JPH05178798A - Production of quaternary ammonium organic acid salt - Google Patents

Abstract

PURPOSE:To simply and efficiently obtain the subject organic acid salt having a reduced halogen content by blending a counter ion of a quaternary ammonium salt with an organic solvent mixed with water and replacing the counter ion with an anion residue having a specific molecular weight and a specific substituent group. CONSTITUTION:A quaternary ammonium salt (e.g. lauryltrimethylammonium chloride) is reacted with a compound for supplying a counter ion to the quaternary ammonium salt in a mixed solvent consisting an organic solvent and water at 20-40 deg.C for 1.0 hour under stirring, allowed to stand for 1.0 hour, separated into plural phases and, from the organic phase, a compound of formula I [at least one of R1 to R3 is 8-10C alkyl or alkenyl and the rest are methyl, ethyl, benzyl, formula II or formula III ((n) is 1-5); R4 is methyl or ethyl; X- is anion residue], replaced with an anion residue containing one or more substituent groups of sulfuric acid, phosphoric ester, phosphonic ester and carboxylic acid having >=7C substituent group or >=300 molecular weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for substituting a halogen ion of a quaternary ammonium inorganic acid salt with an organic acid anion, and more specifically, the organic acid anion has a molecular weight of 300 to 20.
000 oligomers, quaternary ammonium organic acid salts.

[0002]

2. Prior Art and Problems to be Solved by the Invention
In many cases, the quaternary ammonium salt is used to quaternize tertiary ammonium using an alkyl halide or the like, so that the counter anion becomes a halogen element or the like, which easily causes strong phytotoxicity and skin irritation to plants and animals. On the other hand, it has been known so far that these side effects can be reduced by substituting a specific anion for the counter ion, and it is harmful to plants and humans while maintaining the activity in terms of environmental problems and safety to humans. There has been a demand for the development of a quaternary ammonium salt in which a highly safe counter ion having no specific ion is substituted with a specific anion.
Generally, conventional methods for counterion substitution of quaternary ammonium salts include a method using an ion exchange resin and an electrodialysis method. In the ion exchange resin method, an alkali treatment or an acid treatment is performed to regenerate the ion exchange resin. I have to
Further, the resin must be replaced regularly, the manufacturing process is long, the facility cost / manufacturing cost is very high, and the reaction cannot be performed at a high concentration, which is not suitable for mass production.
Further, in the case of the electrodialysis method, if a flammable solvent is used, there is a risk of explosion, so that the use of the solvent is limited and the versatility is lacking. For these reasons, it has been desired to develop a method for replacing a counter ion of a quaternary ammonium salt that is simple, has a low production cost, and is highly safe. For these reasons, it is desired to develop a counterion substitution method for a quaternary ammonium salt that is simple and has a low production cost.

[0003]

[Means for Solving the Problems] The present inventors have found that quaternary ammonium salts are used in the fields of agricultural and horticultural efficacy enhancers, bactericidal / disinfectants, wood preservatives, fiber treating agents, paper treating agents and the like. As a result of intensive research aimed at developing a method for substituting a counter anion for a quaternary ammonium salt to be used while maintaining efficacy and further improving safety, as a result, Molecular weight of anion 300 to 20
000 compounds substituted with anion residues of anionic oligomers or polymers and compounds having anion residues of 7 or more carbon atoms maintain or enhance the efficacy of the intended treating agent, and are effective against plants and animals. The inventors have found that they do not cause chemical damage and skin irritation, and have further found that the quaternary ammonium salt can be easily produced by a method of substituting a counter ion in a solvent, thus completing the present invention.

That is, the present invention mixes a counter ion of a quaternary ammonium salt in a mixed solvent of an organic solvent and water to give a sulfonic acid or a sulfuric acid ester having a substituent having 7 or more carbon atoms or 300 or more molecular weight. There is provided a method for producing a quaternary ammonium organic acid salt, which comprises substituting an anion residue having one or more substituents of phosphoric acid ester, phosphonic acid ester and carboxylic acid. More specifically, the present invention provides a quaternary ammonium organic salt represented by the following general formula:
The above-mentioned 4 characterized by being a compound represented by (I)
A method for producing a quaternary ammonium organic acid salt is provided.

[0005]

[Chemical 5]

[In the formula, at least one of R ₁ , R ₂ and R ₃ is a linear or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, and the rest are —CH ₃ , —CH ₂ CH ₃ and Chemical formula (II), (II
I), (IV)

[0007]

[Chemical 6]

[0008]

[Chemical 7]

[0009]

[Chemical 8]

[0010] In made alone or in combination selected from the group represented (n is 1 to 5), R ₄ is -CH ₃ or -CH ₂ CH _3, the counterion X ^- is an anion of an average molecular weight of 300 to 20,000 It is an anion residue of the acid of the acidic oligomer or polymer. ) The anionic oligomer or polymer of the present invention has the following (1)
It is preferable that the compound includes one or more selected from (3) to (3). (1) A polymer containing one or more kinds selected from the group of monomers consisting of unsaturated carboxylic acids and their derivatives as an essential component. (2) A polymer containing styrene sulfonic acid as an essential constituent monomer. (3) A formaldehyde condensate of a sulfonated product of a polycyclic aromatic compound which may have a hydrocarbon group as a substituent.

[0011] Quaternary ammonium salt represented by the general formula (I) according to the present invention is characterized in counterion, the counterion X ^-
Is an anionic residue of an acid of an anionic oligomer or polymer having a molecular weight of 300 to 20000, and is basically an anionic oligomer or polymer having an anion residue of an acid capable of forming a counter ion X ^−. is important. The anionic oligomer or polymer of the above (1) to (3) according to the present invention will be specifically described. (1) A polymer containing one or more kinds selected from the group of monomers consisting of unsaturated carboxylic acids and their derivatives as an essential component. Examples of the monomer used for producing the polymer (1) include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, and derivatives thereof,
For example, there are alkyl esters (such as methyl esters) of the above acids, or polyoxyethylene esters. In addition to these monomers, a copolymerizable component such as vinyl acetate, isobutylene, diisobutylene, or styrene can be added as a copolymerization component.

The method for polymerizing these monomers is a conventionally known method. The ratio of the monomer components and the degree of polymerization of the polymer are not particularly limited. Specific examples include acrylic acid polymer, methacrylic acid polymer, copolymer of acrylic acid and methacrylic acid, copolymer of acrylic acid and methacrylic acid polyoxyethylene ester, acrylic acid and acrylic. Copolymer with acid methyl ester, copolymer with acrylic acid and vinyl acetate, copolymer with acrylic acid and maleic acid, copolymer with maleic acid and isobutylene, copolymer with maleic acid and styrene Etc. Two or more kinds of these polymers may be used.
Further, a salt with an alkali metal, ammonia, or an organic amine can be used so long as the performance is not impaired.

(2) A polymer containing styrene sulfonic acid as an essential constituent monomer. A styrene sulfonic acid homopolymer can be easily produced by polymerizing styrene sulfonic acid or sulfonation of polystyrene. The polymer of styrene sulfonic acid has a skeleton represented by the following formula.

[0014]

[Chemical 9]

The molecular weight is 300 to 20000, preferably 300 to
It is 10000. Further, a copolymer of styrene sulfonic acid and another monomer copolymerizes styrene sulfonic acid and another monomer, or sulfonates a copolymer of styrene and another monomer. Therefore, it can be easily manufactured. Alkyl acrylate, as a partner of copolymerization,
Hydrophobic monomers such as alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, and acrylic acid, methacrylic acid, maleic acid, fumar Hydrophilic monocarboxylic acids such as acid, maleic anhydride, vinyl alcohol, acrylamide, methacrylamide, diacetone acrylamide, N-vinylpyrrolidone, 2-acrylamido-2-methylpropanesulfonic acid, methacrylsulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid. A quantity is used. A preferable copolymer is (meth) acrylic acid-
Examples thereof include styrene sulfonic acid copolymers. The molar ratio of (meth) acrylic acid and styrene sulfonic acid in the copolymer is
It is 1/10 to 10/1, preferably 1/3 to 4/1. The average molecular weight is 300 to 20000, preferably 1000 to 10000.
Further, sodium salt, potassium salt, ammonium salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, 2-amino-2-methylpropane- There may be a neutralized portion of a salt such as a 1,3-diol salt.

(3) A formaldehyde condensate of a sulfonated product of a polycyclic aromatic compound which may have a hydrocarbon group as a substituent.

Specific examples thereof include formaldehyde condensates such as petroleum sulfonic acid derivatives, lignin sulfonic acid derivatives, naphthalene sulfonic acid derivatives, xylene sulfonic acid derivatives and alkylbenzene sulfonic acid derivatives. The compound (3) according to the present invention, for example, naphthalene, alkyl-substituted benzene, alkyl-substituted naphthalene, anthracene, alkyl-substituted anthracene, lignin, those having an aromatic ring in the petroleum residue, etc. are sulfonated by a general method, It is obtained by subsequent formaldehyde condensation. In this case, the condensation degree is preferably 2 or more, more preferably 3 to 30. Here, when the molecular weight is 300 or less, the effect due to condensation is small, which causes a problem in practical use. As the aromatic compound to be used, various ones can be used, but preferably lignin, xylene, toluene,
Naphthalene or alkylnaphthalene having 1 to 6 carbon atoms may be used, and of course, a mixture thereof may be used. In addition, alkali metals such as sodium and potassium, alkaline earth metals such as calcium, amines, ammonium salts and the like may be used to the extent that performance is not impaired.

The anion residue containing an alkyl group or an alkenyl group having 7 or more carbon atoms of the present invention is preferably the following. Examples of the anion residue include sulfonic acid compounds, carboxylic acid compounds, phosphate compounds, and sulfuric acid ester compounds having a total carbon number of 7 or more and a molecular weight of 300 or more. Examples of sulfonic acid compounds include:
Higher alkyl sulfonic acid having 7 or more carbon atoms, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, sulfonic acid of higher fatty acid ester, sulfonic acid of higher alcohol ether, sulfosuccinic acid ester, alkylphenol sulfonic acid, alkyl sulfonic acid of higher fatty acid amide, Examples thereof include polymers and copolymers of alkylallyl ester sulfonic acid, alkyldiphenyl sulfonic acid, alkylbenzimidazole sulfonic acid, and sulfonic acid. Preferably, the total carbon number is 7 to 30, and particularly preferably 10 to 20.
The above sulfonic acid. Specific examples of such sulfonic acid include cabryl sulfonic acid, lauryl sulfonic acid, myristyl sulfonic acid, palmityl sulfonic acid, stearyl sulfonic acid, oleyl sulfonic acid, dodecylbenzene sulfonic acid, dodecyl naphthalene sulfonic acid and the like. ..

Examples of the carboxylic acid compound include a carboxylic acid having a linear, branched or cyclic alkyl or alkenyl group having a total carbon number of 7 or more, and a carboxylic acid having another functional group in the alkyl group. The above-mentioned carboxylic acids having 7 to 30 carbon atoms, particularly preferably 10 to 20 carbon atoms are preferable. Examples of such carboxylic acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, sulfated fatty acid, sulfonated fatty acid, hydroxylated fatty acid, cyclic fatty acid and the like. ..

Examples of the sulfuric acid ester compounds include sulfuric acid esters having a linear or branched alkyl or alkenyl group having a total carbon number of 7 or more, and preferably a total carbon number of 7
-30, particularly preferably 10-20 of the above sulfates. Such sulfates include decyl sulfate, lauryl sulfate, palmityl sulfate,
Oleyl sulfate, cetyl sulfate, polyoxyalkylene higher alcohol / ether sulfate,
Examples thereof include resin acid alcohol sulfate ester.

Examples of the phosphate compounds include phosphoric acid esters having a linear, branched or cyclic alkyl or alkenyl group having a total carbon number of 7 or more, preferably 7 to 30 carbon atoms, particularly preferably 10 to 20 of the above phosphoric acid esters. Examples of such phosphoric acid ester include dodecyl phosphoric acid, α-naphthyl phosphoric acid, diphenyl phosphoric acid,
Examples include phenylphosphonic acid monooctyl ester, diphenylphosphinic acid, polyoxyethylene alkylphosphoric acid, and the like.

The organic solvent for substituting the anion residue for the counter ion of the quaternary ammonium salt of the present invention is
The following polar solvents such as lower alcohols, higher alcohols and polyhydric alcohols, and non-polar solvents such as chloroform and hexane are preferred. Examples of lower alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, isoamyl alcohol, 3-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol and the like. Be done. Examples of higher alcohols include n-decanol, undecanol, n-dotecanol, tetradecanol, heptadecanol, cyclohexanol, benzyl alcohol and the like. Examples of polyhydric alcohols are ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene. Glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monophenyl ether acetate, ethylene glycol benzyl ether, ethylene glycol monohexyl ether, dimethoxyethanol, ethylene glycol monoacetate , Ethylene glycol diacetate, diethylene glycol, 1,3-butylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, triethylene Glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, polypropylene glycol, butanediol, glycerin, glyceryl monoacetate, glyceryl monobutyrate, trimethylolpropane, preferably, Mention may be made of ethylene glycol, diethylene glycol, and butylene glycol. Among these alcohols, lower alcohols are particularly preferable.

Other organic solvents other than chloroform and hexane include halogenated hydrocarbons such as dichloromethane and dichloroethane, ethyl ether, isopropyl ether, butyl ether, hexyl ether, diisoamyl ether, methylphenyl ether, ethylphenyl ether, amylphenyl. Ethers such as ether, ethylbenzyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, acetone, methylacetone, methylethylketone, methyl-n-butylketone, methylisobutylketone, methyl-n-hexylketone, diethylketone, acetone oil Ketones such as acetonylacetone, phorone, isophorone, cyclohexanone, and methylcyclohexanone, methyl acetate, ethyl acetate, -n-butyl acetate, Acid - n-amyl, isoamyl acetate, methyl acetate isoamyl, methyl propionate, Isoashiru propionic acid, butyric acid - n-butyl, butyl stearate, butyl stearate, amyl stearate,
Methyl lactate, ethyl lactate, ethyl benzoate, propyl benzoate, isoamyl benzoate, benzyl abietic acid,
Esters of diethyl oxalate, dibutyl oxalate, dimethyl malonate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, etc., formamide, N, N-dimethylformamide, acetonyl, morpholine, etc. Nitrogen compounds, and n-pentane, isohexane, n-heptane, n-octane, n-
Hydrocarbon compounds such as decane, petroleum ether, petroleum benzine, cyclohexane, toluene, xylene, ethylbenzene, dimethyl sulfoxide, etc. may be mentioned.

The counterion of the quaternary ammonium salt which is the starting material of the present invention is a residue of halogen, an inorganic acid or an organic acid having 4 or less carbon atoms. As halogen, Cl, Br, I
Etc., but generally Cl. Inorganic acids include sulfuric acid, phosphoric acid, and nitric acid. Examples of the organic acid having 4 or less carbon atoms include sulfonic acid and carboxylic acid.
Specific examples include methylsulfate, ethylsulfate, butylsulfate, diethylsulfate and the like. Further, methyl phosphate, diethyl phosphate and the like can be mentioned.

The method for substituting the counter ion of the quaternary ammonium salt in the present invention has optimum conditions depending on the partition coefficient of the quaternary ammonium compound to be produced, and the quaternary ammonium halide is contained in an amount of 2 to 80% by weight, preferably 10 to 70%. % By weight, 5-80% by weight of organic solvent, preferably 6-15% by weight, 0-80% by weight of water, preferably 12-36% by weight, 2-80% by weight of a compound having a desired substituent, Preferably 10 to 70% by weight is mixed. Mixing may be simply stirring. The mixing ratio of the organic solvent and water is not particularly limited. However, when the amount of water is large, the reactivity is not a problem, but the efficiency is disadvantageous. Considering this point, the weight ratio of the organic solvent and water is preferably 1: 1 to 1: 3. Reaction temperature is 0 to 100 ℃
And particularly preferably 20 to 60 ° C. The reaction pressure may be normal pressure, but may be appropriately increased or reduced pressure. After stirring, the mixture is allowed to stand and the phases are separated. The desired quaternary ammonium salt can be obtained from the organic phase. The solvent can be either a polar solvent such as alcohol or a non-polar solvent such as hexane or chloroform, and can be selected according to the formulation of the drug product later. More preferably, water and an organic solvent are added to the organic phase, and the same treatment as described above is performed to obtain a purer quaternary ammonium salt of interest, which significantly reduces halogen ions contained in the solvent. You can Further, the phase separation can be enhanced by adding an inorganic salt such as Glauber's salt, HgSO ₄ , CaCl ₂ , NaCl, KCl. The amount of the inorganic salts dissolved at the stirring temperature is good, and if the amount is too large, there is a risk of being mixed into the product.
%, Preferably 3 to 15% by weight. When adding inorganic salts, it is preferable to dissolve them in water. Further, the organic solvent may be removed by conventionally known operations such as spray drying and distillation.

[0026]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. Example 1 A stirring reactor equipped with a thermometer was charged with 263.5 g of lauryltrimethylammonium chloride, 348 g of sodium dodecylbenzenesulfonate, 1200 g of water, and 612 g of ethanol as an organic solvent, and the reaction temperature was kept at 20 to 40 ° C. ,
The mixture was stirred for 1.0 hour and reacted. After the reaction, the mixture was allowed to stand for 1.0 hour, the phases were separated, and the aqueous phase was gently extracted. At this time, the substitution rate of the target quaternary ammonium salt contained in the organic phase was 100%.

Example 2 347.5 g of stearyltrimethylammonium chloride, 288.4 g of sodium lauryl sulfate, 1300 g of water, and hexane as an organic solvent were placed in a stirring reactor equipped with a thermometer.
636g, 300g magnesium sulfate to further enhance phase separation
Was charged, the reaction temperature was maintained at 300 ° C., and the reaction was stirred for 45 minutes. After the reaction, the mixture was allowed to stand for 30 minutes for phase separation, and the aqueous phase was gently extracted. At this time, the substitution rate of the target quaternary ammonium salt contained in the organic phase was 100%.

Example 3 A stirring reactor equipped with a thermometer was charged with 345.5 g of dodecylbenzyldimethylammonium chloride, 288.4 g of sodium lauryl sulfate, 1267.8 g of water, and 633.9 g of methanol as an organic solvent, and the reaction temperature was 20. Keep at ~ 40 ° C,
The mixture was stirred for 1.0 hour and reacted. After the reaction, the mixture was allowed to stand for 1.0 hour, the phases were separated, and the aqueous phase was gently extracted. At this time, the substitution rate of the target quaternary ammonium salt contained in the organic phase was 100%.

Example 4 In a stirred reactor equipped with a thermometer, 362.1 g of didecyldimethylammonium chloride, 344.4 g of sodium cetyl phosphate, 1403.0 g of water, and 706.5 g of isobutanol as an organic solvent were charged, and the reaction temperature was changed. The temperature was maintained at 20 to 40 ° C, and the reaction was carried out by stirring for 1.0 hour. After the reaction, the mixture was allowed to stand for 1.0 hour, the phases were separated, and the aqueous phase was gently extracted. At this time, the substitution rate of the target quaternary ammonium salt contained in the organic phase is 100%.
Met.

Example 5 In a stirred reactor equipped with a thermometer, 320 g of palmitoyltrimethylammonium chloride and sodium salt of β-naphthalenesulfonic acid formaldehyde condensate 1000
g, 2640 g of water, and 1320 g of chloroform as an organic solvent
Was charged, the reaction temperature was maintained at 20 to 40 ° C, and the mixture was stirred for 1.0 hour,
It was made to react. After the reaction, the mixture was allowed to stand for 1.0 hour, the phases were separated, and the aqueous phase was gently extracted. Furthermore, 2000g of water and 50g of Glauber's salt in the organic phase
g and 500 g of chloroform were added and the same operation as above was performed to gently extract the aqueous phase. At this time, the substitution rate of the target quaternary ammonium salt contained in the organic phase was 100%.

Comparative Example 1 100 g of ion exchange resin (trade name: Dowex) was treated with 500 ml of 2N sodium hydroxide solution for 10 hours, and then chlorine ion was added to the resin with 3 liters of distilled water or ion exchange water. Wash with water until no more. The ion-exchange resin thus treated was brought into contact with 100 ml of lauryltrimethylammonium chloride dissolved in 2% of 50% ethanol aqueous solution to form lauryltrimethylammonium hydroxide. Dodecylbenzenesulfonic acid was added to this until the isoelectric point was reached to obtain the desired counterion substitution product. The target quaternary ammonium salt obtained by the ion exchange resin method and the method of Example 1 had the same substitution rate and the same performance. Table 1 collectively shows Examples 1 to 5 and Comparative Example 1.

[0032]

[Table 1]

[0033]

According to the method of the present invention, the counter ion (halogen element) of quaternary ammonium halide can be simply and efficiently used.
It is possible to reduce the content of the halogen element remaining in the organic solvent containing the desired quaternary ammonium salt, at the same time.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 309/31 9160-4H 309/36 9160-4H C07D 213/20 C07F 9/09 Z 7106-4H (72) Inventor, Mitsushita Morishita 214-4 Koji, Wakayama City, Wakayama Prefecture

Claims (7)

[Claims] 1. A sulfonic acid having a substituent having 7 or more carbon atoms or 300 or more molecular weight by mixing a counter ion of a quaternary ammonium salt in a mixed solvent of an organic solvent and water,
A method for producing a quaternary ammonium organic acid salt, which comprises substituting an anion residue having at least one substituent of a sulfate ester, a phosphate ester, a phosphonate ester and a carboxylic acid. 2. A quaternary ammonium organic salt has the following general formula:
A compound represented by formula (I), characterized in that
A method for producing the quaternary ammonium organic acid salt described. [Chemical 1] [In the formula, at least one of R ₁ , R ₂ and R ₃ is a linear or branched alkyl group or alkenyl group having 8 to 30 carbon atoms, and the rest are
-CH ₃ , -CH ₂ CH ₃ and the following formulas (II), (III), (IV) [Chemical 3] [Chemical 4] Or a combination thereof (n is 1 to 5) selected from the group represented by, R ₄ is —CH ₃ or —CH ₂ CH ₃ , a counterion X ⁻
Is an anion residue of an acid of an anionic oligomer or polymer having an average molecular weight of 300 to 20000. ) 3. The method for producing a quaternary ammonium organic acid salt according to claim 2, wherein the anionic oligomer or polymer is a compound containing one or more selected from the following (1) to (3). (1) A polymer containing one or more kinds selected from the group of monomers consisting of unsaturated carboxylic acids and their derivatives as an essential component. (2) A polymer containing styrene sulfonic acid as an essential constituent monomer. (3) A formaldehyde condensate of a sulfonated product of a polycyclic aromatic compound which may have a hydrocarbon group as a substituent. 4. The organic solvent is methanol, ethanol,
Characterized by being one or more selected from the group consisting of propanol, isopropanol, isobutanol, hexanol, decanol, diethylene glycol, dimethylformamide, dimethylsulfonamide, hexane, chloroform, acetone, dichloromethane, ethyl acetate, methyl isobutyl ketone. 4 according to claim 1.
Method for producing quaternary ammonium organic acid salt. 5. The quaternary ammonium salt according to claim 1, wherein the quaternary ammonium salt is contained in an amount of 2 to 80% by weight, the organic solvent is in an amount of 5 to 80% by weight, and the water is in an amount of 0 to 80% by weight. Method for producing organic acid salt. 6. The method for producing a quaternary ammonium organic acid salt according to claim 1, further comprising adding an inorganic salt. 7. A quaternary ammonium salt of 2 to 80% by weight, an organic solvent of 5 to 80% by weight, water of 5 to 80% by weight, and an inorganic salt 1
The method for producing a quaternary ammonium organic acid salt according to claim 6, wherein the compounding ratio is from -30% by weight.