JP2022147769A - Aqueous foamable fireproof coating composition - Google Patents

Abstract

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

Description

The present invention relates to water-based foamed fire-resistant coating compositions containing water as a diluent medium.

Since steel rapidly loses its strength at around 500°C, steel-framed structures collapse in the event of a fire, making it impossible to evacuate or extinguish the fire. For this reason, in order to maintain strength for a specified period of time even in the event of a fire, the steel frames of structures are required by the Building Standards Law to be coated with heat-insulating, fire-resistant coatings. The fire resistant coating materials include rock wool fire resistant coatings and foamed fire resistant coatings. Rock wool fireproof coating materials are inexpensive and widely distributed in the market, but they require a thickness of 1 cm to several cm to exhibit fireproof performance, and there is a problem that spraying work is difficult.

On the other hand, the foamed fire-resistant paint is a coating material that expands as the temperature rises in the event of a fire and exhibits heat insulating properties. Unlike rock wool, the fire-resistant coating using foamed fire-resistant paint is a thin film under normal conditions, and does not impair the shape of the structure itself. It is possible to suppress the temperature rise of the structure and delay the collapse of the structure.

As this foaming fire-resistant coating, the present applicant proposed in Patent Document 1 a foaming fire-resistant coating containing a hydrolyzable silyl group-containing resin, a plasticizer, a foaming agent, and a carbonizing agent. In this paint, it is easy to apply a thick coating, and a protective coating film with excellent physical properties such as quick drying, internal hardening, and water resistance can be obtained. It can be formed.

However, the foamed fire-resistant paint described in Patent Document 1 contains an organic solvent as a dilution medium, and has a problem of odor when applied in hospitals, schools, and the like. In addition, there is a problem that it is impossible to carry out work in parallel with electrical work due to scattering of the organic solvent.

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

JP 2018-159065 A JP 2015-59180 A

An object of the present invention is to provide a water-based foaming fire-resistant coating composition which is sufficiently excellent in fire resistance in the event of a fire and in water resistance of the coating film in normal times.

By the way, in order to generate char in the event of a fire, the foaming fire-resistant paint contains a char-forming aid, a carbon source, and a foaming agent. Although the mechanism of char generation by these components is not clear, it is generally believed to be as follows. The ambient temperature of the coating film rises due to the flame, and the char-forming aid contained in the coating film thermally decomposes to generate Lewis acid. The Lewis acid decomposes the carbon source to form a carbonized layer. On the other hand, the high temperature decomposes the foaming agent contained in the coating film to generate gas, which expands the carbonized layer by foaming the molten coating film-forming components, thereby producing char.

The present inventor has earnestly studied a technique for improving the water resistance of a water-based foaming fire-resistant coating composition in normal times.
As a result, by using a specific compound as the carbon source used to generate char in the foaming fire-resistant paint composition, it is possible to achieve excellent water resistance during normal times without significantly reducing fire resistance during fires. We succeeded in obtaining a good coating film.

That is, the present invention
Section 1.
A water-based foamed fire-resistant coating composition comprising a resin, a char-forming aid, a carbon source, a blowing agent and water, wherein the carbon source comprises a polyhydric alcohol phosphate ester as part of its components.
Section 2.
Item 2. The water-based foaming fire-resistant coating composition according to Item 1, wherein the polyhydric alcohol source of the polyhydric alcohol phosphate is pentaerythritol.
Item 3.
Item 3. Aqueous foamed fireproof material according to Item 1 or 2, wherein the polyhydric alcohol phosphate is 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide. paint composition.
Section 4.
Item 4. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 3, wherein the resin contains a carboxyl group.
Item 5.
Item 5. The water-based foaming fire-resistant coating composition according to any one of items 1 to 4, wherein the resin has an acid value of 3 to 100 mgKOH/g.
Item 6.
Item 6. The water-based foaming fire-resistant coating composition according to any one of items 1 to 5, wherein the resin is a copolymer emulsion of a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers.
Item 7.
Item 7. The water-based foaming fire-resistant coating composition according to item 6, wherein the copolymerization amount of the carboxyl group-containing polymerizable unsaturated monomer is in the range of 1 to 10% by mass based on the total polymerizable unsaturated monomer.
Item 8.
Item 8. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 7, further comprising a cross-linking agent.
Item 9.
Item 9. A water-based foaming fire-resistant coating composition according to Item 8, wherein the cross-linking agent is a polyvalent metal compound.
Item 10.
Item 10. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 9, which is a one-component coating composition.
Item 11.
Item 10. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 9, which is a two-component coating composition.
Item 12.
It is a two-component coating composition that is used by mixing the first component (I) and the second component (II) immediately before use, wherein the first component contains a resin, the second component contains a cross-linking agent, and the first Item 12. The aqueous foaming fire-resistant coating composition according to Item 11, wherein the component and/or second component comprises a carbon source, a char-forming aid, a blowing agent and water.
Item 13.
A method of coating a substrate, comprising coating the surface of the substrate with the water-based foaming fire-resistant coating composition according to any one of Items 1 to 12.
Item 14.
A method for protecting a structure from heat and fire, which comprises coating the surface of a substrate with the water-based foaming fire-resistant coating composition according to any one of Items 1 to 12;
Regarding.

According to the present invention, it is possible to obtain a water-based foaming fire-resistant coating composition that can normally form a coating film having excellent physical properties such as water resistance. In addition, the coating film formed from this water-based foaming fire-resistant coating composition is not easily deteriorated by rainwater and the like, and even after a long period of time after coating, it expands at high temperatures such as in the event of a fire, and exhibits excellent heat insulation properties. It can delay the thermal collapse of the structure.

2 is a photograph showing the state of char after the fire resistance test of the water-based fire-resistant coating composition of Example 5 performed in Test Example 2. FIG.

The aqueous foamed fire-resistant coating composition of the present invention comprises a resin, a char-forming aid, a carbon source, a blowing agent and water.

<Resin>
In the present invention, a water-soluble or dispersible resin is used as the resin. The resin type is not particularly limited, and when it is in the form of dispersed particles, it may be in a monolayer or a multi-layered form such as a core-shell type.

Examples of resins that can be used include conventionally known resins without particular limitations as long as they have a coating film-forming ability. Examples include, but are not limited to, epoxy resin emulsions, polyester resin emulsions, alkyd resin emulsions, melamine resin emulsions, and the like. Moreover, these may be used individually or may use 2 or more types together.

The resin preferably contains a carboxyl group.

In the present invention, when the resin has a carboxyl group, the resin preferably has an acid value 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 groups contained in 1 g of the mass of the resin non-volatile matter, which is determined by a conventional method based on alkali neutralization titration.

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

Carboxyl group-containing polymerizable unsaturated monomers include (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, β-carboxyethyl acrylate, and combinations thereof.

When producing the copolymer emulsion, the amount of copolymerization 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, based on 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)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, etc. or cycloalkyl (meth)acrylate;
(meth)acrylates having an isobornyl group such as isobornyl (meth)acrylate; (meth)acrylates having an adamantyl group such as adamantyl (meth)acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene;
Polymerization with alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane sexually unsaturated monomers;
perfluoroalkyl (meth)acrylates such as perfluorobutylethyl (meth)acrylate and perfluorooctylethyl (meth)acrylate; polymerizable unsaturated monomers having fluorinated alkyl groups such as fluoroolefins;
A monomer having a photopolymerizable functional group such as a maleimide group;
Nitrogen-containing compounds such as (meth)acrylonitrile, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, adducts of glycidyl (meth)acrylate and amines a polymerizable unsaturated monomer;
(Meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2 carbon atoms Monoesterified products with dihydric alcohols of ∼8, ε-caprolactone modified products of monoesterified products of (meth)acrylic acid and dihydric alcohols having 2 to 8 carbon atoms, N-hydroxymethyl (meth)acrylamide, allyl alco- a hydroxyl group-containing polymerizable unsaturated monomer such as (meth)acrylate having a polyoxyethylene chain with 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 allyl glycidyl ether;
A (meth)acrylate having a polyoxyethylene chain with an alkoxy group at the molecular end;
sulfonic acid group-containing polymerizable unsaturated monomers such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, sodium styrenesulfonate, sulfoethyl methacrylate, and sodium salts or ammonium salts thereof;
Phosphate group-containing polymerizable unsaturated monomers such as 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate;
Carbonyl groups such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketones having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) containing polymerizable unsaturated monomers;
and combinations thereof.

From the viewpoint of water resistance and fire resistance, alkyl or cycloalkyl (meth)acrylates and/or vinyl aromatic compounds are preferably used as the other polymerizable unsaturated monomers.

The above copolymer emulsion can be obtained by employing an ordinary method, but emulsion polymerization is preferred from the viewpoint of the water resistance of the coating film to be formed. In the emulsion polymerization, a commonly used ionic or nonionic surfactant can be used.

The resin has a non-volatile content of 5 to 50% by mass, more preferably 10 to 35% by mass, in the aqueous foaming fire-resistant coating composition, based on the total mass of non-volatile components in the aqueous foaming fire-resistant coating composition. can exist within the range.

In the present invention, the mass of the non-volatile component in the water-based fire-resistant foaming coating composition is determined by taking a known mass (for example, 0.3 g) of the water-based fire-resistant coating composition as a sample, placing it in a pre-weighed aluminum dish, and measuring the The sample is heated in an oven at 105° C. for 30 minutes, the pan is weighed again, and can be calculated from the pre-heat and post-heat sample masses (see ASTM D2697).

Unless otherwise specified herein, weight percent values are calculated based on the total weight of non-volatile components in the waterborne foam fire-resistant coating composition. In addition, the non-volatile content means the residue after removing the volatile component, and the residue may be solid or liquid at room temperature.

<Char formation aid>
The char-forming aid is for promoting the formation of char when the coating film formed by the water-based foaming fire-resistant coating composition is exposed to fire, and specifically includes ammonium phosphate, ammonium polyphosphate, Phosphorus-containing compounds such as phosphoric acid are used. Among phosphorus-containing compounds, an ammonium phosphate compound that is an ammonium salt of phosphoric acid or polyphosphoric acid is preferred, and ammonium polyphosphate is more preferred. Other char-forming aids may also be used in the present invention instead of or in addition to the phosphorus-containing compound. For example, a combination of ammonium polyphosphate and tris-(2-hydroxyethyl)isocyanurate (THEIC) is one example.

The char-forming aid is contained in the aqueous foaming fire-resistant coating composition in an amount of 10 to 70% by mass, more preferably 20 to 45% by mass, based on the total mass of non-volatile components in the aqueous foaming fire-resistant coating composition. can exist.

<Carbon source>
Aqueous foaming fire-resistant coating compositions contain a carbon source.

In the present invention, the carbon source contains a polyhydric alcohol phosphate as part of its components.

Examples of polyhydric alcohols include pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, cellulose powder, etc. Pentaerythritol is particularly preferred.

In the present invention, 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2. 2] The use of octane 1-oxide is preferred.

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

In the present invention, the carbon source is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the water-based foaming fire-resistant coating composition, based on the total mass of non-volatile components in the water-based foaming fire-resistant coating composition. can be present in an amount of

<Blowing agent>
In the present invention, the water-based foaming fire-resistant coating composition contains a spumific. A blowing agent is one or more compounds that decompose to provide an expanding gas when exposed to heat, usually fire. Sufficient heat to decompose the blowing agent and generate gas is typically about 90° C. or higher.

The temperature at which the blowing agent releases gas should be a temperature at which the organic polymer softens and below the temperature at which char is formed. Aqueous foamed basement coating compositions thus formed can be sufficiently foamed to form char and become a better thermal insulator.

Foaming 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, Glycine, amine phosphate, azodicarbonamide, 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, releasing nitrogen gas. Compounds that release carbon dioxide, water vapor and/or ammonia when exposed to heat, such as ammonium borate, potassium carbonate, citric acid derivatives, expandable graphite can also be used as blowing agents. A preferred blowing agent can be melamine or its derivatives, used alone or in combination.

The blowing agent may preferably be present in the range of 1-30% by weight, more preferably 5-25% by weight, based on the total weight of non-volatile components in the aqueous foaming fire-resistant coating composition.

The aqueous foamed fire-resistant coating composition of the present invention may further comprise one or more of each of a cross-linking agent, a pigment, a plasticizer and a coalescing agent.

<Crosslinking agent>
In the present invention, the water-based foaming fire-resistant coating composition may optionally contain a cross-linking agent. In the present invention, a polyvalent metal compound is preferably used as the cross-linking agent.
The polyvalent metal compound has a metal capable of forming a metal crosslink with the functional group contained in the resin. A metal cross-linking is a cross-linking structure that connects resin molecules via a metal. The present inventor believes that such metal cross-links are decomposed at a lower temperature than cross-link structures formed by covalent bonds between non-metals, so that strong char can be produced without impeding the expansion of the coating film when exposed to flame. think to form.

The polyvalent metal compound is a polyvalent metal compound containing a metal element capable of having a valence of 2 or more, preferably 2 to 4 ion valences, such as Mg, Ca, Ba, Fe, Cu, Zn, Al , Ti, Si, Zr, and Mn.
As the polyvalent metal compound, both an inorganic metal compound and an organic metal compound are preferably used.

Examples of inorganic metal compounds include metal oxides, metal hydroxides, metal nitrates, metal sulfates, and metal phosphates. Among these, metal oxides are preferred.

Examples of organic metal compounds include organic acid metal salts, metal alkoxides, and organic metal complexes. Among these, the use of organic acid metal salts is preferred.

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.

A compound having a functional group capable of reacting with the functional group contained in the resin can also be used as the cross-linking agent. Examples include polyoxazoline compounds, carbodiimide compounds, polyamines, hydrazine compounds, polyhydrazide compounds, polyisocyanate compounds, and the like.

When the water-based foaming fire-resistant coating composition of the present invention uses a cross-linking agent, its amount is in the range of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the nonvolatile content of the resin. can exist.

<Pigment>
The aqueous foamed fire resistant coating compositions of the present invention may optionally contain pigments. The pigment excludes those polyvalent metal compounds described above. As the coloring pigment, those known in the paint field can be used, for example, titanium dioxide (white pigment), carbon black, iron oxide and other colored pigments; barite, talc, calcium carbonate, kaolin, clay and other filler pigments; and fibers. The pigment may be present in the aqueous foaming fire-resistant paint composition in an amount of 1 to 40% by weight, preferably 5 to 30% by weight, based on the total weight of non-volatile components in the aqueous foaming fire-resistant paint composition. .

<Plasticizer and/or film forming aid>
The aqueous foaming fire-resistant coating composition of the present invention may optionally contain a plasticizer and/or coalescing agent.
The plasticizer is a compound that is liquid at room temperature and remains in the coating film, and those known in the field of coatings can be used. Specific examples of plasticizers include fatty acid ester plasticizers, phosphate ester plasticizers, and epoxy plasticizers.

On the other hand, the film-forming aid is an organic solvent with a high boiling point that is compatible with the resin. It remains in the coating film even after the water evaporates, and gradually volatilizes while promoting the coalescence of the resin particles. . Specific examples of film-forming aids include ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, 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 mono-2-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, tripropylene glycol monomethyl ether glycol ether compounds such as propylene glycol monobutyl ether; ester compounds such as 2,2,4-trimethylpentanediol monoisobutyrate and 2,2,4-trimethylpentanediol diisobutyrate;

When a plasticizer and a film-forming aid are contained, the content in that case is 0.1 to 15% by mass, preferably 0.5, based on the total mass of nonvolatile components in the aqueous foaming fire-resistant coating composition. It is within the range of ~10% by mass.

<Water-based foaming fire-resistant paint composition>
The aqueous foam fire-resistant coating composition of the present invention may optionally contain other ingredients such as pigment dispersants, catalysts, organic solvents, additives for modifying melt viscosity, rheology modifiers, and curing agents. , but not limited to.

The coating form of the water-based foaming fire-resistant coating composition of the present invention is not particularly limited. A one-liquid type is also possible.
When the water-based foaming fire-resistant coating composition of the present invention contains a cross-linking agent, it is a two-component coating composition in which the first component (I) and the second component (II) are mixed immediately before use, and the first component contains the resin, the second component contains the cross-linking agent, and the first component and/or the second component contain the carbon source, the char-forming aid, the blowing agent and water.

<Painting method>
The present invention further relates to a method of coating a substrate, comprising coating the surface of the substrate with the above water-based foaming fire-resistant coating composition.

The waterborne foamed fire resistant coating composition of the present invention can be cured and/or dried at ambient temperatures, eg -5°C to 40°C. Therefore, it is suitable for application to large structures where heat curing is impractical.

In the present invention, the thickness of the dry film of the layer of the water-based foaming fire-resistant coating composition can be appropriately selected depending on the application. Typically, for cellulosic fire-resistant applications (eg, architectural applications such as office buildings), it is between 100 μm and 8 mm, preferably between 200 μm and 4 mm.

The present invention further relates to a method of protecting a structure from fire or heat comprising applying to a substrate surface the waterborne fire resistant coating composition described above.

The water-based foaming fire-resistant coating 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 galvanized iron plates, but also wallpaper, plywood, wood, inorganic boards, concrete, mortar, FRP, plastics, paper, cloth, fibers, synthetic resins, rubber, and silicon. , electric wires and cables. Examples of structures include above-ground structures and offshore structures, and particularly suitable structures include buildings defined in Articles 21 and 27 of the Building Standards Law. Some of the specific examples include buildings, schools, hospitals, hotels, movie theaters, stores, warehouses, airports, and the like.

When applying the water-based fire-resistant foaming paint composition of the present invention to the steel frame of an existing structure, after performing surface treatment such as rust removal, apply a primer coating as necessary, and then apply the water-based fire-resistant foaming paint composition of the present invention. can do. Further, after coating the water-based foaming fire-resistant coating composition of the present invention, a known top coating may be applied.

The coating method is not particularly limited, and it can be easily applied by general methods such as brush, trowel, roller, spray, etc. It is possible not only to apply smoothly, but also to form a thick film with uneven patterns. be. These coating methods are appropriately selected according to the purpose of use of the substrate.

The present invention will be further described below with reference to examples. Here, "parts" and "%" mean "mass parts" and "mass%" respectively.

Example 1
<Production of one-liquid water-based foaming fire-resistant coating composition>
Example 1
The following ingredients were placed in a container and stirred and mixed using a planetary mixer until uniform to obtain a one-liquid water-based foaming fire-resistant paint composition (X-1).

[Composition of water-based foaming fire-resistant paint composition (X-1)]
Deionized water 20 parts Melamine 8.09 parts Pentaerythritol phosphate (Note 1) 8.09 parts Titanium oxide 8 parts Ammonium polyphosphate 24.27 parts Rock wool fiber 3 parts 50% acrylic resin emulsion (Note 2) 17. 26 parts 2,2,4-trimethylpentanediol monoisobutyrate 5.9 parts thickener 0.2 parts.

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

<Production of two-component water-based foaming fire-resistant coating composition>
Example 2
The water-based foaming fire-resistant coating composition (X-1) obtained in Example 1 was used as the first component, and 1.625 parts of a 10% zinc acetate aqueous solution was added as the second component and mixed with stirring to form an aqueous foaming composition. A fire resistant coating composition (X-2) was produced.

Examples 3-4 and Comparative Example 1
Each water-based foaming fire-resistant coating composition (X-3) to (X-5) was produced in the same manner as in Example 1 or Example 2 except that the formulation composition was shown in Table 1.

Test example 1
A simple fire resistance test using a cone calorimeter, durability, and blister resistance were evaluated for each of the water-based foaming fire-resistant coating compositions obtained in the above Examples and Comparative Examples.

(*) Fire resistance simple test A blasted steel plate of 100 x 100 x 3.2 mm was coated with “Esco NB Primer” (trade name, manufactured by Kansai Paint Co., Ltd., modified epoxy resin anticorrosive paint), dried, and then each aqueous A test panel was prepared by applying the foaming fire-resistant paint composition to a dry film thickness of 1.0 mm and drying at 23° C. for 3 days and at 50° C. for 1 day.
A thermocouple was attached to the back side of the test panel, and an ignition test was performed using a cone calorimeter with a heating intensity of 50 kw/m ² . After 20 minutes, the temperature of the thermocouple was measured and evaluated according to the following criteria.
○: The temperature of the thermocouple is 500 ° C or less,
x: The temperature of the thermocouple exceeds 500°C.

(*)durability:
Create the same test panel as the test panel created in the simple fire resistance test, immerse in water at 20 ° C for 18 hours, cool to -20 ° C for 3 hours, and heat to 50 ° C for 3 hours. was repeated 10 times to deteriorate the coating film, and then subjected to a simple fire resistance test in the same manner. As a result, the temperature of the deteriorated coating film was higher than that of the new coating film.

The numbers in Table 1 are the temperature difference for the degraded coating minus the temperature for the new coating with respect to the test panel backside temperature after 20 minutes in the cone calorimeter test. It was judged that the smaller the numerical value in the table, the less the fire resistance decreased even when the coating film deteriorated, and the better the durability.
(*) Blister resistance A blasted steel plate of 150 × 70 × 3.2 mm was coated with each water-based fire-resistant paint composition so that the dry film thickness was 2 mm, and dried at 23 ° C. for 7 days. One sheet was left as it was, and the other sheet was further coated with "Cosmo Silicon" (trade name, manufactured by Kansai Paint Co., Ltd., a water-based reaction-curable acrylic silicone paint) so that the dry film thickness was 50 µm, and the temperature was 23°C. A test panel was prepared by drying for a day. Each test panel with and without top coating was immersed in water at 23° C. for 3 weeks, dried at 50° C. for 3 days, and the appearance was evaluated according to the following criteria.
◎: No change before and after immersion,
○: Blisters are very slightly observed,
△: blisters are clearly observed,
x: Large blisters are remarkably observed.

Test example 2
(*) Fire resistance test Example 5
A two-component water-based foaming fire-resistant coating composition (X-6) was produced with the following composition. Prepare a steel material (size 300 mm × 300 mm × 4.5 mm) with a thermocouple attached, and apply the water-based foaming fire-resistant paint composition (X-6) to it with a trowel so that the dry film thickness is 3.3 mm. and dried at 23° C. for 7 days to obtain a specimen. When this test piece was placed in a furnace that was heated to a predetermined temperature with respect to the elapsed time so that the temperature rise curve specified by ISO834 was obtained, a fire resistance test was performed. was 89 minutes. After the fire resistance test of Example 5, the specimen was covered with char as shown in FIG.

[Composition of water-based foaming fire-resistant paint composition (X-6)]
First component 25% zinc acetate aqueous solution 0.65 parts Deionized water 18 parts Melamine 8.09 parts Pentaerythritol phosphate (Note 1) 8.09 parts Titanium oxide 7.94 parts Ammonium polyphosphate 24.27 parts Rock wool Fiber 0.5 parts Second component 50% acrylic resin emulsion (Note 2) 17.26 parts Carbon black 0.01 parts 2,2,4-trimethylpentanediol monoisobutyrate 5.9 parts Thickener 0.1 Department.

Comparative example 2
When the time to reach 500° C. was measured in the same manner as in Example 5 except that the composition was as follows, it was 77 minutes. Comparative Example 2 had a shorter time to reach 500° C. than Example 5, and was judged to be inferior in fire resistance.
[Composition of water-based foaming fire-resistant paint composition (X-7)]
First component 25% zinc acetate aqueous solution 0.65 parts Deionized water 20 parts Melamine 8.09 parts Dipentaerythritol 8.09 parts Titanium oxide 7.94 parts Ammonium polyphosphate 24.27 parts Rock wool fiber 0.5 parts Two-component 50% acrylic resin emulsion (Note 2) 17.26 parts Carbon black 0.01 parts 2,2,4-trimethylpentanediol monoisobutyrate 5.9 parts Thickener 0.1 parts

Claims (14)

A water-based foamed fire-resistant coating composition comprising a resin, a char-forming aid, a carbon source, a blowing agent and water, wherein the carbon source comprises a polyhydric alcohol phosphate ester as part of its components. 2. The water-based foaming fire-resistant coating composition of claim 1, wherein the polyhydric alcohol source of the polyhydric alcohol phosphate is pentaerythritol. Aqueous foam according to claim 1 or 2, wherein the polyhydric alcohol phosphate is 4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide. Fire resistant paint composition. The water-based foaming fire-resistant coating composition according to any one of claims 1 to 3, wherein the resin contains carboxyl groups. The water-based foaming fire-resistant coating composition according to any one of claims 1 to 4, wherein the resin has an acid value of 3 to 100 mgKOH/g. The water-based foaming fire-resistant coating composition according to any one of claims 1 to 5, wherein the resin is a copolymer emulsion of a carboxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers. 7. The water-based foaming fire-resistant coating composition according to claim 6, 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 water-based foaming fire-resistant coating composition according to any one of claims 1-7, further comprising a cross-linking agent. 9. A water-based foaming fire-resistant coating composition according to claim 8, wherein the cross-linking agent is a polyvalent metal compound. The water-based foaming fire-resistant coating composition according to any one of claims 1 to 9, which is a one-component coating composition. The water-based foaming fire-resistant coating composition according to any one of claims 1 to 9, which is a two-component coating composition. It is a two-component coating composition that is used by mixing the first component (I) and the second component (II) immediately before use, wherein the first component contains a resin, the second component contains a cross-linking agent, and the first 12. A water-based foamed fire-resistant coating composition according to claim 11, wherein the component and/or secondary component comprises a carbon source, a char-forming aid, a blowing agent and water. A method of coating a substrate, comprising coating the surface of a substrate with the water-based foaming fire-resistant coating composition according to any one of claims 1 to 12. A method of protecting a structure from heat and fire comprising applying the water-based foamed fire resistant coating composition of any one of claims 1-12 to a substrate surface.

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