Fire extinguishing agent

Abstract

To provide a fire extinguishing agent hat enables the formation of foam with superior heat resistance.SOLUTION: A fire extinguishing agent comprises: a fluorine-based surfactant with a perfluoropolyether group; and an alkanolamine with a tertiary amine structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fire extinguishing agent. [Background technology]

[0002] Foam extinguishing agents are used to prevent the spread of fire and to extinguish flammable liquid fires that are difficult to extinguish with water alone. As foam extinguishing agents, extinguishing agents containing fluorosurfactants are known. As a method for improving the heat resistance of foam formed from extinguishing agents, for example, a method of adding a water-soluble polymer to a fluorosurfactant is known (for example, Patent Document 1).

[0003] Fluorosurfactants have a high surface tension reducing ability, and are additives that realize excellent penetration, wettability, leveling, surface functionality, etc. by mixing with fire extinguishing agents and coating compositions, and various fluorosurfactants have been proposed so far. In general, fluorosurfactants are compounds that have a perfluoroalkyl group for realizing the surface tension reducing ability and a philic group that contributes to affinity for various compositions in the same molecule. Conventional fluorosurfactants have used compounds containing perfluoroalkyl groups with 6 or more carbon atoms, which have high surface orientation and cohesion properties and can reduce surface tension with a small amount of addition, but replacement of these has been promoted in response to fluorine regulations. When fire extinguishing agents using fluorosurfactants other than compounds containing perfluoroalkyl groups with 6 or more carbon atoms were examined, the heat resistance of the foam was insufficient when only a water-soluble polymer was added. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2001-269421 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a fire extinguishing agent capable of forming a foam having excellent heat resistance. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors conducted extensive research and discovered that by using a fluorine-based surfactant having a perfluoropolyether group and an alkanolamine having a tertiary amine structure, a fire extinguishing agent capable of forming foam with excellent heat resistance can be obtained.

[0007] The present invention has been completed based on these findings, and includes the following broad aspects. [Section 1] A fluorosurfactant having a perfluoropolyether group, and A fire extinguishing agent comprising an alkanolamine having a tertiary amine structure. [Section 2] Item 2. The fire extinguishing agent according to item 1, wherein the content of the alkanolamine is 1 to 10 parts by mass per part by mass of the fluorosurfactant. [Section 3] The fluorosurfactant is Item 3. The fire extinguishing agent according to item 1 or 2, which is at least one selected from the group consisting of anionic surfactants and betaine surfactants. [Section 4] The anionic surfactant is a compound represented by the following formula (1) or (2) or a salt thereof: Item 4. The fire extinguishing agent according to item 3, wherein the betaine surfactant is a compound represented by the following formula (3):

[0008] Formula (1):

[0009] [ka]

[0010] (In the formula, Rf1 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 1is a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms. m is an integer of 0 to 5. n is an integer of 1 to 3. Formula (2):

[0011] [ka]

[0012] (In the formula, Rf2 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 2 is a single bond, or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. k is an integer of 0 to 5. Formula (3):

[0013] [ka]

[0014] (In the formula, Rf3 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 3 R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. 4 , R 5 R are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms. 6 is a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms; l is an integer of 0 to 5; and X is a carboxyl group or a sulfo group. [Section 5] 5. The fire extinguishing agent according to any one of items 1 to 4, wherein the alkanolamine is a compound having three or more hydroxyl groups in the molecule. [Section 6] 6. The fire extinguishing agent according to any one of items 1 to 5, wherein the alkanolamine has an acid dissociation constant pKa of 8.5 or less. [Section 7] 7. The fire extinguishing agent according to any one of items 1 to 6, wherein the alkanolamine is a compound represented by the following formula (4):

[0015] Formula (4):

[0016] [ka]

[0017] (In the formula, R 7 , R 8 , R 9 are the same or different and each is an alkyl group having 1 to 5 carbon atoms. Effect of the Invention

[0018] According to the present invention, it is possible to provide a fire extinguishing agent capable of forming foam having excellent heat resistance. [Brief description of the drawings]

[0019] [Figure 1] Schematic diagram of foam heat resistance evaluation method. [Diagram 2] The criteria for evaluating the heat resistance of foam are shown below. [Diagram 3] The following is a hypothetical mechanism by which alkanolamines having a tertiary amine structure have a higher effect of improving the heat resistance of foam than other alkanolamines. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] <Fire extinguishing agent> The fire extinguishing agent of the present invention contains a fluorosurfactant having a perfluoropolyether group, and an alkanolamine having a tertiary amine structure. [Fluorosurfactant] The fluorosurfactant in the present invention has a perfluoropolyether group. The fluorosurfactant is preferably at least one selected from the group consisting of anionic surfactants and betaine surfactants. The fluorosurfactant may be used alone or in combination of two or more.

[0021] The anionic surfactant in the present invention is not particularly limited as long as it has a perfluoropolyether group and the hydrophilic group moiety is a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, or the like. However, it is preferable that the anionic surfactant is a compound represented by the following formula (1) or (2) or a salt thereof.

[0022] Formula (1):

[0023] [ka]

[0024] (In the formula, Rf1 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms. m is an integer of 0 to 5. n is an integer of 1 to 3. Formula (2):

[0025] [ka]

[0026] (In the formula, Rf2 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 2 is a single bond, or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. k is an integer of 0 to 5. The betaine surfactant in the present invention is not particularly limited as long as it is a fluorosurfactant having a perfluoropolyether group and a betaine in its molecular structure, but is preferably a compound represented by the following formula (3): Here, "betaine" refers to an intramolecular salt having a positive charge and a negative charge at non-adjacent positions in the same molecule.

[0027] Formula (3):

[0028] [ka]

[0029] (In the formula, Rf3 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 3 R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. 4 , R 5 R are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms. 6 is a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms; l is an integer of 0 to 5; and X is a carboxyl group or a sulfo group. The content of the fluorosurfactant in the present invention (when multiple types of fluorosurfactants are contained, the total content) is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 parts by mass, and particularly preferably 0.05 to 0.2 parts by mass, relative to 100 parts by mass of the total amount of the extinguishing agent. (Compound represented by formula (1) or a salt thereof) Formula (1):

[0030] [ka]

[0031] (In the formula, Rf1 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms. m is an integer of 0 to 5. n is an integer of 1 to 3. In the formula (1), Rf1 is a perfluoroalkyl group having 1 to 4 carbon atoms, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

[0032] R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms. It is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms.

[0033] Examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms include a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 18 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 18 carbon atoms, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and a substituted or unsubstituted aralkylene group having 7 to 18 carbon atoms.

[0034] Preferred are substituted or unsubstituted alkylene groups having 2 to 10 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 10 carbon atoms, substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, and substituted or unsubstituted aralkylene groups having 7 to 10 carbon atoms, and more preferred are substituted or unsubstituted alkylene groups having 2 to 8 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 8 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 8 carbon atoms, substituted or unsubstituted arylene groups having 6 to 8 carbon atoms, and substituted or unsubstituted aralkylene groups having 7 to 8 carbon atoms.

[0035] Examples of the unsubstituted alkylene group having 2 to 18 carbon atoms include linear alkylene groups having 2 to 18 carbon atoms (such as an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group); branched alkylene groups having 3 to 18 carbon atoms (such as a 1-methylethylene group, a 2-methylethylene group, a 1-ethylethylene group, a 2-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,1-dimethylpropylene group, a 1-hexylpropylene group, a 1-hexylbutylene group, and a 1-octylethylene group).

[0036] Examples of the unsubstituted alkenylene group having 2 to 18 carbon atoms include linear alkenylene groups having 2 to 18 carbon atoms (e.g., ethenylene group, propenylene group, etc.); branched alkenylene groups having 3 to 18 carbon atoms (e.g., 1-ethylethenylene group, 1,2-dimethylethenylene group, 1-butylethenylene group, 1-hexylethenylene group, etc.).

[0037] Examples of the cycloalkylene group having 4 to 18 carbon atoms include a cyclobutylene group, a cyclopentylene group, a 2-methylcyclopentylene group, a cyclohexylene group, a 1,3-dimethylcyclohexylene group, a 1-ethylcyclopentylene group, and a cyclohexanedimethylene group.

[0038] Examples of the arylene group having 6 to 18 carbon atoms include an o-, p- or m-phenylene group, a 2,4-naphthylene group, a biphenylene group, and a tolylene group.

[0039] Examples of the aralkylene group having 7 to 18 carbon atoms include a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenyleneethyl group, and a naphthylmethylene group.

[0040] R 1 In the above, when the hydrocarbon group has a substituent, examples of the substituent that replaces a hydrogen atom in the hydrocarbon group include a halogen atom, an amino group, a hydroxyl group, a thiol group, a carboxyl group, an amide group, a guanidide group, a nitro group, a cyano group, a monoalkylamino group, a dialkylamino group, an alkoxy group, an alkylthio group, an aryloxy group, a halogenated alkyl group (the number of halogen atoms is preferably 1 to 10, more preferably 1 to 7. When there are multiple halogen atoms, they may be the same or different.), an alkylcarbonylamino group, an alkyloxycarbonylamino group, etc. When the hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 5, more preferably 1 to 3. When there are multiple substituents, the substituents may be the same or different.

[0041] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0042] Examples of the alkyl moiety of the monoalkylamino group, dialkylamino group, alkoxy group, alkylthio group, halogenated alkyl group, alkylcarbonylamino group, and alkyloxycarbonylamino group mentioned above as the substituent include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-ethylpentyl group, heptyl group, octyl group, and 2-ethylhexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 8.

[0043] In addition, the aryl moiety of the aryloxy group exemplified as the above-mentioned substituent includes aryl groups having 6 to 10 carbon atoms, such as a phenyl group and a naphthyl group.

[0044] Also, R 1 In the above, the hydrocarbon group having a substituent may have a divalent group containing at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom between carbon atoms of the hydrocarbon group. The number of heteroatoms may be preferably 1 to 10, more preferably 1 to 6. Examples of the divalent group containing at least one heteroatom include -O-, -N<, -S-, -SO2-, -(C=O)-, -(C=O)O-, -O(C=O)-, -NH(C=O)-, -(C=O)NH-, -NH(C=O)O-, -O(C=O)NH-, etc. When such a divalent group is between carbon atoms of the hydrocarbon group, the hydrocarbon chain is interrupted by this group. In addition, R 1 ~R 4 In the above, such a divalent group is inserted between the carbon atoms of the hydrocarbon group, so that R 1 ~R 4 may have a structure having a hetero ring.

[0045] In one embodiment, R 1 is preferably a group represented by the following formula (a).

[0046] Formula (a):

[0047] [ka]

[0048] (In the formula, R a is a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms. Ar is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 15 carbon atoms. * is a bond. In formula (a), R a is a substituted or unsubstituted trivalent hydrocarbon group having 1 to 3 carbon atoms. It is preferably an unsubstituted trivalent hydrocarbon group having 1 to 3 carbon atoms.

[0049] Ar is a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms. Examples of the unsubstituted monovalent aromatic hydrocarbon group include a phenyl group, a tolyl group, and a naphthyl group.

[0050] R a and the substituents in Ar include R 1 is the same as defined above in

[0051] R 1 Examples of such substances include those listed below.

[0052] [ka]

[0053] (In the formula, * represents a bond.) Among these, the following structure represented by formula (a) is R 1 As preferred.

[0054] [ka]

[0055] (In the formula, * represents a bond.) In formula (1), m is an integer of 0 to 5. m is more preferably an integer of 0 to 3, further preferably 1 or 2, and particularly preferably 1. When m is within the above range, the fluorosurfactant has excellent surface tension reducing ability, and the heat resistance of the foam is good. On the other hand, when m exceeds 5, the water solubility of the fluorosurfactant may decrease.

[0056] In formula (1), n ​​is an integer of 1 to 3. n is more preferably 1 or 2, and further preferably 1.

[0057] The molecular weight of the compound represented by formula (1) is preferably 400-1,800, more preferably 400-1,100, and even more preferably 550-900.

[0058] Specific examples of the compound represented by formula (1) include, but are not limited to, the following:

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] As the compound of formula (1), compounds represented by formulas (1-2-1), (1-2-3), (1-2-6), (1-2-7), (1-2-9), (1-2-11), (1-2-16), (1-2-17), (1-2-18), (1-2-19), (1-2-21), (1-2-22), and (1-2-23) are preferred. Compounds represented by formulas (1-2-16) and (1-2-19) are more preferred.

[0065] In a preferred embodiment, the compound represented by formula (1) may be a salt. Examples of the salt include metal salts, amine salts, and ammonium salts. Examples of the metal salt include alkali metal salts, alkaline earth metal salts, and transition metal salts. Specific examples of metal atoms forming metal salts include Li, Na, K, Ca, Mg, Cu, Co, Ni, Zn, Mn, Fe, Pb, Hg, and Zr. Examples of amine compounds or ammonia forming amine salts or ammonium salts include ammonia, trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, morpholine, and pyridine. Among these, sodium salts are preferred. By forming the salt, hydrophilicity can be increased, and stability in water can be increased.

[0066] The compound represented by formula (1) or a salt thereof can be produced, for example, by a method including a step of reacting a perfluoropolyether compound represented by the following formula (5) with an amino acid.

[0067] Formula (5):

[0068] [ka]

[0069] [In the formula, Rf1 is a perfluoroalkyl group having 1 to 4 carbon atoms. 10 is a substituted or unsubstituted hydrocarbon group. m is an integer of 0 to 5. Rf1 and m in formula (5) are the same as defined in formula (1).

[0070] In formula (5), R 10 is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

[0071] Examples of the unsubstituted hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, an allyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a phenyl group. Preferred are a methyl group, an ethyl group, a tert-butyl group, and a benzyl group, and particularly preferred is a methyl group.

[0072] R 10 In the case where the hydrocarbon group has a substituent, the substituent is R 1 The substituents described above in the above can be used without any particular limitation.

[0073] Specific examples of the perfluoropolyether compound represented by formula (5) include, but are not limited to, the following:

[0074] [ka]

[0075] The perfluoropolyether compound represented by formula (5) is also available as a commercial product; for example, CAE-500, CAE-600, and CAE-1000 (all manufactured by Sinochem Corporation) can be used.

[0076] The step of reacting the perfluoropolyether compound represented by formula (5) with an amino acid can be represented, for example, by the following reaction formula.

[0077] [ka]

[0078] In the above reaction formula, R in the amino acid represented by formula (6) 1 and n is the same as defined in formula (1).

[0079] Examples of amino acids represented by formula (6) include, but are not limited to, glycine, alanine, tyrosine, leucine, isoleucine, valine, phenylalanine, serine, threonine, asparagine, glutamine, cysteine, methionine, tryptophan, histidine, aspartic acid, glutamic acid, β-alanine, γ-aminobutyric acid, phenylglycine, o-, p-, or m-aminobenzoic acid, etc.

[0080] The reaction is carried out in the presence of a base, which may include organic bases such as triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, diazabicyclononene, and diazabicycloundecene, inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide, and organic lithiums such as methyllithium and butyllithium.

[0081] The reaction temperature is usually from 0° C. to 100° C. or the boiling temperature of the solvent.

[0082] The reaction time is usually 1 to 48 hours, preferably 1 to 20 hours.

[0083] Examples of the reaction solvent include methanol, ethanol, tetrahydrofuran, diethyl ether, ethyl acetate, acetonitrile, acetone, and methyl ethyl ketone.

[0084] When a solvent is used, the amount of the solvent used is usually 100 parts by mass or less, preferably 1 to 50 parts by mass, per part by mass of the perfluoropolyether compound represented by the formula (5). Two or more kinds of solvents can be mixed and used as needed.

[0085] If necessary, the reaction may be carried out in an atmosphere of an inert gas such as nitrogen, argon, or helium that does not affect the reaction.

[0086] After completion of the reaction, impurities (e.g., unreacted raw materials) can be removed by washing with an organic solvent, the reaction solution can be concentrated, or the like to obtain a compound represented by formula (1). If necessary, further purification can be performed using a known method.

[0087] Furthermore, a salt of the compound represented by formula (1) can be obtained by neutralization with various bases such as sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, etc. (Compound represented by formula (2) or a salt thereof) Formula (2):

[0088] [ka]

[0089] (In the formula, Rf2 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 2 represents a single bond, or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. k is an integer of 0 to 5. In formula (2), Rf2 is a perfluoroalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

[0090] R 2 is a single bond, or a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms. It is preferably a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms.

[0091] Examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms include a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and a substituted or unsubstituted aralkylene group having 7 to 10 carbon atoms.

[0092] Preferred are substituted or unsubstituted alkylene groups having 1 to 8 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 8 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 8 carbon atoms, substituted or unsubstituted arylene groups having 6 to 8 carbon atoms, and substituted or unsubstituted aralkylene groups having 7 to 8 carbon atoms, and more preferred are substituted or unsubstituted alkylene groups having 1 to 6 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 6 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 6 carbon atoms, and substituted or unsubstituted arylene groups having 6 carbon atoms.

[0093] Examples of the unsubstituted alkylene group having 1 to 10 carbon atoms include linear alkylene groups having 1 to 10 carbon atoms (e.g., methylene, ethylene, trimethylene, tetramethylene, and pentamethylene); branched alkylene groups having 3 to 10 carbon atoms (e.g., 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1-hexylpropylene, 1-hexylbutylene, and 1-octylethylene).

[0094] Examples of the unsubstituted alkenylene group having 2 to 10 carbon atoms include linear alkenylene groups having 2 to 10 carbon atoms (e.g., ethenylene group, propenylene group, etc.); branched alkenylene groups having 3 to 10 carbon atoms (e.g., 1-ethylethenylene group, 1,2-dimethylethenylene group, 1-butylethenylene group, 1-hexylethenylene group, etc.).

[0095] Examples of the cycloalkylene group having 4 to 10 carbon atoms include a cyclobutylene group, a cyclopentylene group, a 2-methylcyclopentylene group, a cyclohexylene group, a 1,3-dimethylcyclohexylene group, a 1-ethylcyclopentylene group, and a cyclohexanedimethylene group.

[0096] Examples of the arylene group having 6 to 10 carbon atoms include an o-, p- or m-phenylene group, a 2,4-naphthylene group, a biphenylene group, and a tolylene group.

[0097] Examples of the aralkylene group having 7 to 10 carbon atoms include a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenyleneethyl group, and a naphthylmethylene group.

[0098] R 2 In the case where the hydrocarbon group has a substituent, the substituent is R 1 The substituents described above in the above can be used without any particular limitation.

[0099] R 2 Examples of such substances include those listed below.

[0100] [ka]

[0101] (In the formula, * indicates a bond, and the * on the right side indicates a bond bonded to the sulfur atom of the sulfonic acid group.) Among these, the following structure is R 2 As preferred.

[0102] [ka]

[0103] (In the formula, * indicates a bond, and the * on the right side indicates a bond bonded to the sulfur atom of the sulfonic acid group.) In formula (2), k is an integer of 0 to 5. k is more preferably an integer of 0 to 3, further preferably an integer of 0 to 2, and particularly preferably 1. When k is within the above range, the fluorosurfactant has excellent surface tension reducing ability, and the heat resistance of the foam is good. When k exceeds 5, the water solubility of the fluorosurfactant may decrease.

[0104] The molecular weight of the compound represented by formula (2) is preferably 400-1,400, more preferably 400-1,000, and even more preferably 400-900.

[0105] Specific examples of the compound represented by formula (2) include, but are not limited to, the following:

[0106] [ka]

[0107] As the compound of formula (2), the compounds represented by formulae (2-1-1), (2-1-2), (2-1-3), (2-1-4), (2-2-1), (2-2-2), (2-2-3), and (2-2-4) are preferred, and the compounds represented by formulae (2-2-1), (2-2-2), (2-2-3), and (2-2-4) are more preferred.

[0108] In a preferred embodiment, the compound represented by formula (2) may be a salt. Examples of the salt include metal salts, amine salts, and ammonium salts. Examples of the metal salt include alkali metal salts, alkaline earth metal salts, and transition metal salts. Specific examples of metal atoms forming metal salts include Li, Na, K, Ca, Mg, Cu, Co, Ni, Zn, Mn, Fe, Pb, Hg, and Zr. Examples of amine compounds or ammonia forming amine salts or ammonium salts include ammonia, trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, morpholine, and pyridine. Among these, sodium salts are preferred. By forming the salt, hydrophilicity can be increased, and stability in water can be increased.

[0109] The compound represented by formula (2) or a salt thereof can be produced, for example, by a method including a step of reacting a perfluoropolyether compound represented by the following formula (7) with aminosulfonic acid.

[0110] Formula (7):

[0111] [ka]

[0112] [In the formula, Rf2 is a perfluoroalkyl group having 1 to 4 carbon atoms. 11 is a substituted or unsubstituted hydrocarbon group. k is an integer of 0 to 5. Rf2 and k in formula (2) are the same as defined in formula (1).

[0113] In formula (2), R 11 is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

[0114] Examples of the unsubstituted hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, an allyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a phenyl group. Preferred are a methyl group, an ethyl group, a tert-butyl group, and a benzyl group, and particularly preferred is a methyl group.

[0115] R 11 In the case where the hydrocarbon group has a substituent, the substituent is R 1 The substituents described above in the above can be used without any particular limitation.

[0116] Specific examples of the perfluoropolyether compound represented by formula (7) include, but are not limited to, the following:

[0117] [ka]

[0118] The perfluoropolyether compound represented by formula (7) is also available as a commercial product; for example, CAE-500, CAE-600, and CAE-1000 (all manufactured by Sinochem Corporation) can be used.

[0119] The step of reacting the perfluoropolyether compound represented by formula (7) with aminosulfonic acid can be represented, for example, by the following reaction formula.

[0120] [ka]

[0121] In the above reaction formula, R in the aminosulfonic acid represented by formula (8) 1 and n is the same as defined in formula (1).

[0122] Examples of the aminosulfonic acid represented by formula (8) include, but are not limited to, sulfamic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid (sulfanilic acid), aminomethanesulfonic acid, 2-aminoethanesulfonic acid, and 3-amino-1-propanesulfonic acid.

[0123] The reaction is carried out in the presence of a base, which may include organic bases such as triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, diazabicyclononene, and diazabicycloundecene, inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide, and organic lithiums such as methyllithium and butyllithium.

[0124] The reaction temperature is usually from 0° C. to 100° C. or the boiling temperature of the solvent.

[0125] The reaction time is usually 1 to 48 hours, preferably 1 to 20 hours.

[0126] Examples of the reaction solvent include methanol, ethanol, tetrahydrofuran, diethyl ether, ethyl acetate, acetonitrile, acetone, and methyl ethyl ketone.

[0127] When a solvent is used, the amount of the solvent used is usually 100 parts by mass or less, preferably 0.5 to 50 parts by mass, per part by mass of the perfluoropolyether compound represented by the formula (7). Two or more kinds of solvents can be mixed and used as needed.

[0128] If necessary, the reaction may be carried out in an atmosphere of an inert gas such as nitrogen, argon, or helium that does not affect the reaction.

[0129] After completion of the reaction, the compound represented by formula (2) can be obtained by removing impurities (e.g., unreacted raw materials) by washing with an organic solvent or concentrating the reaction solution, and if necessary, further purification may be performed using a known method.

[0130] Moreover, the salt of the aminosulfonic acid-modified perfluoropolyether compound represented by formula (2) can be obtained by neutralizing it with various bases such as sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, and the like. (Compound represented by formula (3)) Formula (3):

[0131] [ka]

[0132] (In the formula, Rf3 is a perfluoroalkyl group having 1 to 4 carbon atoms. R 3 R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. 4 , R 5 R are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms. 6 is a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms; l is an integer of 0 to 5; and X is a carboxyl group or a sulfo group. In the formula (3), Rf3 is a perfluoroalkyl group having 1 to 4 carbon atoms, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

[0133] R 3 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms. It is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, and more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms.

[0134] Examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms include a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and a substituted or unsubstituted aralkylene group having 7 to 10 carbon atoms.

[0135] Preferably, it is a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 8 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 8 carbon atoms, a substituted or unsubstituted arylene group having 6 to 8 carbon atoms, or a substituted or unsubstituted aralkylene group having 7 to 8 carbon atoms, and more preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms.

[0136] Examples of the unsubstituted alkylene group having 1 to 10 carbon atoms include linear alkylene groups having 1 to 10 carbon atoms (e.g., methylene, ethylene, trimethylene, tetramethylene, and pentamethylene); branched alkylene groups having 3 to 10 carbon atoms (e.g., 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1-hexylpropylene, 1-hexylbutylene, and 1-octylethylene).

[0137] Examples of the unsubstituted alkenylene group having 2 to 10 carbon atoms include linear alkenylene groups having 2 to 10 carbon atoms (e.g., ethenylene group, propenylene group, etc.); branched alkenylene groups having 3 to 10 carbon atoms (e.g., 1-ethylethenylene group, 1,2-dimethylethenylene group, 1-butylethenylene group, 1-hexylethenylene group, etc.).

[0138] Examples of the cycloalkylene group having 4 to 10 carbon atoms include a cyclobutylene group, a cyclopentylene group, a 2-methylcyclopentylene group, a cyclohexylene group, a 1,3-dimethylcyclohexylene group, a 1-ethylcyclopentylene group, and a cyclohexanedimethylene group.

[0139] Examples of the arylene group having 6 to 10 carbon atoms include an o-, p- or m-phenylene group, a 2,4-naphthylene group, a biphenylene group, and a tolylene group.

[0140] Examples of the aralkylene group having 7 to 10 carbon atoms include a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenyleneethyl group, and a naphthylmethylene group.

[0141] R 4 , R 5 are the same or different and are substituted or unsubstituted hydrocarbon groups having 1 to 6 carbon atoms. They are preferably substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms. In addition, the hydrocarbon group is preferably an alkyl group.

[0142] Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an allyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.

[0143] R 6 are the same or different and are substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms. They are preferably substituted or unsubstituted divalent hydrocarbon groups having 1 to 4 carbon atoms. In addition, the hydrocarbon group is preferably an alkylene group.

[0144] Examples of the divalent hydrocarbon group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a 1-methylethylene group, a 2-methylethylene group, an ethenylene group, and a propenylene group.

[0145] R 3 ~R 6 In the case where the hydrocarbon group has a substituent, the substituent is R 1 The substituents described above in the above can be used without any particular limitation.

[0146] In formula (3), l is an integer of 0 to 5. l is more preferably an integer of 0 to 3, further preferably an integer of 0 to 2, and particularly preferably 1. When l is within the above range, the fluorosurfactant has excellent surface tension reducing ability, and the heat resistance of the foam is good. When l exceeds 5, the water solubility of the fluorosurfactant may decrease.

[0147] In formula (3), X is a carboxyl group or a sulfo group.

[0148] The molecular weight of the compound represented by formula (3) is preferably 400-1,700, more preferably 500-1,500, and even more preferably 600-1,200.

[0149] Specific examples of the compound represented by formula (3) include, but are not limited to, the following:

[0150] [ka]

[0151] [ka]

[0152] The compound of formula (3) is preferably a compound represented by formula (3-2-2).

[0153] The compound represented by formula (3) can be produced, for example, by a method including the following (Step i) and (Step ii). (Step i) A step of reacting a perfluoropolyether compound represented by the following formula (9) with a diamine represented by the following formula (10) to synthesize an amide compound. (Step ii) A step of reacting the amide compound obtained in (Step i) with a haloalkyl carboxylate or a haloalkyl sulfonate.

[0154] Formula (9):

[0155] [ka]

[0156] [In the formula, Rf3 is a perfluoroalkyl group having 1 to 4 carbon atoms. 12 is a substituted or unsubstituted hydrocarbon group. l is an integer of 0 to 5. Equation (10):

[0157] [ka]

[0158] [In the formula, R 3 R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. 4 , R 5 are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.] Rf3 and l in formula (9) are the same as defined in formula (3).

[0159] In formula (9), R 12 is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

[0160] Examples of the unsubstituted hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, an allyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a phenyl group. Preferred are a methyl group, an ethyl group, a tert-butyl group, and a benzyl group, and particularly preferred is a methyl group.

[0161] R 12 In the case where the hydrocarbon group has a substituent, the substituent is R 1The substituents described above in the above can be used without any particular limitation.

[0162] Specific examples of the perfluoropolyether compound represented by formula (9) include, but are not limited to, the following:

[0163] [ka]

[0164] The perfluoropolyether compound represented by formula (9) is also available as a commercial product; for example, CAE-500, CAE-600, and CAE-1000 (all manufactured by Sinochem Corporation) can be used.

[0165] R in Equation (10) 3 , R 4 , R 5 is the same as defined in equation (3).

[0166] Specific examples of the compound represented by formula (10) include N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dipropylethylenediamine, N,N-dihexylethylenediamine, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dipentyl-1,3-propanediamine, N,N-dihexyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N- Dimethyl-1,5-pentanediamine, N,N-diethyl-1,5-pentanediamine, N,N-dipropyl-1,5-pentanediamine, N,N-dimethyl-1,6-hexanediamine, N,N-diethyl-1,6-hexanediamine, N,N-dipropyl-1,6-hexanediamine, N,N-dimethyl-1,8-octanediamine, N,N-dimethyl-1,10-decanediamine, N,N,2,2-tetramethyl-1,3-propanediamine, 4-amino-1-diethylaminopentane, N,N-dimethyl-1,4-cyclohexanediamine, N-(3-aminopropyl)-N-methylaniline, N,N-dimethyl-1,4-phenylenediamine, N,N-diethyl-1,4-phenylenediamine, and the like are included, but are not limited thereto. Among these, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dimethyl-1,3-propanediamine, and N,N-diethyl-1,3-propanediamine are preferred, and N,N-dimethyl-1,3-propanediamine is more preferred.

[0167] The step (step i) of reacting the perfluoropolyether compound represented by formula (9) with the diamine represented by formula (10) can be carried out by a method similar to that described in, for example, US Pat. No. 2,764,603.

[0168] Examples of haloalkyl carboxylates used in (step ii) include, but are not limited to, sodium chloroacetate, sodium 3-chloropropionate, sodium 4-chlorobutyrate, sodium 5-chlorovalerate, etc. Examples of haloalkyl sulfonic acids include, but are not limited to, sodium 2-chloroethanesulfonate, sodium 2-bromoethanesulfonate, sodium 3-bromopropanesulfonate, sodium 4-bromobutanesulfonate, sodium 5-bromopentanesulfonate, etc.

[0169] The step (step ii) of reacting the amide compound obtained in (step i) with a haloalkyl carboxylate or haloalkyl sulfonate can be carried out based on the method described in, for example, US Pat. No. 3,839,425. [Alkanolamines] The alkanolamine in the present invention has a tertiary amine structure. The alkanolamine is preferably a compound having one or more amine nitrogens in the molecule, all of which constitute tertiary amines, and more preferably a compound having one amine nitrogen in the molecule, all of which constitute tertiary amines. The alkanolamine may be used alone or in combination of two or more.

[0170] In one embodiment, the alkanolamine in the present invention is preferably a compound having three or more hydroxyl groups in the molecule. With such a constitution, the water retention of the foam film can be increased, and the heat resistance of the foam can be improved.

[0171] A compound having three or more hydroxyl groups in the molecule is preferably a compound represented by the following formula (4), for example.

[0172] Formula (4):

[0173] [ka]

[0174] (In the formula, R 7 , R 8 , R 9 are the same or different and are alkylene groups having 1 to 5 carbon atoms. In formula (4), R 7 , R 8 , R 9 are the same or different and are alkylene groups having 1 to 5 carbon atoms, more preferably alkylene groups having 1 to 4 carbon atoms, and particularly preferably alkylene groups having 1 to 3 carbon atoms.

[0175] Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a 1-methylethylene group, a 2-methylethylene group, a 1-ethylethylene group, a 2-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, and a 1,1-dimethylpropylene group.

[0176] In one embodiment, the acid dissociation constant pKa of the alkanolamine in the present invention is preferably 8.5 or less. The acid dissociation constant pKa of the alkanolamine is more preferably 7 to 8.5, and even more preferably 7 to 8. This configuration can increase the water retention of the foam film and improve the heat resistance of the foam. In this specification, the "acid dissociation constant pKa of the alkanolamine" means the pKa of the conjugate acid of the amine in the alkanolamine. The acid dissociation constant pKa of the alkanolamine can be a literature value, a database value, a ChemDraw calculated value, or the like.

[0177] The molecular weight of the alkanolamine in the present invention is preferably 50-300, and more preferably 100-250.

[0178] Examples of alkanolamines in the present invention include triethanolamine, triisopropanolamine, 1-[bis(2-hydroxyethyl)amino]-2-propanol, 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol), bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N-methyldiethanolamine, and dimethylaminoethanol. Of these, triethanolamine, triisopropanolamine, 1-[bis(2-hydroxyethyl)amino]-2-propanol, and 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol) are preferred.

[0179] The content of the alkanolamine in the present invention is preferably 0.01 to 1 part by mass, more preferably 0.02 to 1 part by mass, and particularly preferably 0.05 to 0.5 part by mass, relative to 100 parts by mass of the total amount of the extinguishing agent.

[0180] The content of the alkanolamine is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 1 part by mass of the fluorosurfactant. [water] The extinguishing agent of the present invention preferably contains water as a solvent. The content of water in the extinguishing agent of the present invention is preferably 90 to 99.9 parts by mass, more preferably 95 to 99.8 parts by mass, relative to 100 parts by mass of the total amount of the extinguishing agent. Various types of water such as pure water, fresh water, and seawater can be used as the water. [Other additives] The fire extinguishing agent of the present invention may contain various additives within the range that does not impair the object of the present invention. Examples of additives include water-soluble organic solvents (e.g., esters, ethers, ketones, alcohols, glycols, etc.), hydrocarbon surfactants (e.g., alkylsulfonic acid, alkylamino, alkyl polyoxyethylene, polyoxypropylene, alkyl betaine, polyoxyethylene alkyl phenol, etc.), rust inhibitors (e.g., sodium tungstate, sodium molybdate, sodium nitrite, sodium benzoate, monoethanolamine, diethanolamine, triethanolamine, 1,2,3-benzotriazole, etc.), preservatives (e.g., methylparaben, ethylparaben, benzoates, phenoxyethanol, etc.), foam stabilizers (e.g., polyethyleneimine, natural proteins and hydrolyzed proteins obtained by hydrolyzing them, polyacrylamide, etc.), freezing point depressants (e.g., lower alcohols such as isopropyl alcohol, butanol, and octanol, glycols such as ethylene glycol and propylene glycol, polyacrylamide, polyethyleneimine, urea, or various inorganic salts, etc.), and buffers. These may be used alone or in combination of two or more. These additives can each be used in an amount of 0.01 to 1 part by mass relative to 100 parts by mass of the total amount of the extinguishing agent. <Production of fire extinguishing agents> The fire extinguishing agent of the present invention can be produced by mixing a fluorosurfactant, an alkanolamine, water, and (if necessary) additives.

[0181] In one embodiment, a fire extinguishing agent may be prepared by preparing a fire extinguishing agent concentrate containing a fluorosurfactant, an alkanolamine, water (and additives as necessary) and then diluting it with water such as pure water, fresh water, seawater, etc. In this case, the fire extinguishing agent concentrate preferably contains the following amounts of each component per 100 parts by mass of the total amount.

[0182] Fluorine-based surfactant: preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass.

[0183] Alkanolamine: preferably 0.2 to 20 parts by mass, more preferably 0.5 to 15 parts by mass.

[0184] Water: preferably 40 to 95 parts by mass, more preferably 60 to 90 parts by mass.

[0185] The extinguishing agent of the present invention is preferably used in a neutral to basic range, and the pH of the extinguishing agent is preferably 7.0 to 9.0. <How to use, etc.> The extinguishing agent of the present invention can be used by being filled in a fire extinguisher, a parking lot fire extinguishing system, a fixed hazardous material fire extinguishing system, a packaged fire extinguishing system, etc. It can also be suitably used in spray heads such as closed type sprinkler heads and open type sprinkler heads, mist heads, etc.

[0186] The fire extinguishing agent of the present invention can be used for fire extinguishing by forming foam by blowing in air, nitrogen, carbon dioxide gas, low-boiling point fluorocarbons such as difluorodichloromethane, or a suitable non-flammable gas, or by mixing these gases to form foam.

[0187] The fire extinguishing agent of the present invention can be used in combination with a powder fire extinguishing agent, a protein foam fire extinguishing agent, a synthetic interface foam fire extinguishing agent, and the like.

[0188] Since the heat resistance of the foam of the fire extinguishing agent of the present invention is good, it can be suitably used for extinguishing various fires such as general building fires, city and urban fires, various liquid hazardous material fires, hazardous material facility fires, automobile fires, tunnel fires, aircraft fires, underground parking lot fires, and underground mall fires. EXAMPLES

[0189] The present invention will be further described below with reference to examples, but the present invention is not limited thereto. (Materials used) F-SAA1: Betaine type surfactant (synthesized based on US 3839425)

[0190] [ka]

[0191] ·F-SAA2: Anionic surfactant

[0192] [ka]

[0193] CAE-600 (Sinochem, C3F7OCF(CF3)CF2OCF(CF3)COOCH3, 2.82g, 0.00553mol) and L-tyrosine (1.00g, 0.00552mol), 1,8-diazabicyclo[5.4.0]undecene-7 (1.64g, 0.0108mol), and methanol (2.82g, 0.0881mol) were added to a 50mL eggplant flask equipped with a stirrer, and the mixture was stirred at 60°C for 2 hours. Hydrochloric acid and meta-xylene hexafluoride were added to the reaction solution, and the reaction solution was separated into layers. After separating the lower layer, the upper layer was extracted with meta-xylene hexafluoride. The lower layer and the extract were placed in a recovery flask, and the solvent was removed using a rotary evaporator to recover 3.61 g (yield: 99.0%) of an amino acid-modified perfluoropolyether compound.

[0194] Then, the same mole amount of sodium hydroxide as the amino acid modified perfluoropolyether compound was added to form a sodium salt, and water and hexylene glycol were added to adjust the concentration to 30 mass % (water:hexylene glycol = 1:1, weight ratio) to obtain F-SAA2. TEA: Triethanolamine (pKa: 7.8, literature value) TIPA: Triisopropanolamine (pKa: 8.0, literature value) AC-1200: 1,1'-[(2-hydroxyethyl)imino]bis(2-propanol) (pKa: 7.9 (ChemDraw calculated value)) ·AMP: 2-amino-2-methyl-1-propanol (pKa: 9.7, literature value) MEA: Monoethanolamine (pKa: 9.5, literature value) DEA: Diethanolamine (pKa: 8.9, literature value) DIPA: Diisopropanolamine (pKa: 9.0, literature value) ·CMC-Na: Sodium carboxymethylcellulose PAA: Polyacrylic acid Example 1 0.1 parts by mass of F-SAA1, 0.1 parts by mass of TEA, and 99.8 parts by mass of ion-exchanged water were mixed to prepare a test liquid. The method for evaluating the heat resistance of the foam of the test liquid is shown in Figure 1. The test liquid was placed in a pump bottle (manufactured by Daiso Industries Co., Ltd., product number 4984343991910), and the test liquid (3 pumps) discharged from the pump bottle was poured into an aluminum cup (manufactured by Sogo Rikagaku Glass Manufacturing Co., Ltd., No. 2001, 12 mL). The aluminum cup was then placed on a hot plate heated to 100°C and allowed to stand at 100°C. After 10 minutes, the state of the foam was observed. The criteria for evaluating the heat resistance of the foam are as follows and shown in Figure 2. The results are shown in Table 1. <Judgment criteria> ◎: Maintains voluminous foam ○: Bubbles present on the bottom △: Bubbles were confirmed ×: No bubbles (Examples 2 to 12, Comparative Examples 1 to 5, 8 to 12, and 15 to 19) A test liquid was prepared in the same manner as in Example 1, except that the formulation was changed to that shown in Tables 1 to 3, and the heat resistance of the foam was evaluated. The results are shown in Tables 1 to 3. Note that a 30% by mass solution of F-SAA2 was used. Therefore, for example, the solid content of F-SAA2 in Example 5 is 0.1 parts by mass (0.3 parts by mass x 30% by mass). (Comparative Examples 6, 7, 13, 14, 20, and 21) Test solutions were prepared in the same manner as in Example 1, except that a water-soluble polymer was used instead of the alkanolamine having a tertiary amine structure and the formulation was changed to that shown in Tables 1 to 3, and the heat resistance of the foam was evaluated. The results are shown in Tables 1 to 3.

[0195] [Table 1]

[0196] [Table 2]

[0197] [Table 3]

[0198] Comparing Examples 1 to 4 with Comparative Example 1, Examples 5 to 8 with Comparative Example 8, and Examples 9 to 12 with Comparative Example 15, it was found that the heat resistance of the foam was improved by adding an alkanolamine having a tertiary amine structure to a fluorine-based surfactant. This was the same regardless of the type of surfactant, such as anionic surfactant or betaine surfactant, and the same effect was obtained for the mixed system of these.

[0199] In addition, when Examples 1, 3, 4 and Comparative Examples 2 to 5, Examples 5, 7, 8 and Comparative Examples 9 to 12, and Examples 9, 11, 12 and Comparative Examples 16 to 19 are compared, it is clear that the heat resistance of the foam is improved by using an alkanolamine having a tertiary amine in its structure. The reason for such an effect is unclear, but the following is expected. Since an alkanolamine having a tertiary amine in its structure has a lower pKa than other alkanolamines such as MEA, it is considered that the amount of free base in the composition is large. Since free bases do not easily interact with surfactants, it is presumed that a large number of alkanolamine molecules are present in the bulk of the foam film, and the OH group interacts with water to reduce the drainage rate, thereby improving the heat resistance of the foam (Figure 3). On the other hand, since other alkanolamines such as MEA have a high pKa, it is considered that the proportion of alkanolamines that are conjugated acids (protonated and charged with "+") is high. It is believed that molecules in the conjugated acid state easily interact with surfactants, so they gather on the surface of the foam film, decreasing the proportion of molecules present in the bulk of the foam film. As a result, it is assumed that the water in the bulk is more likely to escape, and the heat resistance of the foam did not improve (Figure 3).

[0200] Furthermore, when comparing Examples 1, 3, and 4 with Comparative Examples 6 and 7, Examples 5, 7, and 8 with Comparative Examples 13 and 14, and Examples 9, 11, and 12 with Comparative Examples 20 and 21, it became clear that the use of an alkanolamine having a tertiary amine in its structure improves the heat resistance of the foam compared to the use of a water-soluble polymer.

Claims

1. A fluorosurfactant having a perfluoropolyether group, and A fire extinguishing agent comprising an alkanolamine having a tertiary amine structure.

2. 2. The fire extinguishing agent according to claim 1, wherein the content of the alkanolamine is 1 to 10 parts by mass per 1 part by mass of the fluorosurfactant.

3. The fluorosurfactant is 2. The fire extinguishing agent according to claim 1, which is at least one selected from the group consisting of anionic surfactants and betaine type surfactants.

4. The anionic surfactant is a compound represented by the following formula (1) or (2) or a salt thereof: The fire extinguishing agent according to claim 3, wherein the betaine type surfactant is a compound represented by the following formula (3): Formula (1): 【Chemistry 1】 (wherein, Rf １ R is a perfluoroalkyl group having 1 to 4 carbon atoms. １ is a substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms; m is an integer of 0 to 5; and n is an integer of 1 to 3. Formula (2): 【Chemistry 2】 (wherein, Rf ２ R is a perfluoroalkyl group having 1 to 4 carbon atoms. ２ is a single bond or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. k is an integer of 0 to 5. Formula (3): 【Chemistry 3】 (wherein, Rf ３ R is a perfluoroalkyl group having 1 to 4 carbon atoms. ３ R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. ４ , R ５ are the same or different and each is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms. ６ is a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms; l is an integer of 0 to 5; and X is a carboxyl group or a sulfo group.

5. 2. The fire extinguishing agent according to claim 1, wherein the alkanolamine is a compound having three or more hydroxyl groups in the molecule.

6. 2. The fire extinguishing agent according to claim 1, wherein the alkanolamine has an acid dissociation constant pKa of 8.5 or less.

7. The fire extinguishing agent according to claim 1, wherein the alkanolamine is a compound represented by the following formula (4): Formula (4): 【Chemistry 4】 (In the formula, R ７ , R ８ , R ９ are the same or different and are alkylene groups having 1 to 5 carbon atoms.

Images