequent water reduction amount exceeds 500 cc / m ² and is 1000 cc / m ² or less), the evaluation of hot water resistance is x (blisters are uniformly generated on the entire test plate surface), and the evaluation of weather resistance is Δ (The gloss retention was 50% or more and the color difference ΔE was 3 or more and less than 6).

For Comparative Example 9 (corresponding to the case where the sealer layer was formed using the water-based foam fire-resistant paint composition (C1), which is the acrylic sealer produced in Comparative Example 1), the total calorific value for 20 minutes after the start of heating was 8 MJ / m ² was exceeded (ISO5660Part1 unacceptable level criterion pyrogenic test compliant).

  For Comparative Example 10 (corresponding to the case where the sealer layer was formed using the water-based foamed fire-resistant paint composition (C4) of Comparative Example 4), the total heat generation amount and the heat generation rate exceeded the specified values, so the evaluation result was × Met. Further, the evaluation of weather resistance was Δ (gloss retention was 50% or more, color difference ΔE was 3 or more and less than 6).

  The water-based foam fire-resistant paint composition of the present invention and the multilayer coating film formed using the same are effective in increasing the temperature of the outer wall base material by quickly forming a foam insulation layer when exposed to a flame. Therefore, the present invention can be preferably applied to a painted material that requires fire resistance, such as an outer wall of a house.

Claims (8)

An organic-inorganic hybrid emulsion (1) containing an organic binder component and an inorganic binder component, and a foam filler (2), wherein the foam filler (2) is composed of a polyphosphate (2-1) and a chlorinated resin. An aqueous foam refractory paint composition comprising an emulsion (2-2),
The chlorine element concentration in the coating film provided by the coating composition is 1 to 20% by mass,
The organic mass ratio in the coating composition is 5 to 30%.
Water-based foam fireproof coating composition.   2. The solid content ratio (1) :( 2) between the organic-inorganic hybrid emulsion (1) and the foam filler (2) is 1: 9 to 7: 3 by mass ratio. Water-based foam fireproof coating composition.   The solid content ratio (2-1) :( 2-2) of the polyphosphate (2-1) and the emulsion (2-2) of the chlorinated resin is 9: 1 to 3: The water-based foam fire-resistant paint composition according to claim 1 or 2, which is 7.   The water-based foam refractory paint composition according to any one of claims 1 to 3, wherein the chlorinated resin has a number average molecular weight of 500 to 5,000.   The density | concentration of the chlorine element in the coating film which the said coating composition gives is 2-18 mass%, and the organic mass ratio in the said coating composition is 5-20% in any one of Claim 1-4 The water-based foam fireproof coating composition as described.   The organic-inorganic hybrid emulsion (1) contains at least one (a) selected from an organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane, and a radical polymerizable vinyl monomer (b). The aqueous foam fire-resistant paint composition according to any one of claims 1 to 5, which is an aqueous dispersion obtained by hydrolysis, condensation reaction, and radical polymerization of the mixture in an emulsified state. A sealer layer is formed using the water-based foam fire-resistant paint composition according to any one of claims 1 to 6, and at least a base enamel layer, a top enamel layer, and a clear layer are provided in this order on the sealer layer. Forming a layer, a method for forming a multilayer coating film,
The organic mass in the multilayer coating film calculated by a measurement method based on the fact that the maximum heat generation rate in a corn calorimeter is 50 KW / m ² or less and does not show continuous combustion is 5 to 75 g / m ² . A method for forming a multilayer coating film. A coated article comprising a multilayer coating film obtained by the multilayer coating film forming method according to claim 7 on a substrate.