Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/18—Fireproof paints including high temperature resistant paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to a water-based foaming fire-resistant paint composition containing water as a diluent medium.
• 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.
• foaming fire-resistant paint is a coating material that expands due to the temperature rise in the event of a fire, demonstrating heat insulation.
• 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.
• Patent Document 1 the present applicant proposed a foamed fire-resistant coating containing a hydrolyzable silyl group-containing resin, a plasticizer, a foaming agent, and a carbonizing agent as this foamed fire-resistant coating.
• 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.
• the foamed fire-resistant paint described in Patent Document 1 contains an organic solvent as a dilution medium, and there is a problem of odor when it is applied in hospitals, schools, etc. 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.
• Patent Document 2 discloses a foaming fire-resistant coating composition containing an acrylic resin emulsion as a binder component as a synthetic resin emulsion.
• JP 2018-159065 A JP-A-2005-89670
• Water-based paints for painting on buildings must form a durable coating film even under normal temperature drying conditions. Therefore, an acrylic resin emulsion, which is said to have high durability, is generally used as a coating film-forming component.
• acrylic resin emulsions using acrylic resin emulsions have the problem that foaming of the paint film is difficult in the event of a fire, resulting in insufficient fire resistance.
• An object of the present invention is to propose a water-based foaming fire-resistant coating composition capable of forming a foaming coating film resistant to flames or heat in the event of a fire.
• an aqueous foaming fire-resistant coating composition containing a high-styrene emulsion in which a large amount of styrene is copolymerized has excellent fire resistance.
• a water-based foamable fire-resistant coating composition comprising a high styrene emulsion (A), a char forming aid (B), a carbon source (C), a blowing agent (D) and water, wherein the high styrene emulsion (A) is styrene
• a water-based foaming fire-resistant coating composition comprising a copolymer of polymerizable unsaturated monomers comprising: Section 2.
• Item 2 The water-based foaming fire-resistant coating composition according to Item 1, wherein the polymerizable unsaturated monomer comprises a hydroxyl group-containing polymerizable unsaturated monomer.
• Section 4. Item 4. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 3, further comprising a plasticizer (E) and/or a film forming aid (F). Item 5.
• Item 5. The water-based foaming fire-resistant coating composition according to any one of items 1 to 4, further comprising a co-solvent (G).
• Item 6. 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 5.
• Item 7. A method for protecting a structure from heat and fire, comprising coating the surface of a substrate with the water-based foaming fire-resistant coating composition according to any one of Items 1 to 5.
• a flame- or heat-resistant coating film can be formed. Therefore, the temperature rise of the base material such as steel can be delayed.
• (meth)acrylate means acrylate and/or methacrylate
• (meth)acrylic acid means acrylic acid and/or methacrylic acid
• (Meth)acryloyl refers to acryloyl and/or methacryloyl
• (Meth)acrylamide” refers to acrylamide and/or methacrylamide.
• the water-based foaming fire-resistant coating composition of the present invention contains a high styrene emulsion (A), a char-forming aid (B), a carbon source (C), a blowing agent (D) and water.
• the high styrene emulsion (A) contains a copolymer of polymerizable unsaturated monomers containing styrene, and the proportion of styrene in the total polymerizable unsaturated monomers constituting the copolymer is 40% by mass or more. is a resin emulsion. If the proportion of styrene is less than 40% by mass, the formed coating film has insufficient fire resistance, which is undesirable. Also, the proportion of styrene is preferably 55% by mass or more, more preferably in the range of 70 to 95% by mass.
• the high styrene emulsion (A) can contain a polymerizable unsaturated monomer other than styrene as a constituent component of the copolymer.
• the 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
• alkyl or cycloalkyl (meth)acrylates alkyl or cycloalkyl (meth)acrylates; (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 ⁇ -methylstyrene and vinyltoluene; Polymerization with alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, ⁇ -(meth)acryloyloxypropyltrimethoxysilane, ⁇ -(meth)acryloyloxypropyltriethoxysilane sexually unsaturated monomers; (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, ⁇ -carboxyethyl acrylate polymerizable uns
• a sulfonic acid group-containing polymerizable unsaturated monomer 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.
• Phosphate group-containing polymerizable unsaturated monomers such as 2-acryloyloxyethyl acid phosphate, 2-methacryl
• the amount of polymerizable unsaturated monomers other than styrene in the total polymerizable unsaturated monomers constituting the copolymer is not particularly limited, but is, for example, 5 to 60% by mass.
• the polymerizable unsaturated monomers other than styrene comprise alkyl or cycloalkyl (meth)acrylates, and the proportion of alkyl or cycloalkyl (meth)acrylates in the total polymerizable unsaturated monomers is from 5 to 60 mass. %.
• the high styrene emulsion (A) preferably has hydroxyl groups.
• the hydroxyl value is preferably in the range of 0.1 to 100 mgKOH/g, particularly preferably in the range of 2 to 60 mgKOH/g.
• the hydroxyl value is a value (mgKOH/g) represented by the number of mg of potassium hydroxide that is equimolar to the hydroxyl group contained in 1 g of the non-volatile matter of the resin.
• the polymerizable unsaturated monomer that is a constituent component of the copolymer contains a hydroxyl group-containing polymerizable unsaturated monomer.
• hydroxyl group-containing polymerizable unsaturated monomer examples include monomers having a hydroxyl group among the above-mentioned polymerizable unsaturated monomers other than styrene.
• the polymerizable unsaturated monomer is preferably in the range of 0.05 to 10% by weight, particularly preferably in the range of 0.1 to 5% by weight.
• the high styrene emulsion (A) preferably has an acid group from the viewpoint of the storage stability of the water-based foamed fire-resistant coating composition.
• a carboxyl group is mentioned as an acid group.
• the acid value is preferably 3 to 100 mgKOH/g, particularly preferably 5 to 80 mgKOH/g.
• 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 acid group-containing polymerizable unsaturated monomer, particularly the carboxyl group-containing polymerizable unsaturated monomer include the above-mentioned compounds, and the copolymerization amount thereof is preferably 1 to 20% by mass in the total polymerizable unsaturated monomer. , 3 to 10% by weight is particularly preferred.
• the high styrene emulsion (A) can be obtained by adopting a normal production method for a resin emulsion, but from the viewpoint of the water resistance of the formed coating film, it is preferably produced by an emulsion polymerization method.
• the monomer components constituting the copolymer are polymerized using a polymerization initiator in the presence of water and an emulsifier to obtain a high styrene emulsion (A), which is an aqueous dispersion of the copolymer. be able to.
• the high styrene emulsion (A) preferably contains 5 to 50% by mass, more preferably It can be present in the range of 10-35% by weight.
• the non-volatile content means the residue after removing the volatile components, and the residue may be solid or liquid at room temperature.
• the residue may be solid or liquid at room temperature.
• a component remaining when a 0.3 g sample is heated at 105° C. for 30 minutes and dried is treated as a non-volatile component.
• the char-forming aid (B) is a substance for promoting the formation of char when the coating film formed from the water-based foaming fire-resistant coating composition is exposed to fire.
• a Lewis acid is generally considered to have an auxiliary function to form char, and specifically phosphorus-containing compounds such as ammonium phosphate, ammonium polyphosphate and phosphoric acid are used.
• 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.
• a combination of ammonium polyphosphate and tris-(2-hydroxyethyl)isocyanurate (THEIC) is one example.
• the char-forming auxiliary agent (B) is preferably 10 to 70% by mass, more preferably 20 to 45% by mass in the water-based foaming fire-resistant coating composition based on the total mass of non-volatile matter in the water-based foaming fire-resistant coating composition. % can be present.
• the water-based foaming fire-resistant coating composition contains a carbon source (C).
• Examples of the carbon source (C) include pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, cellulose powder and the like.
• the carbon source (C) is preferably in an amount of 1 to 50% by mass, more preferably 5 to 30% by mass in the aqueous foaming fire-resistant coating composition, based on the total mass of non-volatile matter in the aqueous foaming fire-resistant coating composition. can exist in
• the water-based foaming fire-resistant coating composition of the present invention contains a foaming agent (D).
• a blowing agent (D) 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 foaming agent (D) releases gas is preferably a temperature at which the organic polymer softens and a temperature lower than the temperature at which char is formed.
• the water-based foaming fire-resistant coating composition thus formed can be sufficiently foamed to form char and become a better thermal insulator.
• Foaming agents (D) include melamine, melamine formaldehyde, methylolated melamine, hexamethoxymethyl melamine, melamine monophosphate, melamine diphosphate, melamine polyphosphate phosphate, melamine pyrophosphate, melamine cyanurate, urea, nitrourea, dimethylurea, dicyandiamide, guanyl.
• Urea phosphate, glycine, amine phosphate, azodicarbonamide, 4,4'-oxybis(benzenesulfonylhydrazide), p-toluenehydrazide, p-toluenesulfonyl semicarbazide, dinitrosopentamethylenetetramine, 5-phenyltetrazole, diazoaminobenzene etc. can be used.
• 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 in the present invention can be melamine or its derivatives, used alone or in combination.
• the foaming agent (D) can be present in a range of preferably 1 to 30% by mass, more preferably 5 to 25% by mass, based on the total mass of nonvolatile matter in the aqueous foaming fire-resistant coating composition. .
• the water-based foaming fireproof coating composition of the present invention contains water.
• Water is the diluent medium.
• the amount of water in the aqueous foaming fire-resistant coating composition can be appropriately selected by those skilled in the art, but is preferably 5 to 60% by mass, more preferably 5 to 60% by mass, based on the total mass of nonvolatile matter in the aqueous foaming fire-resistant coating composition It is within the range of 10 to 50% by mass.
• the water-based foaming fire-resistant coating composition of the present invention can optionally contain a plasticizer (E) and/or coalescing agent (F).
• the plasticizer (E) is a component that remains in the coating film, and has a weight average molecular weight of preferably 250 or more, more preferably 300 or more, and a weight average molecular weight of preferably 2000 or less, from the viewpoint of fire resistance. Substances below 1900 are preferred.
• the film-forming aid (F) is an organic solvent with a high boiling point that is compatible with the high styrene emulsion (A). It is a component that gradually volatilizes while promoting The weight average molecular weight of the film forming aid (F) is less than 250, for example.
• the weight average molecular weight of a substance whose chemical formula is clear is the molecular weight calculated from the chemical formula.
• the weight average molecular weight of a substance whose chemical formula is not clear is the retention time (retention volume) measured using gel permeation chromatography (GPC), and the retention time (retention volume) of standard polystyrene with a known molecular weight measured under the same conditions. ) converted into the molecular weight of polystyrene.
• HEC-8120GPC (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph
• TSKgel G4000HXL "TSKgel G3000HXL”
• TSKgel G2500HXL and "TSKgel G2500HXL” are used as columns.
• TSKgel G2000HXL (trade name, both manufactured by Tosoh Corporation) using a total of four, using a differential refractometer as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 mL / min. can be measured under the conditions of
• plasticizer (E) examples include fatty acid ester plasticizers and phosphate ester plasticizers.
• Fatty acid ester plasticizers include adipates, citrates, benzoates, myristates, acetates, succinates, glutarates, sebacates, and these. A combination is mentioned.
• a plasticizer using adipic acid or citric acid as a raw material is particularly preferred.
• Phosphate plasticizers include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl Diphenyl phosphate, dicresylphenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, isodecyl diphenyl phosphate, hydroxyphenyl diphenyl phosphate, resorcinol bis diphenyl phosphate, triaryl isopropyl phosphate, these with various substituents Modified compounds, various condensation types thereof, and the like.
• the film forming aid (F) 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, 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, tri Ethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl
• the aqueous foaming fire-resistant coating composition of the present invention contains a plasticizer (E) and/or a film forming aid (F), the content in that case is preferably based on the non-volatile content in the aqueous foaming fire-resistant coating composition.
• the amount of the plasticizer (E) is preferably in the range of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass from the viewpoint of fire resistance, and the amount of the film-forming aid (F) is , preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, from the viewpoint of tackiness.
• the aqueous foamed fire-resistant coating composition of the present invention can optionally contain a co-solvent (G).
• the presence of the co-solvent (G) is effective in improving the tackiness and crack resistance of the coating film formed from the water-based foaming fire-resistant coating composition of the present invention.
• the co-solvent (G) is an organic solvent having a molecular weight of less than 250 and an evaporation rate higher than that of water
• the film-forming aid (F) is a solvent having a molecular weight of less than 250 and an evaporation rate lower than that of water. do.
• the evaporation rate can be measured according to ASTM D 3539, for example. Specifically, it is obtained as a relative rate to the amount of weight loss of butyl acetate per unit time when the temperature is 25° C. and the relative humidity is 55% RH.
• the evaporation rate of butyl acetate is 1, and the larger this number is, the easier it is to evaporate.
• Specific examples of such a co-solvent (G) include ethyl alcohol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, t-butyl alcohol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid.
• Examples include isoamyl, ethylene glycol monoethyl ether, methyl isobutyl ketone, methyl ethyl ketone, methyl isoamyl ketone, n-hexane, cyclohexane, toluene and xylene.
• the aqueous foaming fire-resistant coating composition of the present invention contains a co-solvent (G), the content in that case is based on the non-volatile matter in the aqueous foaming fire-resistant coating composition, preferably the amount of the co-solvent (G) is 0 .1 to 20% by weight, more preferably 0.5 to 15% by weight.
• the aqueous foam fire-resistant coating composition of the present invention optionally comprises other ingredients such as pigments, pigment dispersants, catalysts, fibers, organic solvents, additives for modifying melt viscosity, rheology modifiers, curing agents. can be, but are not limited to.
• pigments include colored pigments such as titanium dioxide (white pigment), carbon black, and iron oxide; filler pigments such as baryte, talc, calcium carbonate, kaolin, and clay.
• the pigment is preferably present in the water-based foaming fire-resistant coating composition in an amount of 1 to 40% by mass, more preferably 5 to 30% by mass, based on the total mass of non-volatile matter in the water-based foaming fire-resistant coating composition. can be done.
• 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 water-based foaming fire-resistant coating 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 impractical.
• the thickness of the dry film of the layer of the water-based foaming fire-resistant coating composition can be appropriately selected according to the application. Typically, it is preferably 100 ⁇ m to 8 mm, more preferably 200 ⁇ m to 4 mm for cellulosic refractory applications (eg, architectural applications such as office buildings).
• the present invention further relates to a method of protecting a structure from fire or heat, comprising coating the surface of a substrate with the water-based foaming fire-resistant coating composition.
• the water-based foaming fireproof 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.
• the structure comprises a substrate.
• 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.
• the water-based fire-resistant foaming paint composition of the present invention When applying the water-based fire-resistant foaming paint composition of the present invention to the steel frame of an existing structure, after performing a surface treatment such as rust removal, the water-based fire-resistant foaming paint composition of the present invention is applied after applying a primer coating as necessary. You can paint things. 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 water-based foaming fire-resistant coating composition of the present invention can also have the following constitution.
• Section 1. A water-based foamable fire-resistant coating composition comprising a high styrene emulsion (A), a char forming aid (B), a carbon source (C), a blowing agent (D) and water, wherein the high styrene emulsion (A) is styrene
• a water-based foaming fire-resistant coating composition comprising a copolymer of polymerizable unsaturated monomers comprising: Section 2.
• Item 2. The water-based foaming fire-resistant coating composition according to Item 1, wherein the polymerizable unsaturated monomer includes a hydroxyl group-containing polymerizable unsaturated monomer.
• Item 3 The water-based foaming fire-resistant coating composition according to Item 1 or 2, wherein the polymerizable unsaturated monomer contains an acid group-containing polymerizable unsaturated monomer. Section 4. Item 4. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 3, further comprising a plasticizer (E) and/or a film forming aid (F). Item 5. Item 5. The water-based foaming fire-resistant coating composition according to any one of items 1 to 4, further comprising a co-solvent (G).
• Item 6. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 5, wherein the high styrene emulsion (A) contains a polymerizable unsaturated monomer other than styrene as a constituent of the copolymer.
• Item 7. Item 7. The water-based foaming fire-resistant coating composition according to Item 6, wherein the ratio of the polymerizable unsaturated monomers other than styrene in the total polymerizable unsaturated monomers constituting the high styrene emulsion (A) is 5 to 60% by mass.
• the polymerizable unsaturated monomer other than styrene is an alkyl or cycloalkyl (meth)acrylate, an isobornyl group-containing (meth)acrylate, an adamantyl group-containing (meth)acrylate, a vinyl aromatic compound, or an alkoxysilyl group-containing polymerizable monomer.
• Unsaturated monomers polymerizable unsaturated monomers having carboxyl groups, perfluoroalkyl (meth)acrylates, polymerizable unsaturated monomers having fluorinated alkyl groups, monomers having photopolymerizable functional groups, nitrogen-containing polymerizable unsaturated monomers , a hydroxyl group-containing polymerizable unsaturated monomer, an epoxy group-containing polymerizable unsaturated monomer, a sulfonic acid group-containing polymerizable unsaturated monomer, a phosphoric acid group-containing polymerizable unsaturated monomer, a carbonyl group-containing polymerizable unsaturated monomer, and these Item 8.
• Item 9. Item 9. The water-based foaming fire-resistant coating composition according to any one of Items 1 to 8, wherein the char-forming auxiliary agent (B) contains a phosphorus-containing compound.
• Item 11 The water-based foaming fire-resistant coating composition according to any one of items 1 to 10, wherein the carbon source (C) comprises pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, or cellulose powder.
• the carbon source (C) comprises pentaerythritol, dipentaerythritol, polyvinyl alcohol, starch, or cellulose powder.
• Item 12. Any one of items 1 to 11, wherein the carbon source (C) is 1 to 50% by mass in the water-based foaming fire-resistant coating composition based on the total mass of non-volatile matter in the water-based foaming fire-resistant coating composition.
• the foaming agent (D) is melamine, melamine formaldehyde, methylolated melamine, hexamethoxymethylmelamine, melamine monophosphate, melamine diphosphate, melamine polyphosphate phosphate, melamine pyrophosphate, melamine cyanurate, urea, nitrourea, dimethylurea, dicyandiamide, guanyl urea phosphate, glycine, amine phosphate, azodicarbonamide, 4,4'-oxybis(benzenesulfonylhydrazide), p-toluenehydrazide, p-toluenesulfonyl semicarbazide, dinitrosopentamethylenetetramine, 5-phenyltetrazole, or diazoamino Item 13.
• Item 16 Item 5. The water-based foaming fire-resistant coating composition according to Item 4, wherein the plasticizer (E) is contained in an amount of 0.1 to 15% by mass based on the non-volatile matter in the water-based foaming fire-resistant coating composition.
• Item 17. Item 5. The water-based foaming fire-resistant coating composition according to Item 4, wherein the film-forming aid (F) contains a glycol ether-based compound or an ester-based compound.
• Item 18. Item 5. The water-based foaming fire-resistant coating composition according to Item 4, containing 0.1 to 15% by mass of the film-forming aid (F) based on the non-volatile matter in the water-based foaming fire-resistant coating composition.
• 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 18.
• Item 20 A method for protecting a structure from heat and fire, comprising coating the surface of a substrate with the water-based foaming fire-resistant coating composition according to any one of Items 1 to 18.
• Example 1 Preparation of water-based foaming fire-resistant coating composition
• X-1 water-based foaming fire-resistant coating composition
• Deionized water 17 parts Dispersant 1.24 parts Melamine 8.6 parts Pentaerythritol 8.6 parts Titanium oxide 8.5 parts Ammonium polyphosphate 25.8 parts
• Examples 2-7 and Comparative Examples 1-2 Water-based foaming fire-resistant coating compositions (X-2) to (X-9) were prepared in the same manner as in Example 1 except that the resin emulsion (A3) used in Example 1 was changed to the resin emulsion shown in Table 1 below. ).
• Table 2 shows the monomer composition of each resin emulsion.
• Evaluation test Fire resistance evaluation Each water-based foamed fire-resistant coating composition (X-1) to (X-9) obtained in Examples and Comparative Examples was applied to a blasted steel plate of 100 mm ⁇ 100 mm ⁇ 3.2 mm so that the dry film thickness was 1.0 mm. and dried at 23°C for 7 days. Specifically, a thermocouple was attached to the back side of the test panel, an ignition test was performed using a cone calorimeter with a heating intensity of 50 kw/m 2 , and the temperature of the thermocouple was recorded after 20 minutes. Table 1 shows the results. In the table, the lower the numerical value, the better the result.
• Examples 8-15 Water-based foaming fire-resistant coating compositions (X-10) to (X-17) were obtained in the same manner as in Example 1 except that the formulations were as shown in Table 3 below. Table 3 is an actual compounding display.
• 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 , and the fire resistance and char foaming state were evaluated according to the following criteria.
• the temperature of the thermocouple was recorded 20 minutes after ignition and evaluated according to the following criteria.
• Evaluations A and B were judged to have good fire resistance, and evaluations C and D were judged to have poor fire resistance.
• Tackiness A glass plate is coated with each water-based fire-resistant coating composition so that the dry film thickness is 2 mm, dried at 23 ° C.
• Examples 1-15 are water-based foamed fire resistant coating compositions using the styrene-rich emulsions defined in the present invention.
• Comparative Examples 1 and 2 are water-based foamed fire-resistant coating compositions outside the scope of the present invention in terms of styrene copolymerization amount.
• Fire resistance improves as the amount of styrene relative to the total polymerizable unsaturated monomers constituting the copolymer in the resin emulsion contained in the water-based fire-resistant paint composition increases.
• the styrene copolymerization amount which serves as a boundary for improving fire resistance, is 40% by mass.
• Inclusion of a co-solvent in the waterborne foam fire resistant coating composition improves tack and crack resistance without compromising fire resistance.

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• 2022
  • 2022-11-22 JP JP2023563688A patent/JPWO2023095772A1/ja active Pending
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