JP2021188037A - Aqueous foamable fire proof coating composition - Google Patents

Abstract

To propose an aqueous foamable fireproof coating composition excellent in both of water proofness of a coated film in a normal period and fire proofness of an expanded coated film generated in a fire disaster.SOLUTION: The aqueous foamable fireproof coating composition includes: a polyvalent metal compound (A) containing a metal element which can take an ion atomic valence of bivalent or more; a resin (B) having a functional group capable of forming a metal cross linking with the metal element containing the polyvalent metal compound; a char-forming auxiliary material (C); and water. A method of coating a substrate includes coating a substrate surface with the aqueous foamable fireproof coating composition. A method of protecting a structure from heat and a fire disaster includes coating a substrate surface with the aqueous foamable fireproof coating composition.SELECTED DRAWING: None

Description

The present invention relates to an aqueous foam fireproof coating composition containing water as a dilution medium.

Since iron suddenly loses its strength at around 500 ° C, the steel-framed structure collapses in the event of a fire, making it impossible to evacuate or extinguish the fire. Therefore, in order to maintain the strength for a specified time even in the event of a fire, it is obligatory by the Building Standards Law to apply a fireproof coating with heat insulating properties to the steel frame of the structure. The fireproof coating material includes rock wool fireproof coating material and foamed fireproof paint. Rock wool fireproof coating materials are inexpensive and widely distributed in the market, but they require a thickness of 1 cm to several cm in order to exhibit fireproof performance, and there is a problem that spraying work is difficult.

On the other hand, the foamed refractory paint is a coating material that exhibits heat insulating properties by expanding the coating film due to the temperature rise at the time of fire. Unlike rock wool, the fire-resistant coating using foam fire-resistant paint is a thin film in normal times, does not impair the shape of the structure itself, expands and carbonizes in the event of a fire, and is made of iron by a flame-retardant heat insulating layer called char. It is possible to suppress the temperature rise of the structure and delay the collapse of the structure.

As the foamed fireproof paint, the present applicant has proposed in Patent Document 1 a foamed fireproof paint containing a hydrolyzable silyl group-containing resin, a plasticizer, a foaming agent, and a carbonizing agent. With this paint, a protective coating film that is easy to apply thickly and has excellent physical properties such as quick-drying, internal curability, and water resistance can be obtained, and a foam layer with excellent fire resistance under fire conditions can be obtained. It can be formed.

However, the foamed refractory paint described in Patent Document 1 contains an organic solvent as a diluting medium, and has a problem of odor when it is applied in a hospital, school, or the like. In addition, there is a problem that it is not possible to perform parallel work with electrical work due to the scattering of organic solvent, and there is an increasing demand for water-based foam refractory paint using water as a dilution medium.

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

Japanese Unexamined Patent Publication No. 2018-159065 Japanese Unexamined Patent Publication No. 2015-59180

Refractory paints are required to have physical properties such as coating workability and water resistance in normal times, and fire resistance in the event of a fire. In order to improve the physical properties such as water resistance of the coating film in normal times, it is effective to crosslink the resin that forms the coating film, but if this method is used, the coating film will not easily expand in the event of a fire, and it will have sufficient fire resistance. Often the sex is not obtained. In this way, there is a trade-off between the water resistance of the coating film in normal times and the fire resistance in the event of a fire. Moreover, since it is difficult to form a film of a coating film formed from a water-based paint as compared with an organic solvent-based paint, an effective method for achieving both of these has not been found.

An object of the present invention is to obtain a water-based foamed refractory paint composition in which both the water resistance of the coating film in normal times and the fire resistance of the expanded coating film generated in the event of a fire are good without limiting the applicable range of the foamed refractory paint. To make a suggestion.

The present inventors have diligently studied the above-mentioned problems. As a result, according to the metal cross-linking formed by the metal element contained in the polyvalent metal compound and the functional group in the resin, water resistance can be ensured by the dense cross-linking structure in normal times, and at high temperature such as in a fire. It has been found that the crosslinked structure is decomposed to form a coating film exhibiting high fire resistance without hindering expansion.

That is, the present invention is described in Item 1.
Multivalent metal compound (A) containing a metal element capable of having an ionic valence of divalent or higher,
A water-based foam fireproof coating composition containing a resin (B) having a functional group capable of forming a metal crosslink with a metal element contained in the polyvalent metal compound (A), a char forming auxiliary agent (C), and water.
Item 2
Item 2. The aqueous foam fireproof coating composition according to Item 1, wherein the polyvalent metal compound (A) is a metal oxide.
Item 3
Item 2. The aqueous foam fire-resistant coating composition according to Item 1, wherein the polyvalent metal compound (A) is an organic acid metal salt.
Item 4
Any one of Items 1 to 3, wherein the amount of the polyvalent metal compound (A) used is in the range of 0.1 to 2.0 equivalents with respect to 1 equivalent of the functional group contained in the resin (B). The water-based foam fireproof coating composition according to the section.
Item 5
Item 6. The aqueous foam fireproof coating composition according to any one of Items 1 to 4, wherein the functional group in the resin (B) is a carboxyl group.
Item 6
Item 6. The water-based foamed refractory paint composition according to any one of Items 1 to 5, wherein the resin (B) has an acid value of 3 to 100 mgKOH / g.
Item 7
Item 5. The aqueous foam fireproof coating composition according to Item 5 or 6, wherein the resin (B) is a copolymer emulsion of a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers.
Item 8
Item 2. The aqueous foam fireproof coating composition according to Item 7, wherein the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is in the range of 1 to 10% by mass in the total polymerizable unsaturated monomer.
Item 9
Item 6. The aqueous foam fireproof coating composition according to any one of Items 1 to 8, further comprising a carbon source.
Item 10
Item 6. The water-based foaming fireproof coating composition according to any one of Items 1 to 9, further comprising a foaming agent.
Item 11
A two-component paint composition in which the first component (I) and the second component (II) are mixed immediately before use, and the first component (I) contains a polyvalent metal compound (A), and the second component (I) is contained. Item 6. The water-based foamed refractory paint composition according to any one of Items 1 to 10, wherein the component (II) contains a resin (B).
Item 12
A method for coating a substrate, which comprises coating the surface of the substrate with the aqueous foam fireproof coating composition according to any one of Items 1 to 11.
Item 13
A method for protecting a structure from heat and fire, which comprises applying the aqueous foam fireproof coating composition according to any one of Items 1 to 11 to the surface of a substrate.
Regarding.

The water-based foam refractory coating composition of the present invention has good coating workability, and a coating film having a good appearance can be obtained.
Since this coating film forms a dense crosslinked structure in normal times, it has excellent physical properties such as water resistance, and can protect the structure from stimuli such as ultraviolet rays and rainwater. The coating film formed by this water-based foamed refractory paint composition expands at a high temperature such as in a fire and exhibits excellent heat insulating properties, so that it is possible to delay the disintegration of the structure due to heat.

In the present invention, the mass of the non-volatile component in the water-based foam fire-resistant coating composition is a sample of a water-based foam fire-resistant coating composition having a known mass (for example, 0.3 g), which is placed in a pre-weighed aluminum dish. The sample can be heated in an oven at 105 ° C. for 30 minutes, the mass of the dish can be measured again and calculated from the mass before heating and the mass of the sample after heating (see ASTM D2697).

In the present specification, the non-volatile component means a residue excluding volatile components, and the residue may be solid or liquid at room temperature.

The water-based foam fire-resistant coating composition of the present invention comprises a polyvalent metal compound (A) containing a metal element having an ionic valence of 2 or more, and a metal cross-linking with the metal element contained in the polyvalent metal compound (A). It contains a resin (B) having a formable functional group, a char forming aid (C), and water.

<Multivalent metal compound (A)>
In the present invention, the polyvalent metal compound (A) is a polyvalent metal compound containing a metal element having a divalent or higher valence, preferably 2 to 4 valences, and is, for example, Mg, Ca, Ba, and the like. Examples thereof include compounds containing metal elements such as Fe, Cu, Zn, Al, Ti, Si, Zr and Mn.
As the multivalent metal compound, either an inorganic metal compound or an organometallic compound is preferably used.

Examples of the inorganic metal compound include metal oxides, metal hydroxides, metal nitrates, metal sulfates, metal phosphates and the like. Of these, metal oxides are preferable.

Examples of the organic metal compound include organic acid metal salts, metal alkoxides, organic metal complexes and the like. Of these, organic acid metal salts are preferable.

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

The amount of the polyvalent metal compound (A) used is a functional group capable of forming a metal crosslink contained in the resin (B) described later from the viewpoint of the water resistance of the cured coating film and the fire resistance of the char generated during heating. It is suitable that the metal equivalent is adjusted to be within the range of 0.1 to 2.0 equivalents, preferably 0.15 to 1.0 equivalents with respect to 1 equivalent.

<Resin (B)>
In the present invention, as the resin (B), a resin that can be dissolved or dispersed in water is used. The resin type is not particularly limited, and in the form of dispersed particles, it may be in the form of a single layer or a multi-layered form such as a core-shell type.

As the resin (B), conventionally known ones can be used without particular limitation as long as they have the ability to form a coating film, and specific examples thereof include an acrylic resin emulsion, an acrylic silicon resin emulsion, a urethane resin emulsion, and a fluororesin emulsion. , Emulsion resin emulsion, polyester resin emulsion, alkyd resin emulsion, melamine resin emulsion and the like, but are not limited thereto. In addition, these may be used alone or in combination of two or more.

The resin (B) has a functional group capable of forming a metal crosslink with a metal element contained in the polyvalent metal compound (A). Metal cross-linking is a cross-linking structure that connects molecules of a resin via a metal. The present inventors decompose such metal crosslinks at a lower temperature than the cross-linking structure by covalent bonds between non-metals, so that they do not hinder the expansion of the coating film when exposed to a flame and have heat insulating properties. I thought it would form an excellent char. Examples of the functional group capable of forming the metal bridge include a carboxyl group, a hydroxyl group, an acid anhydride group (-COOCO-) and the like, and a carboxyl group or an acid anhydride group is particularly preferable.

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

Examples of the resin (B) include copolymer emulsions of carboxyl group-containing polymerizable unsaturated monomers and other polymerizable unsaturated monomers.

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

When producing a copolymer emulsion, the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is preferably in the range of 1 to 20% by mass, particularly 3 to 10% by mass in the total polymerizable unsaturated monomer. be.

Other polymerizable unsaturated monomers include
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n- Hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl acrylate ( Alkyl such as Osaka Organic Chemical Industry Co., Ltd., trade name), cyclohexyl (meth) acrylicate, methylcyclohexyl (meth) acrylicate, t-butylcyclohexyl (meth) acrylicate, cyclododecyl (meth) acrylicate, etc. Or cycloalkyl (meth) acrylate;
(Meta) acrylate having an isobornyl group such as isobornyl (meth) acrylate;
(Meta) acrylate having an adamantyl group such as adamantyl (meth) acrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene;
Polymerization with an alkoxysilyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane Sexual unsaturated monomer;
Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate;
Polymerizable unsaturated monomer having a fluorinated alkyl group such as a fluoroolefin;
Monomer having a photopolymerizable functional group such as a maleimide group;
Nitrogen-containing (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, adducts of glycidyl (meth) acrylate and amines, etc. Polymerizable unsaturated monomer;
(Meta) acrylic acid such as 2-hydroxyethyl (meth) acrylicate, 2-hydroxypropyl (meth) acrylicate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2 carbon atoms. Monoesterified product of ~ 8 dihydric alcohol, ε-caprolactone modified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms, N-hydroxymethyl (meth) acrylamide, allylalco- Le, a hydroxyl group-containing polymerizable unsaturated monomer such as (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end;
Glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate , Epoxy group-containing polymerizable unsaturated monomers such as allylglycidyl ether;
A (meth) acrylate having a polyoxyethylene chain whose molecular end is an alkoxy group;
2-acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, sodium styrenesulfonic acid, sulfoethylmethacrylate, and sulfonic acid group-containing polymerizable unsaturated monomers such as sodium salts or ammonium salts thereof;
Phosphoric acid group-containing polymerizable unsaturated monomers such as 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate;
A carbonyl group such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone). Containing polymerizable unsaturated monomer;
And combinations thereof.
As the other polymerizable unsaturated monomer, it is preferable to use an alkyl or cycloalkyl (meth) acrylate and / or a vinyl aromatic compound from the viewpoint of water resistance and fire resistance.

The above-mentioned copolymer emulsion can be obtained by adopting a usual method, but the emulsion polymerization method is preferable from the viewpoint of water resistance of the formed coating film. For emulsion polymerization, commonly used ionic or nonionic surfactants can be used.

The resin (B) has a non-volatile content mass of 5 to 50% by mass, more preferably 10 to 35 in the water-based foamed refractory paint composition, based on the total mass of the non-volatile components in the water-based foamed refractory paint composition. It can be in the range of% by mass.

<Char formation aid (C)>
The char forming aid (C) is for promoting the formation of char when the coating film formed by the aqueous foam fire resistant coating composition is exposed to fire. Lewis acid is generally considered to play an auxiliary function of forming char, and specifically, phosphorus-containing compounds such as ammonium phosphate, ammonium polyphosphate, and phosphoric acid are used. Among the phosphorus-containing compounds, an ammonium phosphate compound which is an ammonium salt of phosphoric acid or polyphosphate is preferable, and ammonium polyphosphate is more preferable. In the present invention, it is also possible to use other char formation aids in place of or in addition to the phosphorus-containing compounds. For example, the combination of ammonium polyphosphate and tris- (2-hydroxyethyl) isocyanate (THEIC) is one example.
The char forming auxiliary agent (C) is 10 to 70% by mass, more preferably 20 to 45% by mass in the water-based foamed refractory paint composition, based on the total mass of the non-volatile components in the water-based foamed refractory paint composition. Can exist in the amount of.

The aqueous foam fireproof coating composition of the present invention may further contain one or more of each of a carbon source, a foaming agent, a pigment, a plasticizer, and a film-forming auxiliary.

<Carbon source>
The water-based foam refractory paint composition can optionally contain a carbon source. Examples of carbon sources include pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, cellulose powder and the like.

The carbon source is present in the aqueous foam refractory coating composition in an amount of preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the non-volatile components in the aqueous foam refractory coating composition. can do.

<Effervescent agent>
In the present invention, the aqueous foam refractory paint composition can optionally contain a foaming agent (spumific). A foaming agent is one or more compounds that, when exposed to heat (usually fire), decompose to provide an expanding gas. The heat sufficient for the foaming agent to decompose and generate gas is usually about 90 ° C. or higher.

It is desirable that the temperature at which the foaming agent releases the gas is a temperature at which the organic polymer becomes soft and a temperature lower than the temperature at which the char is formed. The water-based foamed underground paint composition thus formed can be sufficiently foamed before forming chars, resulting in a better heat insulating body.

Effervescent agents include melamine, melamine formaldehyde, methylolated melamine, hexamethoxymethylmelamine, melamine monophosphate, melamine diphosphate, melamine polyphosphate phosphate, melamine pyrophosphate, melamine cyanurate, urea, nitrourea, dimethylurea, dicyandiamide, guanylurea phosphate, Glycin, amine phosphate, azodicarboxylic amide, 4,4'-oxybis (benzenesulfonylhydrazide), p-toluenehydrazide, p-toluenesulfonyl semicarbazide, dinitrosopentamethylenetetramine, 5-phenyltetrazole, diazoaminobenzene, etc. are used. It is possible. The compound decomposes when exposed to heat and releases nitrogen gas. In addition, compounds such as ammonium borate, potassium carbonate, and citric acid derivatives that release carbon dioxide, water vapor and / or ammonia when exposed to heat, and expansive graphite can also be used as foaming agents.

Preferred foaming agents can be melamine or derivatives thereof and are used alone or in combination.

When the water-based foaming fire-resistant coating composition of the present invention contains a foaming agent, the amount thereof is preferably 1 to 30% by mass, more preferably 5 to 30% based on the total mass of the non-volatile components in the water-based foaming fire-resistant coating composition. It can be in the range of 25% by weight.

<Pigment>
The water-based foam refractory paint composition of the present invention may optionally contain a pigment. Pigments are excluded from the above-mentioned polyvalent metal compound (A). The pigment is preferably a colored pigment, and as the colored pigment, those known in the paint field can be used, for example, colored pigments such as titanium dioxide (white pigment), carbon black, iron oxide; barite, talc, calcium carbonate. , Kaolin, filler pigments such as clay; and fibers.
The pigment is preferably present in the water-based foamed refractory paint composition in the range of preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on the total mass of the non-volatile components in the water-based foamed refractory paint composition. be able to.

<Plasticizer and / or film-forming aid>
The water-based foam refractory paint composition of the present invention may optionally contain a plasticizer and / or a film-forming auxiliary.
The plasticizer is a compound that remains in the coating film and is liquid at room temperature, and those known in the field of coating materials can be used. Specific examples of the plasticizer include fatty acid ester-based plasticizers, phosphate ester-based plasticizers, epoxy-based plasticizers, and the like.

On the other hand, the film-forming auxiliary is a high-boiling organic solvent that is compatible with the resin (B) and remains in the coating film even after water has volatilized, gradually promoting the fusion of the resin (B) particles. It is a volatile component. Specific examples of the film-forming auxiliary include ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monohexyl ether, ethylene glycol mono2-ethylhexyl ether, and diethylene glycol monomethyl ether. , Diethylene glycol diethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monophenyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol mono2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Butyl ether, polyethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tri Glycol ether compounds such as propylene glycol monobutyl ether; ester compounds such as 2,2,4-trimethylpentanediol monoisobutyrate and 2,2,4-trimethylpentanediol diisobutyrate may be mentioned.

When the aqueous foam fireproof coating composition of the present invention contains a plasticizer and a film-forming auxiliary, the total content in that case is preferably 0.1 to 15% by mass, more preferably 0. It is in the range of 5 to 10% by mass.

<Aqueous foam refractory paint composition>
The aqueous foam fire resistant coating composition of the present invention may optionally contain other components such as a pigment dispersant, a catalyst, an organic solvent, an additive for changing the melt viscosity, a rheology adjuster, and a curing agent. , Not limited to these.

The coating form of the aqueous foam fireproof coating composition of the present invention is not particularly limited, but is a two-component coating composition in which the first component (I) and the second component (II) are mixed and used immediately before use. The first component (I) contains the polyvalent metal compound (A), the second component (II) contains the resin (B), and the first component (I) and / or the second component (II) is a char formation aid. It is preferable that the form contains (C) and water. In other words, the present invention is for producing a water-based foam refractory paint composition comprising a first component (I) containing a polyvalent metal compound (A) and a second component (II) containing a resin (B). Includes a system.

When the coating material is a multi-component system, the components other than the polyvalent metal compound (A) and the resin (B) may be contained in either the first component (I) or the second component (II). .. In some embodiments, the components other than the polyvalent metal compound (A) and the resin (B) are contained in the second component (II). In some specific embodiments, the second component (II) comprises a char-forming aid (C) and water. In some specific embodiments, the second component (II) comprises a char forming aid (C), a carbon source, a foaming agent, a pigment (particularly a colored pigment), and water.

<Painting method>
The present invention further relates to a method for coating a substrate, which comprises coating the surface of the substrate with the aqueous foam fireproof coating composition.

The aqueous foam refractory paint composition of the present invention can be cured and / or dried at ambient temperatures such as −5 ° C. to 40 ° C. Therefore, it is suitable for application to large structures where heat curing is not practical.

In the present invention, the thickness of the dry film of the layer of the aqueous foam refractory coating composition can be appropriately selected depending on the intended use. Typically, for cellulosic fireproof applications (for example, applied to buildings such as office buildings), it is 100 μm to 8 mm, preferably 200 μm to 4 mm.

The present invention further relates to a method of protecting a structure from flames or heat, comprising coating the surface of a substrate with the aqueous foam fire resistant coating composition.

The water-based foam refractory paint composition of the present invention can be applied to various substrates.

Examples of base materials include not only metals such as steel frames, aluminum, and zinc iron plates, but also wallpaper, plywood, wood, inorganic boards, concrete, mortar, FRP, plastics, paper, cloth, fibers, synthetic resins, rubber, and silicon. , Electric wire cable and the like. Examples of the structure include above-ground structures and offshore structures, and particularly suitable structures include buildings stipulated in Articles 21 and 27 of the Building Standards Act. Specific examples thereof include buildings, schools, hospitals, hotels, movie theaters, stores, warehouses, airports, and the like.

When the water-based foam fire-resistant paint composition of the present invention is applied to a steel frame of an existing structure, the water-based foam fire-resistant paint of the present invention is applied after performing a base treatment such as rust removal and, if necessary, applying an undercoat paint. You may. Further, a known top coat may be applied after the water-based foam refractory coating composition of the present invention is applied.

The coating method is not particularly limited, and it can be easily applied by a general method such as a brush, a trowel, a roller, or a spray, and it is possible not only to apply a smooth coating but also to form an uneven pattern with a thick film. be. These coating methods are appropriately selected according to the intended use of the base material.

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

Manufacture of main ingredient component Production example 1
The following components were placed in a container and stirred and mixed using a planetary mixer until uniform to obtain a main component (X-1) for an aqueous foamed refractory paint composition.
Melamine 8.95 parts Pentaerythritol 8.95 parts Ammonium polyphosphate 26.83 parts Titanium oxide 8.72 parts Deionized water 23.72 parts 50% acrylic resin emulsion (B-1) (Note 1) 18.03 parts 2 , 2,4-trimethylpentanediol monoisobutyrate 4.27 parts thickener 0.47 parts (Note 1) 50% acrylic resin emulsion (B-1): styrene / 2-ethylhexyl acrylate / methacrylic acid = 81. 5/15 / 3.5, emulsified polymer, non-volatile content 50%, acid value 23 mgKOH / g.

<Manufacturing of water-based foam refractory paint composition using various multivalent metals>
Example 1
2.18 parts of a 10% nickel acetate aqueous solution was added to 50 parts of the main agent component (X-1) obtained in Production Example 1 and mixed by stirring. 1 was manufactured.

Examples 2 to 17 and Comparative Examples 1 to 2
In Example 1, each aqueous foam refractory paint composition Sample No. No. 1 is the same as in Example 1 except that the types and amounts of the cross-linking agents are shown in Table 1. 2-No. 19 was manufactured.

In the table, Ni (Ac) ₂ means nickel acetate, Mn (Ac) ₂ means manganese acetate, Co (Ac) ₂ means cobalt acetate, and Zn (Ac) ₂ means zinc acetate.

(Note 2) 6.9% ZnO aqueous solution A zinc oxide aqueous solution was prepared with the following composition and mixed with the main agent.
<Composition of zinc oxide aqueous solution>
Deionized water 68.3 parts Zinc oxide 6.9 parts Ammonium carbonate 12.7 parts Ammonia water 12.1 parts (Note 3) SVO2:
"Carbodilite SV02", trade name, manufactured by Nisshinbo Co., Ltd., a cross-linking agent for an aqueous resin consisting of a carbodiimide solution, a carbodiimide equivalent of 430, and an active ingredient of 40%.

Performance evaluation:
(*)water resistant:
Each water-based foam refractory paint composition No. The back surface and side surfaces of the coated panel coated with 1 to 19 so as to have a dry film thickness of 2 mm were sealed with an epoxy / amine-based paint, and the test panel was forcibly dried at 50 ° C. for 1 week as a test panel. After that, the test panel was immersed in water at 23 ° C., and the time until one or more blisters having a size of 5 mm or more were generated on the painted surface of the test panel was recorded. In the table, the larger the value, the better the result.
(*) Fire resistance:
A blasted steel sheet of 100 mm × 100 mm × 3.2 mm was coated with each aqueous foam refractory paint composition so that the dry film thickness was 0.7 mm, and dried at 23 ° C. for 7 days as a test panel, and corn calories were used. It was subjected to a meter test. Specifically, a thermocouple was attached to the back surface side of the test panel ^{and subjected to an ignition test using a cone calorimeter having a heating intensity of 50 kW / m 2} , and the temperature of the thermocouple after 20 minutes was recorded. In the table, the lower the value, the better the result.

<Manufacturing of water-based foam fireproof paint composition using acrylic resin emulsions with different acid values>
Examples 18-21
With the compounding composition shown in Table 2 below, the water-based foam refractory paint composition No. 20-23 were manufactured.

(Note 4) 50% acrylic resin emulsion (B-2): styrene / 2-ethylhexyl acrylate / methacrylic acid = 80/15/5, emulsified polymer, non-volatile content 50%, acid value 33 mgKOH / g
(Note 5) 50% acrylic resin emulsion (B-3): styrene / 2-ethylhexyl acrylate / methacrylic acid = 78.5 / 15 / 6.5, emulsified polymer, non-volatile content 50%, acid value 42 mgKOH / g
(Note 6) 50% acrylic resin emulsion (B-4): styrene / 2-ethylhexyl acrylate / methacrylic acid = 77/15/8, emulsified polymer, non-volatile content 50%, acid value 52 mgKOH / g.

Performance evaluation:
(*) 500 degree arrival time:
A test panel was prepared by the same method as the above-mentioned fire resistance test, subjected to a cone calorimeter test, and the time when the temperature of the thermocouple reached 500 degrees was recorded. In the table, the larger the value, the better the result.
(*) Water resistance A water resistance test was conducted in accordance with the "immersion method" of JIS K 5600-6-1.
Specifically, each steel sheet was coated with each water-based refractory paint composition so as to have a dry film thickness of 1.5 mm, and dried at 23 ° C. for 7 days as a test panel. This test panel was immersed in water at 23 ° C. for 96 hours, and the appearance was evaluated according to the following criteria.
◎: No change before and after immersion,
〇: Very slight blisters are observed before and after immersion.
Δ: Blisters are observed before and after immersion.
X: Blisters are noticeably observed before and after immersion.

<Discussion>
From the results of Tables 1 and 2, the effects of the present invention will be considered below.

Examples 1 to 21 are water-based foamed refractory paint compositions within the range specified in the present invention.
Comparative Example 1 is an aqueous foam fireproof coating composition that is outside the scope of the present invention in that it utilizes a crosslinking reaction with a carboxyl group and a carbodiimide instead of metal crosslinking.
Comparative Example 2 is a water-based foamed refractory coating composition that does not introduce metal crosslinks and is non-crosslinked, which is outside the scope of the present invention.

From the water resistance and fire resistance test results of the water-based foam refractory paint composition prepared as described above, the following can be said.

A water-based foam refractory paint composition that achieves both the water resistance of a coating film formed at room temperature and the fire resistance of an expanded coating film formed by heating by combining a polyvalent metal compound capable of metal cross-linking and a functional group-containing resin. Is obtained. (Examples 1 to 21)
When cross-linking by metal cross-linking is applied, both water resistance and fire resistance are improved as compared with the case of non-cross-linking. (Comparison between Example 1 and Comparative Example 2)
When cross-linking with carbodiimide is applied, the water resistance is improved but the fire resistance is lowered as compared with the case of non-cross-linking. (Comparison between Comparative Example 1 and Comparative Example 2)
When cross-linking by metal cross-linking is applied, the fire resistance is dramatically improved as compared with the carbodiimide cross-linking. (Comparison between Examples 4, 6, 10, 13, 17 and Comparative Example 1)

Claims (13)

Multivalent metal compound (A) containing a metal element capable of having an ionic valence of divalent or higher,
A water-based foam fireproof coating composition containing a resin (B) having a functional group capable of forming a metal crosslink with a metal element contained in the polyvalent metal compound (A), a char forming auxiliary agent (C), and water. The aqueous foam fireproof coating composition according to claim 1, wherein the polyvalent metal compound (A) is a metal oxide. The aqueous foam fireproof coating composition according to claim 1, wherein the polyvalent metal compound (A) is an organic acid metal salt. Any of claims 1 to 3, wherein the amount of the polyvalent metal compound (A) used is in the range of 0.1 to 2.0 equivalents with respect to 1 equivalent of the functional group contained in the resin (B). The water-based foam fireproof coating composition according to item 1. The aqueous foam fireproof coating composition according to any one of claims 1 to 4, wherein the functional group in the resin (B) is a carboxyl group. The water-based foamed refractory paint composition according to any one of claims 1 to 5, wherein the resin (B) has an acid value of 3 to 100 mgKOH / g. The aqueous foam fireproof coating composition according to claim 5 or 6, wherein the resin (B) is a copolymer emulsion of a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers. The aqueous foam fireproof coating composition according to claim 7, wherein the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is in the range of 1 to 10% by mass in the total polymerizable unsaturated monomer. The aqueous foam fireproof coating composition according to any one of claims 1 to 8, further comprising a carbon source. The water-based foaming fireproof coating composition according to any one of claims 1 to 9, further comprising a foaming agent. A two-component paint composition in which the first component (I) and the second component (II) are mixed immediately before use, and the first component (I) contains a polyvalent metal compound (A), and the second component (I) is contained. The aqueous foam fireproof coating composition according to any one of claims 1 to 10, wherein the component (II) contains the resin (B). A method for coating a substrate, which comprises coating the surface of the substrate with the aqueous foam fireproof coating composition according to any one of claims 1 to 11. A method for protecting a structure from heat and fire, which comprises applying the aqueous foam fireproof coating composition according to any one of claims 1 to 11 to the surface of a substrate.