JP7463588B2 - Mixed liquid agent, polyurethane composition, cartridge container for caulking gun, pressure-resistant container for spray, and mixing system - Google Patents

Description

The present invention relates to a polyurethane composition, a cartridge container for a caulking gun, a pressure-resistant container for a spray, and a mixing system.

Traditionally, polyurethane foams have been used as insulation materials in vehicles such as automobiles, railway cars, and ships, as well as in buildings. They are also used as repair agents to fill defects in vehicles, buildings, etc. Recently, there has been an increasing need to impart flame retardancy to these insulation materials and repair agents.

Two-component polyurethane foams are widely used, in which a polyol liquid and an isocyanate liquid are mixed in separate containers to form the foam. One way to impart flame retardancy to this polyurethane foam is to increase the isocyanate index of the polyisocyanate.

For example, Patent Document 1 discloses a two-liquid aerosol flame-retardant polyisocyanurate foam in which an isocyanate component containing isocyanate and a propellant as main components and filled in an aerosol can is reacted with a polyol component containing polyol, a trimerization catalyst, and a propellant as main components and filled in another aerosol can so that the NCO/OH ratio is 1.5 to 5.0.

Japanese Patent Application Laid-Open No. 11-49837

When using two-component polyurethane as in Patent Document 1, small devices such as caulking guns and spray cans are used. These small devices are equipped with a static mixer, such as a static mixer, as a mixer for promoting mixing of the two components.
However, when increasing the isocyanate index, a large amount of trimerization catalyst is required to obtain a foam with excellent flame retardancy. When a large amount of trimerization catalyst is used, the residual liquid in the static mixer hardens in a short time and causes clogging. As a result, there is a problem that the static mixer needs to be replaced more frequently.

One solution would be to reduce the amount of trimerization catalyst used, but this would make it more difficult for the trimerization reaction to proceed, resulting in a decrease in the flame retardancy of the polyurethane foam that is formed.

The present invention aims to provide a mixed liquid agent that prevents the residual liquid from hardening in a static mixer and can form a polyurethane foam with high flame retardancy even when a small amount of trimerization catalyst is used.

As a result of intensive research aimed at solving the above-mentioned problems, the inventors of the present invention discovered that by using a resinification catalyst together with a trimerization catalyst and setting the contents of these catalysts within a prescribed range, hardening of the residual liquid in a static mixer can be prevented, and a highly flame-retardant polyurethane foam can be produced without using a large amount of a trimerization catalyst, thereby completing the present invention.
That is, the present invention is as follows.

[1] A mixed liquid agent comprising a polyol compound, a resinification catalyst, a trimerization catalyst, and a blowing agent, wherein the content of the resinification catalyst is 0.1 to 5 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst is 0.5 to 5 parts by mass relative to 100 parts by mass of the polyol compound.
[2] The mixed liquid agent according to [1], wherein the content of the resinification catalyst:the content of the trimerization catalyst is in the range of 1:1 to 1:50.
[3] The polyol mixture according to [2], wherein the content of the resinification catalyst:the content of the trimerization catalyst is in the range of 1:1 to 1:10.
[4] The mixed solution according to any one of [1] to [3], wherein the content of the resinification catalyst is 0.1 to 2 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst is 0.5 to 3 parts by mass relative to 100 parts by mass of the polyol compound.
[5] The mixture according to any one of [1] to [4], further comprising a flame retardant, the flame retardant being at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides.
[6] The mixed liquid agent according to [5], wherein the content of the flame retardant is 50 to 150 parts by mass per 100 parts by mass of the polyol compound.
[7] A polyurethane composition formed from a mixture of the mixed solution according to any one of [1] to [6] and an isocyanate solution containing a polyisocyanate, using a static mixer.
[8] The polyurethane composition according to [7], which constitutes a polyurethane foam.
[9] The polyurethane composition according to [7] or [8], which is used as a thermal insulation material for a vehicle or a building.
[10] A cartridge container for a caulking gun, filled with the mixed liquid agent according to any one of [1] to [6].
[11] A pressure-resistant spray container filled with the mixed liquid formulation according to any one of [1] to [6].
[12] A mixing system comprising: a first container filled with the mixed liquid agent according to any one of [1] to [6]; a second container filled with an isocyanate liquid agent containing a polyisocyanate compound; and a static mixer that mixes the mixed liquid agent discharged from the first container and the isocyanate liquid agent discharged from the second container.

The present invention provides a mixed liquid agent that can prevent the hardening of the residual liquid in the static mixer and can form a polyurethane foam with high flame retardancy even when a small amount of trimerization catalyst is used.

[Mixed liquid agent]
The mixed solution of the present invention includes a polyol compound, a resinification catalyst, a trimerization catalyst, and a blowing agent. The reaction rate of the resinification reaction, including the foaming reaction, of the mixed solution of the mixed solvent of the present invention and the isocyanate solution containing polyisocyanate is faster than the reaction rate of the trimerization reaction. Therefore, by setting the amounts of these components within a specific range, even if the mixed solution of the present invention and the isocyanate solution are mixed in a static mixer, the viscosity increase of the mixture due to the trimerization reaction is slow, and clogging in the static mixer due to the trimerization reaction of the mixed solution is unlikely to occur. Furthermore, after the mixture is discharged from a discharger such as a caulking gun or spray, the trimerization reaction of the mixture mainly proceeds, so that a polyurethane foam with high flame retardancy can be obtained even if the amount of the trimerization catalyst used is small. The mixed solution will be described in detail below.

(Polyol Compound)
The mixed liquid of the present invention contains a polyol compound.
Examples of the polyol compound used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.
Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols.
Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid, etc. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol, etc.
Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

Examples of polymer polyols include polymers obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate with aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, polybutadiene polyols, and modified polyols of polyhydric alcohols or hydrogenated products thereof.

Examples of modified polyols of polyhydric alcohols include those obtained by reacting a raw material polyhydric alcohol with an alkylene oxide to modify it.
Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; and condensates of phenol and formaldehyde (novolaks).

Although the method for modifying the polyhydric alcohol is not particularly limited, a method of adding an alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of the AO include AOs having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide.
Among these, from the viewpoints of properties and reactivity, PO, EO and 1,2-butylene oxide are preferred, and PO and EO are more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition or random addition, or a combination of these may be used.

Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, and tetrahydrofuran, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. Examples of low molecular weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and amines such as ethylenediamine and butylenediamine.

The polyol compounds used in the present invention are preferably polyester polyols and polyether polyols. Also, polyols having two hydroxyl groups are preferred. Among them, polyester polyols obtained by dehydration condensation of polybasic acids having aromatic rings, such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), with dihydric alcohols, such as bisphenol A, ethylene glycol, and 1,2-propylene glycol, are more preferred.

The hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH/g, more preferably 30 to 250 mgKOH/g, and even more preferably 50 to 220 mgKOH/g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the viscosity of the mixed liquid agent is likely to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing its strength.
The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

The content of the polyol compound in the mixed solution of the present invention is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 25 to 60% by mass. When the content of the polyol compound is equal to or greater than the lower limit, the polyol compound and the polyisocyanate compound are easily reacted. On the other hand, when the content of the polyol compound is equal to or less than the upper limit, the viscosity of the mixed solution does not become too high, and the handling property is improved.

(Resinification catalyst)
The mixed liquid agent of the present invention contains a resinification catalyst. The resinification catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. In the present invention, the resinification catalyst also includes a foaming catalyst that catalyzes the reaction between water and isocyanate. Examples of the resinification catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts.
Examples of the imidazole compound include tertiary amines in which the secondary amine at the 1-position of the imidazole ring is substituted with an alkyl group, an alkenyl group, or the like. Specific examples include N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. In addition, examples include imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group.
Furthermore, examples of the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine.
Examples of the amine catalyst include, in addition to imidazole compounds and piperazine compounds, various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, and tripropylamine.

Examples of the metal catalyst include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and are preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferred are organic acid tin salts such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, and organic acid bismuth salts such as bismuth trioctate, bismuth tris(2-ethylhexanoate), and among these, organic acid bismuth salts are preferred.
The resinification catalyst may be used alone or in combination of two or more. Among the above, it is preferable to use one or more selected from triethylenediamine and bismuth tris(2-ethylhexanoate).

The content of the resinification catalyst (the total when two or more kinds are contained) is 0.1 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1.5 parts by mass, relative to 100 parts by mass of the polyol compound. If the content of the resinification catalyst is less than the lower limit, it becomes difficult to form a urethane bond, and the reaction does not proceed quickly. On the other hand, if it is more than the upper limit, it becomes difficult to control the reaction rate, and the mixture of the mixed liquid agent and the isocyanate liquid agent containing the polyisocyanate compound hardens, making it easy for clogging to occur in the static mixer.
The mixed liquid agent of the present invention may contain a substance containing impurities other than the resinification catalyst component that functions as a resinification catalyst together with the resinification catalyst. In this case, the mass of only the resinification catalyst component excluding the impurities from the substance is the "content of the resinification catalyst."

(Trimerization Catalyst)
The mixed solution of the present invention contains a trimerization catalyst. The trimerization catalyst is a catalyst that reacts isocyanate groups contained in polyisocyanate to trimerize them and promote the formation of isocyanurate rings. As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, alkali metal salts of carboxylates such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate, tertiary ammonium salts such as trimethylammonium salts, triethylammonium salts, and triphenylammonium salts, and quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts, tetraphenylammonium salts, triethylmonomethylammonium salts, and quaternary ammonium salts of carboxylates can be used. These may be used alone or in combination of two or more.

Among the above, one or more carboxylates selected from the group consisting of alkali metal carboxylates and quaternary ammonium carboxylates are preferred. These carboxylate trimerization catalysts proceed immediately from the start of the trimerization reaction, and can reduce the amount of unreacted isocyanate. As a result, the flame retardancy of the polyurethane foam can be improved.

The content of the trimerization catalyst (the total when two or more kinds are contained) is 0.5 to 5 parts by mass, preferably 0.5 to 3 parts by mass, and more preferably 1 to 3 parts by mass, based on 100 parts by mass of the polyol compound. If the content of the trimerization catalyst is less than the lower limit, the trimerization of the polyisocyanate is difficult to occur, and the flame retardancy of the resulting polyurethane foam is reduced. On the other hand, if the content of the trimerization catalyst is more than the upper limit, it becomes difficult to control the reaction, and the mixture of the mixed liquid agent and the isocyanate liquid agent containing the polyisocyanate hardens, making it easy for clogging to occur in the static mixer.
The mixed liquid agent of the present invention may contain a substance containing impurities other than the trimerization catalyst component that functions as a trimerization catalyst together with the trimerization catalyst. In this case, the "content of the trimerization catalyst" is the mass of only the trimerization catalyst component obtained by excluding the impurities from the substance.

The total content of the trimerization catalyst and the resinification catalyst in the mixed solution of the present invention is not particularly limited, but is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 6 parts by mass. When the total content of both catalysts in the mixed solution of the present invention is equal to or greater than these lower limits, the formation of urethane bonds and trimerization proceed appropriately, and the flame retardancy of the polyurethane foam is likely to be good. When the total content of both catalysts in the mixed solution of the present invention is equal to or less than these upper limits, the urethane formation and trimerization reactions are easily controlled, and the mixture of the mixed solution and the isocyanate solution containing a polyisocyanate compound is less likely to harden and cause clogging in a static mixer.

In the mixed solution of the present invention, the preferred range of the resinification catalyst content: trimerization catalyst content is 1:1 to 1:50, more preferably 1:1 to 1:20, and even more preferably 1:1 to 1:10. When the trimerization catalyst content/resinification catalyst content is equal to or greater than the lower limit, the formation of urethane bonds and trimerization proceed properly, and the flame retardancy of the polyurethane foam is likely to be good. On the other hand, when the trimerization catalyst content/resinification catalyst content is equal to or less than the upper limit, the resinification catalyst and trimerization catalyst contents are reduced, and the mixture of the mixed solution and the isocyanate solution containing a polyisocyanate compound hardens, making it less likely to cause clogging in the static mixer.

(Foaming Agent)
The mixed liquid of the present invention contains a foaming agent. When the dispenser of the mixture of the mixed liquid of the present invention and the isocyanate liquid containing a polyisocyanate compound by a static mixer is a caulking gun, specific examples of the foaming agent include hydrofluoroolefins, hydrofluorocarbons, etc. One or more of these are used as the foaming agent.
When the dispenser is a spray, specific examples of the foaming agent include hydrocarbons having 2 to 5 carbon atoms, dimethyl ether, etc. One or more of these are used as the foaming agent.

Examples of hydrofluoroolefins include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefins may be hydrochlorofluoroolefins having a chlorine atom, and therefore may be chlorofluoroalkenes having about 3 to 6 carbon atoms. Preferred hydrofluoroolefins are fluoroalkenes having 3 or 4 carbon atoms, and more preferred hydrofluoroolefins are fluoroalkenes having 3 carbon atoms.
More specific examples include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specifically, examples thereof include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and 1,1,1,4,4,4-hexafluorobut-2-ene. Of these, HFO-1233zd is preferred.
These hydrofluoroolefins may be used alone or in combination of two or more kinds.

Specific examples of hydrofluorocarbons include hydrochlorofluorocarbon compounds such as trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane, HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), etc. Among these, HFC-245fa and HFC-365mfc are preferred.
These hydrofluorocarbons may be used alone or in combination of two or more kinds.

Specific examples of the hydrocarbon having 2 to 5 carbon atoms include propane, isobutane, normal butane, etc. Specific preferred examples of the at least one blowing agent selected from the group consisting of the hydrocarbon having 2 to 5 carbon atoms and dimethyl ether include dimethyl ether, and a mixed solvent of dimethyl ether and propane, isobutane, or normal butane, etc.

The content of the blowing agent is preferably 10 to 60 parts by mass, more preferably 20 to 55 parts by mass, even more preferably 25 to 50 parts by mass, and even more preferably 25 to 40 parts by mass, per 100 parts by mass of the polyol compound. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted and the density of the resulting polyurethane foam can be reduced. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be suppressed.

The mixed liquid of the present invention may contain water from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling.

(Flame retardants)
The mixed solution of the present invention may contain a flame retardant. The polyurethane foam produced using the mixed solution of the present invention has excellent flame retardancy because it contains an isocyanurate bond formed by trimerization of a polyisocyanate compound, but the flame retardancy of the polyurethane foam can be further improved by using a flame retardant.
The flame retardant used in the present invention is preferably at least one selected from the group consisting of phosphoric acid esters, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. The phosphoric acid ester may be a liquid flame retardant that is liquid at room temperature (23°C) and normal pressure (1 atm). By including a liquid flame retardant, the flame retardancy of the polyurethane composition of the present invention can be improved without substantially decreasing the discharge flow rate and mixability of the mixed liquid agent of the present invention.

As the phosphate ester, it is preferable to use monophosphate ester, condensed phosphate ester, etc. Examples of monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate, halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate, and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate. Among them, halogen-containing phosphate esters, particularly tris(β-chloropropyl)phosphate, etc. are preferred.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Commercially available condensed phosphate esters include, for example, "CR-733S", "CR-741", and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STAB PFR" and "FP-600" manufactured by ADEKA Corporation.

Among these, monophosphate esters are preferred, and tris(β-chloropropyl)phosphate is more preferred, from the viewpoint of reducing the viscosity of the mixture of the present invention and the isocyanate liquid agent containing a polyisocyanate compound, thereby facilitating the production of polyurethane foam, and from the viewpoint of improving the flame retardancy of polyurethane foam.

Examples of the phosphate-containing flame retardant include phosphates formed from salts of various phosphoric acids and at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring.
The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
Examples of metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amine include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine, etc.

Specific examples of the phosphate-containing flame retardant include monophosphates such as aluminum triphosphate, pyrophosphates, polyphosphates, etc. Here, the polyphosphates are not particularly limited, but include, for example, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, etc.
The phosphate-containing flame retardant may be one or more of the above-mentioned compounds. In the present invention, aluminum tertiary phosphate is preferred.

Red phosphorus may consist of red phosphorus alone, may be coated with a resin, a metal hydroxide, a metal oxide, or the like, or may be mixed with a resin, a metal hydroxide, a metal oxide, or the like. The resin with which red phosphorus is coated or mixed with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described below.

The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at room temperature and pressure. Examples of the bromine-containing flame retardant include brominated aromatic ring-containing aromatic compounds.
Examples of the brominated aromatic ring-containing aromatic compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A.

The brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.Specific examples of the brominated aromatic ring-containing aromatic compound include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin.Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like.
In addition, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may be used.
These bromine-containing flame retardants may be used alone or in combination of two or more. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among them, monomeric organic bromine compounds such as hexabromobenzene are preferred.

The boron-containing flame retardant used in the present invention includes borax, boron oxide, boric acid, borate, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium. Specific examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardants may be used alone or in combination of two or more kinds.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

Examples of antimony-containing flame retardants include antimony oxide, antimony salts, pyroantimony salts, etc. Examples of antimony oxide include antimony trioxide and antimony pentoxide, etc. Examples of antimony salts include sodium antimonate and potassium antimonate, etc. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate, etc.
The antimony-containing flame retardants may be used alone or in combination of two or more. The preferred antimony-containing flame retardant for use in the present invention is antimony trioxide.

Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. The metal hydroxides may be used alone or in combination of two or more. The preferred metal hydroxide used in the present invention is aluminum hydroxide.

When the mixed liquid agent of the present invention contains a flame retardant, the content is preferably 10 to 200 parts by mass, more preferably 20 to 180 parts by mass, even more preferably 40 to 170 parts by mass, and even more preferably 50 to 150 parts by mass, per 100 parts by mass of the polyol compound. When the content of the flame retardant is equal to or greater than the lower limit, sufficient flame retardancy can be imparted to the polyurethane foam produced using the mixed liquid agent. On the other hand, when the content of the flame retardant is equal to or less than the upper limit, foaming during production of the polyurethane foam is not inhibited.

(Foam stabilizer)
The mixed solution of the present invention may contain a foam stabilizer for the purpose of facilitating foaming of the mixture of the mixed solution and the isocyanate solution containing the polyisocyanate compound.
Examples of the foam stabilizer include polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone foam stabilizers such as organopolysiloxanes. These foam stabilizers may be used alone or in combination of two or more.

The content of the foam stabilizer in the mixed solution of the present invention is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the polyol compound. When the content of the foam stabilizer is equal to or greater than the lower limit, it becomes easier to foam the mixture of the mixed solution and the isocyanate solution containing the polyisocyanate compound, making it possible to obtain a homogeneous polyurethane foam. Furthermore, when the content of the foam stabilizer is equal to or less than the upper limit, the balance between the production cost and the obtained effect is optimal.

(Anti-settling agent)
The mixed solution of the present invention may contain an anti-settling agent. By using the anti-settling agent, the solid flame retardant dispersed in the mixed solution can be prevented from settling. In addition, by using the anti-settling agent, the solid flame retardant can be easily dispersed uniformly. The anti-settling agent is generally a solid at room temperature and normal pressure, and usually becomes a solid content (insoluble content) in the mixed solution.

The anti-settling agent is not particularly limited, but it is preferable to use one or more selected from, for example, carbon black, powdered silica, hydrogenated castor oil wax, fatty acid amide wax, organic clay, etc., and among these, powdered silica is more preferable.
The carbon black used in the anti-settling agent may be produced by a furnace method, a channel method, a thermal method, etc. The carbon black may be appropriately selected from commercially available products.
As the powdered silica, fumed silica, colloidal silica, silica gel, etc. can be used. Among these, fumed silica is preferred, and hydrophobic fumed silica is particularly preferred. As the fumed silica, Aerosil (registered trademark) from Nippon Aerosil Co., Ltd. can be used.
Hydrogenated castor oil wax, fatty acid amide wax, etc., form a swollen gel structure in liquid. These are generally commercially available under the names of thixotropic agents, thickeners, anti-settling agents, anti-sagging agents, etc., and commercially available products can be appropriately selected and used.

The content of the anti-settling agent is not particularly limited, but is, for example, 0.5 to 20 parts by mass, preferably 1 to 12 parts by mass, and more preferably 2 to 8 parts by mass, relative to 100 parts by mass of the polyol compound. By setting the content of the anti-settling agent within the above range, it is possible to prevent the settling of the solid flame retardant and improve its dispersibility without increasing the solid content more than necessary.

(Other ingredients)
The mixed liquid agent of the present invention may contain components other than the polyol compound, the resinification catalyst, the trimerization catalyst, the foaming agent, the flame retardant and the anti-settling agent, for example, it may contain an inorganic filler.
Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, and zirconia fiber. These inorganic fillers may be used alone or in combination of two or more.
When the mixed liquid agent of the present invention contains an inorganic filler, the content of the inorganic filler is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 20 to 70 parts by mass, relative to 100 parts by mass of the polyol compound.

The mixed liquid agent of the present invention may contain one or more selected from phenol-based, amine-based, sulfur-based and other antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, etc., as necessary, within the scope of the present invention.

(Method of manufacturing mixed liquid agent)
The method for producing the mixed solution of the present invention is not particularly limited, and for example, in the case of use as a caulking gun, each component other than the foaming agent is stirred, for example, by a known stirring device, and then the foaming agent is added to the obtained raw material, stirred, and filled into a cartridge container for a caulking gun to produce the mixed solution. In addition, in the case of use as a spray, each component other than the foaming agent is mixed, and then filled into a pressure-resistant container for spray together with the foaming agent to produce the mixed solution.

[Polyurethane composition]
The polyurethane composition of the present invention is formed from a mixture obtained by mixing the mixed liquid of the present invention with an isocyanate liquid containing a polyisocyanate in a static mixer.

(Isocyanate liquid)
The polyisocyanate used in the isocyanate liquid agent may be any known polyisocyanate compound used in the formation of polyurethane foam, such as aromatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.
Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and polymethylene polyphenyl polyisocyanates are more preferred. The polyisocyanate compounds may be used alone or in combination of two or more.
In addition, the isocyanate liquid may appropriately contain known additives contained in polyisocyanate compounds before being mixed with the mixed liquid.

It is preferable that the mixed liquid agent and the isocyanate liquid agent have substantially the same volume. Specifically, the volume ratio of the isocyanate liquid agent to the mixed liquid agent is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

(Isocyanate Index)
The isocyanate index of the polyurethane composition of the present invention is not particularly limited, but is preferably 200 or more. If the amount of the polyisocyanate compound relative to the polyol compound is excessive, a large amount of the trimerization catalyst is required, but in the present invention, a specific amount of the resinification catalyst is used together with the trimerization catalyst, so that the amount of the trimerization catalyst used can be reduced. If the isocyanate index is equal to or greater than the lower limit, the amount of the polyisocyanate compound relative to the polyol compound becomes excessive, which makes it easier to generate isocyanurate bonds due to the trimerization of the polyisocyanate compound, and as a result, the flame retardancy of the polyurethane foam is improved. In addition, it is possible to impart non-flammability. Furthermore, if the isocyanate index is equal to or greater than the above lower limit, it is easy to produce a polyurethane foam having isocyanurate bonds, i.e., a polyurethane foam having both flame retardancy and heat insulation at a high level. From these viewpoints, the isocyanate index is more preferably 250 or more, more preferably 300 or more, and particularly preferably 350 or more.
The isocyanate index is preferably not more than 1000, more preferably not more than 800, and particularly preferably not more than 500. When the isocyanate index is not more than the upper limit, the resulting polyurethane foam has a good balance between flame retardancy and production costs.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalents of polyisocyanate compound ÷ (equivalents of polyol compound + equivalents of water) × 100
Here, each equivalent number can be calculated as follows:
Equivalent number of polyisocyanate compound = Amount of polyisocyanate compound used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100
Equivalent number of polyol compound = OHV x amount of polyol compound used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value (mg KOH/g) of the polyol compound.
Number of water equivalents = amount of water used (g) / molecular weight of water (mol) × number of OH groups in water In each of the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmole), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

(Method for producing polyurethane composition)
The method for producing the polyurethane composition of the present invention is not particularly limited, but the polyurethane composition is formed by mixing the mixed liquid of the present invention and an isocyanate liquid containing a polyisocyanate compound in a static mixer and discharging the mixture from a dispenser such as a caulking gun or a spray.
The method for forming the polyurethane composition of the present invention using a caulking gun is, for example, carried out as follows: Two liquid agents are discharged from cartridge containers each filled with the mixed liquid agent of the present invention and an isocyanate liquid agent containing a polyisocyanate compound, and mixed in a static mixer such as a static mixer, and the mixture is sprayed from a caulking gun to cause foaming.
The method for forming the polyurethane composition of the present invention by spraying is, for example, carried out as follows: Two liquid agents are discharged from pressure-resistant spray containers each filled with the mixed liquid agent of the present invention and an isocyanate liquid agent containing a polyisocyanate compound, and mixed in a static mixer such as a static mixer, and the mixture is sprayed from a nozzle to cause foaming.

(Uses of polyurethane composition)
In the present invention, the polyurethane composition can be used in various applications, but is preferably used as a heat insulating material. The polyurethane composition is preferably used to form a polyurethane foam. By forming a polyurethane foam, a large number of bubbles are formed, which provides a heat insulating effect.
The polyurethane composition is more preferably used as a heat insulating material for vehicles or buildings. Examples of vehicles include railroad cars, automobiles, ships, and aircraft. The polyurethane composition of the present invention has high flame retardancy by using the above-mentioned mixed liquid agent. Therefore, from the viewpoint of disaster prevention and safety, it can be suitably used for applications in vehicles or buildings.

The mixed solution of the present invention can be formed into polyurethane foam with a simple configuration using a caulking gun and a spray can as described above. In addition, since the polyurethane composition of the present invention is formed using a caulking gun and a spray can, it is particularly suitable when the surface to be treated is relatively small. Therefore, for example, the mixed solution of the present invention is preferably used for repair purposes in which the mixed solution of the present invention is sprayed onto areas of an existing heat-resistant material that have deteriorated or been damaged, for example, to repair the area. Of course, the use is not limited to such uses, and the mixed solution of the present invention may also be used to form a new heat-resistant material.

(Caulking gun cartridges, spray pressure containers, mixing systems)
The mixing system of the present invention includes a first container filled with the mixed liquid, a second container filled with an isocyanate liquid containing a polyisocyanate compound, and a static mixer that mixes the mixed liquid discharged from the first container and the isocyanate liquid discharged from the second container.
The mixing system of the present invention is not limited to a specific system. When the mixing system of the present invention is a caulking gun, the first container filled with the mixed liquid agent is a cartridge container for the caulking gun. The second cartridge container for the caulking gun may or may not be filled with a blowing agent other than water together with the polyisocyanate compound, but preferably, no blowing agent is filled.
When the mixing system of the present invention is a pressure-resistant spray container, the first container filled with the mixed liquid is the pressure-resistant spray container, and the second pressure-resistant spray container is filled with a foaming agent other than water.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these.

The components used in the examples and comparative examples are shown below, and the content (parts by mass) of each component is shown in Tables 1 and 2.

1) Polyol compound: polyester polyol (Maximol RLK-087, manufactured by Kawasaki Chemical Industries, Ltd.)
2) Foam stabilizer: Polyoxyalkylene foam stabilizer (SH-193, manufactured by Toray Dow Corning Co., Ltd.)
3) Trimerization catalyst A-1: catalyst containing tetramethylammonium acetate salt (TOYOCAT-TRX manufactured by Tosoh Corporation, tetramethylammonium acetate salt concentration 65% by mass)
A-2: Catalyst containing potassium 2-ethylhexanoate (DABCO K-15 manufactured by Eponic Japan, potassium ethylhexanoate concentration 75% by mass)
4) Resinification catalyst B-1: Triethylenediamine-containing catalyst (DABCO 33LV manufactured by Eponic Japan, triethylenediamine concentration 33% by mass)
B-2: bismuth compound-containing catalyst (U-600 manufactured by Nitto Kasei Co., Ltd., bismuth compound concentration 55% by mass)
5) Blowing agent: Water, trans-1-chloro-3,3,3-trifluoropropene (Honeywell Solstice LBA, HFO)
Dimethyl ether (DME)
6) Flame retardant C-1: Red phosphorus (Nova Excel 140 manufactured by Rinkagaku Kogyo Co., Ltd.)
C-2: Tris(β-chloropropyl)phosphate (TMCPP manufactured by Daihachi Chemical Industry Co., Ltd.)
C-3: Aluminum phosphate tribasic (manufactured by Taihei Chemical Industry Co., Ltd.)
C-4: Hexabromobenzene (manufactured by Manac Corporation)
C-5: Antimony trioxide (Patox C, manufactured by Nippon Seiko Co., Ltd.)
C-6: Aluminum hydroxide (B-325 manufactured by Armolix)
7) Anti-settling agent: Aerosil (R756S manufactured by Nippon Aerosil Co., Ltd.)
8) Polyisocyanate (isocyanate compound): Polymeric MDI (MR-400 manufactured by Mitsui Chemicals, Inc.)

Examples 1 to 10 and Comparative Examples 1 and 2
Each operation was carried out according to the formulations shown in Tables 1 and 2. First, the components other than trans-1-chloro-3,3,3-trifluoropropene (hereinafter referred to as "HFO") were stirred in a 1000 ml beaker at 1500 rpm for 3 minutes using a three-one motor. Then, HFO was further added and stirred for 3 minutes under the same conditions to obtain a mixed liquid.

The obtained mixed solution and the polyisocyanate compound, which is the isocyanate solution, were each filled into a 100 ml cartridge (AC200-01-10-01, manufactured by Mixpack). Next, each cartridge was installed in a gas-driven caulking gun (DP200-70-01/SP, 100 x 100, manufactured by Mixpack). A spray static mixer (SM616SP, manufactured by Mixpack) with an inner diameter of 6 mm and 16 elements was attached to the gas-driven caulking gun. In addition, a 7 ^m3 compressed nitrogen cylinder was used to drive the caulking gun, and the secondary operating pressure of the cylinder was adjusted to 0.3 MPa.
The trigger of the caulking gun was pressed to discharge from each cartridge. The mixed solution and the isocyanate solution discharged from each cartridge were mixed in a static mixer and discharged onto a gypsum board having a thickness of 12 mm to obtain a polyurethane foam.
The re-dischargeability of the mixture and the flame retardancy of the polyurethane foam were evaluated as follows. The results are shown in Tables 1 and 2.

(1) Re-ejectability of mixture A mixture of the mixed liquid and the isocyanate liquid was ejected for 2 seconds. If it could be ejected again after 60 seconds, it was rated as A. If it could be ejected again after 30 seconds, it was rated as B. If it could not be ejected again after 30 seconds, it was rated as C.

(2) Flame retardancy of polyurethane foam The gypsum board and polyurethane foam were cut to 10 cm x 10 cm. Next, the polyurethane foam was cut together with the gypsum board so that the thickness of the polyurethane foam was 30 mm, and the total heat generation amount when the obtained sample was heated for 5 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with the test method of ISO-5660 was measured using a cone calorimeter. The total heat generation amount for 5 minutes was evaluated as A when it was 8 MJ or less, B when it was more than 8 MJ and 10 MJ or less, and C when it exceeded 10 MJ.

Examples 11 and 12 and Comparative Examples 3 and 4
Each operation was carried out according to the formulation shown in Tables 1 and 2. First, the components other than DME were stirred in a 1000 ml beaker at 1500 rpm for 3 minutes using a three-one motor to obtain a mixed solution. The mixed solution and DME were filled into a 100 ml aerosol test bottle (manufactured by Tokyo Polymer Co., Ltd.). In addition, an isocyanate solution containing polyisocyanate and DME was filled into another aerosol test bottle. The two aerosol test bottles were connected to a static mixer (ACF Helix 08-18 manufactured by Ritter Co., Ltd.), and the mixed solution and polyisocyanate were simultaneously sprayed onto a gypsum board having a thickness of 12 mm from a nozzle (manufactured by Maruichi Co., Ltd.) with a stem hole of 0.5 x 2 to obtain a polyurethane foam. The re-ejectability of the mixture and the flame retardancy of the polyurethane foam were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

In Tables 1 and 2 above, the unit of the content of each component is parts by mass. The trimerization catalyst component mass is the mass (unit: parts by mass) of only the trimerization catalyst component, excluding impurities, from the substance contained in the mixed liquid as a trimerization catalyst. The resinification catalyst component mass is the mass (unit: parts by mass) of only the resinification catalyst component, excluding impurities, from the substance contained in the mixed liquid as a resinification catalyst. Trimerization/resinification catalyst is the mass ratio of only the trimerization catalyst component/only the resinification catalyst component.

The Examples were good in both re-ejection evaluation and flame retardancy evaluation, but the polyurethane foams of Comparative Examples 1 and 3, in which the resinification catalyst and trimerization catalyst contents were too low, had low flame retardancy. In addition, the mixture of the mixed liquid agent and polyisocyanate used in Comparative Examples 2 and 4, in which the resinification catalyst and trimerization catalyst contents were too high, had low re-ejection properties.

Claims (7)

The present invention comprises a pressure-resistant container for aerosol spray and a mixed liquid agent filled in the pressure-resistant container for aerosol spray,
the mixed solution agent contains a polyol compound, a resinification catalyst, a trimerization catalyst , a flame retardant , and a foaming agent, the content of the resinification catalyst being 0.1 to 5 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst being 0.5 to 5 parts by mass relative to 100 parts by mass of the polyol compound,
the content of the flame retardant is 20 to 200 parts by mass relative to 100 parts by mass of the polyol compound,
the trimerization catalyst comprises at least one selected from the group consisting of alkali metal carboxylates and quaternary ammonium carboxylates,
The pressure-resistant container for aerosol spray filled with a mixed liquid agent, wherein the resinification catalyst contains an organic acid bismuth salt . 2. The pressure-resistant container for aerosol sprays filled with a mixed solution according to claim 1, wherein the content of said resinification catalyst: the content of said trimerization catalyst is in the range of 1:1 to 1:50. 3. The pressure-resistant container for aerosol sprays filled with a mixed solution according to claim 2, wherein the content of the resinification catalyst:the content of the trimerization catalyst is in the range of 1:1 to 1:10. The pressure-resistant container for aerosol sprays filled with a mixed solution according to any one of claims 1 to 3, wherein the content of the resinification catalyst is 0.1 to 2 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst is 0.5 to 3 parts by mass relative to 100 parts by mass of the polyol compound. The pressure - resistant container for aerosol sprays filled with a mixed solution according to any one of claims 1 to 4, wherein the flame retardant is at least one selected from the group consisting of phosphoric acid esters, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boron-containing flame retardants, antimony- containing flame retardants, and metal hydroxides. The pressure-resistant container for aerosol sprays filled with a mixed solution according to any one of claims 1 to 5, wherein the content of the flame retardant is 50 to 150 parts by mass per 100 parts by mass of the polyol compound. a polyol compound, a resinification catalyst, a trimerization catalyst , a flame retardant , and a foaming agent, the content of the resinification catalyst being 0.1 to 5 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the trimerization catalyst being 0.5 to 5 parts by mass relative to 100 parts by mass of the polyol compound,
the content of the flame retardant is 20 to 200 parts by mass relative to 100 parts by mass of the polyol compound,
the trimerization catalyst comprises at least one selected from the group consisting of alkali metal carboxylates and quaternary ammonium carboxylates,
A step of discharging the mixed solution from a first pressure-resistant container for aerosol spray in which the mixed solution is filled, the mixed solution containing the resinification catalyst containing an organic acid bismuth salt ;
A step of discharging an isocyanate liquid agent from a second pressure-resistant container for aerosol spray in which an isocyanate liquid agent containing a polyisocyanate compound is filled;
A method for producing a polyurethane foam, comprising a step of mixing the mixed liquid agent discharged from the first pressure-resistant container for aerosol spray and the isocyanate liquid agent discharged from the second pressure-resistant container for aerosol spray.