Organic ammonium salts having phosphonate or phosphinate anions and formulations capable of forming such salts

Abstract

To provide: a novel organic ammonium salt which has excellent freezing point lowering function; and a composition which is capable of forming the salt.SOLUTION: An organic ammonium salt according to the present invention contains a cation and an anion; the cation is an ammonium cation that is represented by a formula (I) (wherein each R1 independently represents an organic group having 1 to 22 carbon atoms; each R2 independently represents a hydroxy hydrocarbon group that has one or more hydroxyl groups and a hydrocarbon moiety having 1 to 22 carbon atoms and optionally having an oxygen atom, or the like; and each of l, m and n represents an integer of 0 to 4, with the total of l, m and n being 4); and the anion is a phosphonate ion or a phosphinate ion.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to organic ammonium salts having phosphonate or phosphinate anions and to formulations capable of forming such salts. [Background technology]

[0002] The present inventors have proposed various organic ammonium salts as ionic liquids that are liquid at room temperature (Patent Documents 1 to 5).

[0003] Conventionally, freezing-point depressing properties have been investigated for various substances because of their usefulness in a variety of fields, including the preservation of animals and plants at low temperatures, the preservation of biological materials such as enzymes and proteins at low temperatures, the preservation of biological tissues such as organs at low temperatures, food preservation, refrigerant solvents, low-temperature thermometers, the cold resistance of plants, snowfall regulators, and antifreezing coatings on material surfaces (freezer defrosters, car window defrosters, defrosters, and tunnel defrosters). However, the development of novel substances with more pronounced freezing-point depressing properties is highly desirable in the industry. Patent Document 5 proposes a heat transfer medium using a corrosion-resistant organic ammonium salt and describes the freezing-point depressing properties of the organic ammonium salt, but does not provide any specific examples using phosphonate or phosphinate ions as counter anions to the ammonium cation, nor does it disclose that a combination of these anions with the ammonium cation can produce a low-viscosity organic ammonium salt with excellent freezing-point depressing properties. The same is true for Patent Documents 1 to 4.

[0004] Patent Document 6 describes a method for producing an organic ammonium salt having a phosphate ester anion, but does not describe organic ammonium salts having a phosphonate ion or a phosphinate ion. There is no description or suggestion that a combination of a phosphonate anion and a phosphinate anion results in an organic ammonium salt with low viscosity or an excellent freezing point depressant. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-012313 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-031137 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-131974 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-131975 [Patent Document 5] Japanese Patent Application Laid-Open No. 2012-241018 [Patent Document 6] Japanese Patent Application Laid-Open No. 2014-167003 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel organic ammonium salt having an excellent freezing point depressing effect and a compound capable of forming the salt. [Means for solving the problem]

[0007] In order to solve the above problems, the organic ammonium salt of the present invention is an organic ammonium salt containing a cation and an anion, wherein the cation is represented by the following formula (I):

[0008] [ka]

[0009] (In the formula, R 1 each independently represents an organic group having 1 to 22 carbon atoms; R 2each independently represent a hydroxyhydrocarbon group having one or more hydroxyl groups and a hydrocarbon moiety of 1 to 22 carbon atoms which may contain an oxygen atom, a carboxyhydrocarbon group having one or more carboxy groups and a hydrocarbon moiety of 1 to 22 carbon atoms which may contain an oxygen atom, or a hydroxycarboxyhydrocarbon group having one or more hydroxyl groups and one or more carboxy groups and a hydrocarbon moiety of 1 to 22 carbon atoms which may contain an oxygen atom, and l, m, and n each represent an integer of 0 to 4, and the sum of l, m, and n is 4.), and the anion is a phosphonate ion or a phosphinate ion.

[0010] The formulation of the present invention comprises the following components (A) and (B): (A) Amine or ammonium compound (B) Phosphonic acid or phosphinic acid or its salt A blend of The component (A) and the component (B) are organic ammonium salts containing a cation and an anion, and the cation is an ammonium cation of an amine of the component (A) and a proton derived from the component (B), or an ammonium cation derived from the ammonium compound of the component (A), and is represented by the following formula (I):

[0011] [ka]

[0012] (In the formula, R 1 each independently represents an organic group having 1 to 22 carbon atoms; R 2each independently represent a hydroxyhydrocarbon group having one or more hydroxyl groups and a hydrocarbon moiety of 1 to 22 carbon atoms which may contain an oxygen atom, a carboxyhydrocarbon group having one or more carboxy groups and a hydrocarbon moiety of 1 to 22 carbon atoms which may contain an oxygen atom, or a hydroxycarboxyhydrocarbon group having one or more hydroxyl groups and one or more carboxy groups and a hydrocarbon moiety of 1 to 22 carbon atoms which may contain an oxygen atom, and l, m, and n each represent an integer of 0 to 4, and the sum of l, m, and n is 4.) and is capable of forming an organic ammonium salt in which the anion is a phosphonate ion or phosphinate ion derived from component (B). [Effects of the Invention]

[0013] The novel organic ammonium salts of the present invention and compounds capable of forming such salts have excellent freezing point depressing properties. Furthermore, the anhydrous and hydrated forms can be converted into low-viscosity liquids at 25°C, making them highly useful. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below. (organic ammonium salts)

[0015] The organic ammonium salt of the present invention is an organic ammonium salt containing a cation and an anion, wherein the cation is an ammonium cation represented by the above formula (I) and the anion is a phosphonate ion or a phosphinate ion. The organic ammonium salt of the present invention may be an anhydride or a hydrate.

[0016] In the ammonium cation represented by the above formula (I), R 1 each independently represents an organic group having 1 to 22 carbon atoms. The organic group is preferably a hydrocarbon group.

[0017] [Organic group] In this specification, the organic group essentially contains a carbon atom and may also contain at least one atom selected from the group consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a halogen atom. The atomic group contained in the organic group is not particularly limited, and examples thereof include hydrocarbon groups, heterocyclic groups, and the substituents described in the "Substituents" section below. For example, the substituents described in the "Substituents" section below may be substituted for hydrogen atoms in the hydrocarbon group, may interrupt the hydrocarbon group, and / or may be present at the base end of the hydrocarbon group, or may form a condensed ring with an aromatic hydrocarbon group.

[0018] The organic group has 1 to 22 carbon atoms, and from the viewpoints of freezing point depression and low viscosity, it preferably has 1 to 18 carbon atoms, more preferably has 1 to 12 carbon atoms, still more preferably has 1 to 8 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.

[0019] [Hydrocarbon group] In this specification, the hydrocarbon group is not particularly limited, but examples thereof include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and hydrocarbon groups that are combinations thereof. Depending on the context, the group may be monovalent or polyvalent, and examples of the monovalent saturated or unsaturated aliphatic hydrocarbon group include, but are not particularly limited to, linear or branched alkyl groups, alkenyl groups, alkynyl groups, and the like. The alkyl group may be linear or branched, and is not particularly limited to, for example, a methyl group, an ethan-1-yl group, a propan-1-yl group, a 1-methylethan-1-yl group, a butan-1-yl group, a butan-2-yl group, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a pentan-1-yl group, a pentan-2-yl group, a hexane-1-yl group, a heptan-1-yl group, an octan-1-yl group, a 2-ethylhexan-1-yl group, a 1,1,3,3-tetramethylbutan-1-yl group, a nonan-1-yl group, a 2-ethylhexan-1-yl group, a 1,1,3,3-tetramethylbutan-1-yl group, a 2-methylpropan-2-yl group, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl group, a 2-methylpropan-1-yl group, a 2-methylhexan-1-yl group, a 1,1,3,3-tetramethylbutan-1-yl group, a 2-methylhex ... 1-yl group, decan-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecan-1-yl group, hexadecan-1-yl group, 2-hexyldecan-1-yl group, heptadecan-1-yl group, octadecan-1-yl group, nonadecan-1-yl group, icosan-1-yl group, henicosan-1-yl group, docosan-1-yl group, 4,8,12-trimethyltridecan-1-yl group, benzyl group, and α,α-dimethylbenzyl group.The alkenyl group may be linear or branched, and is not particularly limited to, but examples thereof include vinyl, prop-1-en-1-yl, allyl, isopropenyl, but-1-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 2-methylprop-2-en-1-yl, 1-methylprop-2-en-1-yl, pent-1-en-1-yl, pent-2-en-1-yl, pent-3-en-1-yl, and pent-4-en-1-yl. group, 3-methylbut-2-en-1-yl group, 3-methylbut-3-en-1-yl group, hex-1-en-1-yl group, hex-2-en-1-yl group, hex-3-en-1-yl group, hex-4-en-1-yl group, hex-5-en-1-yl group, 4-methylpent-3-en-1-yl group, 4-methylpent-3-en-1-yl group, hept-1-en-1-yl group, hept-6-en-1-yl group, oct-1-en-1-yl group, oct-7-en-1 -yl group, non-1-en-1-yl group, non-8-en-1-yl group, dec-1-en-1-yl group, dec-9-en-1-yl group, undec-1-en-1-yl group, undec-10-en-1-yl group, dodec-1-en-1-yl group, dodec-11-en-1-yl group, tridec-1-en-1-yl group, tridec-12-en-1-yl group, tetradec-1-en-1-yl group, tetradec-13-en-1-yl group, pentadec-1-en-1-yl group, Examples thereof include a pentadec-14-en-1-yl group, a hexadec-1-en-1-yl group, a hexadec-15-en-1-yl group, a heptadec-1-en-1-yl group, a heptadec-16-en-1-yl group, an octadec-1-en-1-yl group, an octadec-9-en-1-yl group, an octadec-17-en-1-yl group, a nonadec-1-en-1-yl group, an icos-1-en-1-yl group, a henicos-1-en-1-yl group, and a docos-1-en-1-yl group.The alkynyl group includes a straight-chain or branched-chain alkynyl group, and is not particularly limited to, but examples thereof include ethynyl, prop-1-yn-1-yl group, prop-2-yn-1-yl group, but-1-yn-1-yl group, but-3-yn-1-yl group, 1-methylprop-2-yn-1-yl group, pent-1-yn-1-yl group, pent-4-yn-1-yl group, hex-1 ... -yl group, hex-5-yn-1-yl group, hept-1-yn-1-yl group, hept-6-yn-1-yl group, oct-1-yn-1-yl group, oct-7-yn-1-yl group, non-1-yn-1-yl group, non-8-yn-1-yl group, dec-1-yn-1-yl group, dec-9-yn-1-yl group, undec-1-yn-1-yl group, undec-10 -yn-1-yl group, dodec-1-yn-1-yl group, dodec-11-yn-1-yl group, tridec-1-yn-1-yl group, tridec-12-yn-1-yl group, tetradec-1-yn-1-yl group, tetradec-13-yn-1-yl group, pentadec-1-yn-1-yl group, pentadec-14-yn-1-yl group, hexadec-1-yn-1-yl group group, hexadec-15-yn-1-yl group, heptadec-1-yn-1-yl group, heptadec-16-yn-1-yl group, octadec-1-yn-1-yl group, octadec-17-yn-1-yl group, nonadeca-1-yn-1-yl group, icos-1-yn-1-yl group, henicos-1-yn-1-yl group, docos-1-yn-1-yl group, and the like.

[0020] As the saturated or unsaturated alicyclic hydrocarbon group, a saturated alicyclic hydrocarbon group is preferable, and although not particularly limited, examples thereof include monovalent groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and groups containing alicyclic residues such as residues thereof.

[0021] The aromatic hydrocarbon group is not particularly limited, but examples thereof include a phenyl group, a naphthalene group, an anthracene group, and groups containing aromatic ring residues such as these residues. The aromatic hydrocarbon group may form a fused ring together with the substituents described below under [Substituents]. The monovalent aromatic hydrocarbon group is not particularly limited, and examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 4-ethylphenyl group, a 4-propylphenyl group, a 4-isopropylphenyl group, a 4-butylphenyl group, a 4-tert-butylphenyl group, a 4-pentylphenyl group, a 4-tert-pentylphenyl group, a 2,4-bis(4-tert-pentyl)phenyl group, a 1,1,3,3-tetramethylbutylphenyl group, a 2-methyl-5-tert-butylphenyl group, a 4-pentylphenyl group, a 4-hexylphenyl group, a 4-heptylphenyl group, a 4- Examples thereof include an octylphenyl group, a 4-nonylphenyl group, a 4-decanylphenyl group, a 4-undecylphenyl group, a 4-dodecylphenyl group, a 4-tridecylphenyl group, a 4-tetradecylphenyl group, a 4-pentadecylphenyl group, a 4-hexadecylphenyl group, a 4-heptadecylphenyl group, a 4-octadecylphenyl group, a 4-biphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a 3-ethoxyphenyl group, a 4-ethoxyphenyl group, a 2-chlorophenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, a 2-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 4-hydroxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and a 9-anthracenyl group.

[0022] Examples of the divalent hydrocarbon group include groups in which one hydrogen atom has been removed from the above groups.

[0023] [Substituent] The substituent is not particularly limited, and examples thereof include hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, halogens, etc. The substituent also includes groups to which these substituents are bonded.

[0024] Examples of the hydrocarbon group include those listed above under [Hydrocarbon group].

[0025] The oxygen-containing group is not particularly limited, but examples thereof include a hydroxyl group, an alkoxy group, an acetoxy group, an acetyl group, an aldehyde group, a carboxy group, a carboxylate group, a urea group, a urethane group, an amide group, an imide group, an ether group, a carbonyl group, an ester group, an oxazole group, a morpholine group, a carbamate group, a carbamoyl group, a polyoxyethylene group, a tocopheryl group, a chroman group, a dihydropyran group, a glyceryl group, and a glyceryl ether group.

[0026] The nitrogen-containing group is not particularly limited, but examples thereof include a cyano group, a cyanato group, an isocyanate group, a nitro group, a nitroalkyl group, an amide group, a urea group, a urethane group, an imide group, a carbodiimide group, an azo group, a pyridine group, an imidazole group, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, and an aminoalkyl group.

[0027] The sulfur-containing group is not particularly limited, but examples thereof include a sulfate group, a sulfonyl group, a sulfonic acid group, a mercapto group, a thioether group, a thiocarbonyl group, a thiourea group, a thiocarboxy group, a thiocarboxylate group, a dithiocarboxy group, a dithiocarboxylate group, a sulfate ester, a thiophene group, a thiazole group, a thiol group, a sulfo group, a sulfide group, a disulfide group, a thioester group, a thioamide group, a thiocarbamate group, a dithiocarbamate group, and esters thereof.

[0028] The phosphorus-containing group is not particularly limited, but examples thereof include a phosphate group, a phosphite group, a phosphonic acid group, a phosphinic acid group, a phosphonous acid group, a phosphinous acid group, a pyrophosphate group, a phosphate ester group, a phosphite ester group, a phosphonic acid ester group, a pyrophosphate group, and ester groups thereof.

[0029] Halogens include fluorine, chlorine, bromine and iodine.

[0030] Examples of the organic group include hydrocarbon groups which may have a substituent and in which the hydrocarbon moiety may contain an oxygen atom. For the hydrocarbon group, see the contents described in the above section [Hydrocarbon Group]. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group (alkyl group). In terms of, for example, freezing point depression and low viscosity, the alkyl group is preferably a linear or branched group having 1 to 18 carbon atoms, more preferably a linear or branched group having 1 to 6 carbon atoms, and even more preferably a linear or branched group having 1 to 4 carbon atoms. A linear group is particularly preferred.

[0031] The hydrocarbon group may have a substituent, and the substituent is not particularly limited, but examples thereof include those described in the above [Substituent] column.

[0032] The hydrocarbon moiety may contain an oxygen atom, and in this case, the hydrocarbon moiety contains the above-mentioned oxygen-containing group, for example, an ether bond, a carbonyl group, a hydroxyl group, a carboxylate group, an ester bond, an amide bond, a urea bond, or a urethane bond. Therefore, in the present invention, the phrase "the hydrocarbon moiety contains an oxygen atom" includes cases where the alkyl moiety is interrupted by a group that may also contain a heteroatom such as a nitrogen atom as an atomic group containing an oxygen atom, or where such a group is contained at the base end, or where a hydrogen atom is substituted by such a group.

[0033] In the ammonium cation represented by the above formula (I), R 2each independently represent a hydroxyhydrocarbon group having one or more hydroxyl groups and a linear or branched hydrocarbon moiety of 1 to 22 carbon atoms, which may contain an oxygen atom; a carboxyhydrocarbon group having one or more carboxy groups and a linear or branched hydrocarbon moiety of 1 to 22 carbon atoms, which may contain an oxygen atom; or a hydroxycarboxyhydrocarbon group having one or more hydroxyl groups and one or more carboxy groups, which are linear or branched hydrocarbon moieties of 1 to 22 carbon atoms, which may contain an oxygen atom.

[0034] Examples of the hydroxy hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, each having one or more hydroxy groups, as well as hydrocarbon groups that are a combination thereof.

[0035] The hydroxy hydrocarbon group has one or more hydroxyl groups, and the hydrocarbon moiety is preferably linear or branched and has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0036] The carboxy hydrocarbon group has one or more carboxy groups, and the hydrocarbon moiety is preferably linear or branched and has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0037] The hydroxycarboxy hydrocarbon group has one or more hydroxyl groups and one or more carboxy groups, and the hydrocarbon moiety is preferably linear or branched and has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0038] Furthermore, the hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group (alkyl group). Among these, a saturated aliphatic hydrocarbon group having one hydroxy group (monohydroxyalkyl group) or a saturated aliphatic hydrocarbon group having two or more hydroxy groups (polyhydroxyalkyl group) is preferred, and a straight-chain one is preferred.

[0039] The saturated aliphatic hydrocarbon group having one hydroxy group (monohydroxyalkyl group) is not particularly limited, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropan-1-yl group, a 2-hydroxypropan-1-yl group, a 3-hydroxypropan-1-yl group, a 1-hydroxypropan-2-yl group, a 2-hydroxypropan-2-yl group, a 2-hydroxymethylpropan-2-yl group, a 2-hydroxyethylpropan-2-yl group, a 1-hydroxybutan-1 ...methylpropan-2-yl group, a 2-hydroxyethylpropan-2-yl group, a 1-hydroxybutan-1-yl group, a 2-hydroxymethylpropan-2-yl group, a 2-hydroxymethylpropan-2-yl group, a 2-hydroxymethylpropan-2-yl group, a 2-hydroxymethylpropan-2- Dihydroxybutan-1-yl group, 3-hydroxybutan-1-yl group, 4-hydroxybutan-1-yl group, 1-hydroxy-2-methylpropan-1-yl group, 2-hydroxy-2-methylpropan-1-yl group, 3-hydroxy-2-methylpropan-1-yl group, 1-hydroxybutan-2-yl group, 2-hydroxybutan-2-yl group, 3-hydroxybutan-2-yl group, 4-hydroxybutan-2-yl group, 1-hydroxy-2-methylpropan-2-yl group, 5-hydroxypentan-1-yl group, 2-hydroxymethylpentan-2-yl group 1-hydroxy-2-methylpropan-2-yl group, 1-hydroxy-3-methylbutan-2-yl group, 2-hydroxyethylpentan-2-yl group, 6-hydroxyhexan-1-yl group, 7-hydroxyheptan-1-yl group, 8-hydroxyoctan-1-yl group, 9-hydroxynonan-1-yl group, 10-hydroxydecan-1-yl group, 2-methyl-1-hydroxypropan-2-yl group, 2-methyl-1-propan-2-yl group, 1-hydroxy-2-methylpropan-2-yl group, 1-hydroxy-3-methylbutan-2-yl group, 2-hydroxy-2-methylpropan-2-yl group, 2-hydroxy-2-methylbutan- 2-yl group, 2-ethyl-2-hydroxybutan-2-yl group, 2-hydroxy-3-methylpentan-2-yl group, 3-ethyl-2-hydroxypentan-2-yl group, 2-ethyl-1-hydroxy-3-methylbutan-2-yl group, 1-hydroxy-3-methyl-2-(1-methylethyl)butan-2-yl group, 2-ethyl-1-hydroxypentan-2-yl group, 1-hydroxy-2-propylpentan-2-yl group, 4-ethyl-3-hydroxyhexan-4-yl group, 3-ethyl-2-hydroxy-2-methylpentan-3-yl group,Examples of the monohydroxyalkyl group include a 2-ethyl-1-hydroxyhexan-2-yl group, a 1-hydroxy-2-propylhexan-2-yl group, a 2-ethyl-1-hydroxyheptan-2-yl group, a 2-ethyl-1-hydroxy-4-methylpentan-2-yl group, a 1-hydroxy-2-(1-methylethyl)pentan-2-yl group, and a 3-ethyl-4-hydroxyheptan-3-yl group. The monohydroxyalkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0040] Examples of saturated aliphatic hydrocarbon groups having two or more hydroxy groups (polyhydroxyalkyl groups) include di-, tri-, tetra-, penta-, hexa-, hepta-, or octahydroxyalkyl groups. Specific examples include, but are not limited to, dihydroxyethyl groups such as 1,2-dihydroxyethyl groups; dihydroxypropan-1-yl groups such as 1,2-dihydroxypropan-1-yl groups and 2,3-dihydroxypropan-1-yl groups; dihydroxypropan-2-yl groups such as 1,2-dihydroxypropan-2-yl groups and 1,3-dihydroxypropan-2-yl groups; trihydroxypropan-1-yl groups; tri ... Hydroxypropan-2-yl group; dihydroxybutan-1-yl groups such as 1,2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group, 1,4-dihydroxybutan-1-yl group, 2,3-dihydroxybutan-1-yl group, 2,4-dihydroxybutan-1-yl group, and 3,4-dihydroxybutan-1-yl group; 1,2,3 trihydroxybutan-1-yl group, 1,2,4 trihydroxybutan-1-yl group, 1,3,4 trihydroxybutan-1-yl group, and 2,3,4 Trihydroxybutan-1-yl groups such as trihydroxybutan-1-yl group; tetrahydroxybutan-1-yl group; dihydroxy-2-methylpropan-1-yl groups such as 1,2-dihydroxy-2-methylpropan-1-yl group, 1,3-dihydroxy-2-methylpropan-1-yl group, and 2,3-dihydroxy-2-methylpropan-1-yl group; trihydroxy-2-methylpropan-1-yl group; tetrahydroxy-2-methylpropan-1-yl group; 1,2-dihydroxybutan-2-yl dihydroxybutan-2-yl groups such as 1,3-dihydroxybutan-2-yl group, 1,4-dihydroxybutan-2-yl group, 2,3-dihydroxybutan-2-yl group, 2,4-dihydroxybutan-2-yl group, and 3,4-dihydroxybutan-2-yl group; tetrahydroxybutan-2-yl group; 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, and 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group;Tetrahydroxybutan-2-yl group; 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, 1,2-dihydroxypropan-3-yl group, 1,1-dihydroxybutan-2-yl group, 1,1-dihydroxypentan-2-yl group, 1,1-dihydroxy-5-methylhexan-2-yl group, 1,1-dihydroxy Examples of suitable polyhydroxyalkyl groups include hydroxypropan-2-yl group, 1,1-dihydroxy-4-(-4-hydroxyphenyl)butan-2-yl group, di-, tri-, tetra-, or pentahydroxypentan-1-yl group, di-, tri-, tetra-, penta-, or hexahydroxyhexan-1-yl group, di-, tri-, tetra-, penta-, hexa-, or heptahydroxyheptan-1-yl group, and di-, tri-, tetra-, penta-, hexa-, hepta-, or octahydroxyoctan-1-yl group. The polyhydroxyalkyl group preferably has 2 to 8 hydroxyl groups, more preferably 2 to 6 hydroxyl groups. The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Preferred examples of branched polyhydroxyalkyl groups include those represented by the following formula:

[0041] [ka]

[0042] (In the formula, R 11 represents a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), or a linear hydroxyalkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms).

[0043] The group of the above formula is not particularly limited, but examples thereof include 1,2-dihydroxypropan-1-yl group, 2,3-dihydroxypropan-1-yl group, 1,2-dihydroxypropan-2-yl group, 1,3-dihydroxypropan-2-yl group, trihydroxypropan-1-yl group, trihydroxypropan-2-yl group, trihydroxypropan-1-yl group, trihydroxypropan-2-yl group, 1,2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group, 1,4-dihydroxybutan-1-yl group, 2,3- Dihydroxybutan-1-yl group, 2,4-dihydroxybutan-1-yl group, 3,4-dihydroxybutan-1-yl group, 1,2,3-trihydroxybutan-1-yl group, 1,2,4-trihydroxybutan-1-yl group, 1,3,4-trihydroxybutan-1-yl group, 2,3,4-trihydroxybutan-1-yl group, tetrahydroxybutan-1-yl group, 1,2-dihydroxy-2-methylpropan-1-yl group, 1,3-dihydroxy-2-methylpropan-1-yl group, 2,3-dihydroxy-2-methylpropan-1-yl group, trihydroxybutan-1-yl group, trihydroxy-2-methylpropan-1-yl group, tetrahydroxy-2-methylpropan-1-yl group, 1,2-dihydroxybutan-2-yl group, 1,3-dihydroxybutan-2-yl group, 1,4-dihydroxybutan-2-yl group, 2,3-dihydroxybutan-2-yl group, 2,4-dihydroxybutan-2-yl group, 3,4-dihydroxybutan-2-yl group, tetrahydroxybutan-2-yl group, 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3- Dihydroxy-2-hydroxymethylpropan-2-yl group, tetrahydroxybutan-2-yl group, 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, 1,2-dihydroxypropan-3-yl group, 1,1-dihydroxybutan-2-yl group, 1,1-dihydroxypentan-2-yl group, 1,1-dihydroxy-5-methylhexan-2-yl group, 1,1-dihydroxypropan-2-yl group, 1,Examples of the hydroxyl group include 1-dihydroxy-4-(-4-hydroxyphenyl)butan-2-yl group, di-, tri-, tetra-, or pentahydroxypentan-1-yl group, di-, tri-, tetra-, penta-, or hexahydroxyhexan-1-yl group, di-, tri-, tetra-, penta-, hexa-, or heptahydroxyheptan-1-yl group, and di-, tri-, tetra-, penta-, hexa-, hepta-, or octahydroxyoctan-1-yl group.

[0044] Of the above polyhydroxyalkyl groups, 2,3-dihydroxypropan-1-yl, 1,3-dihydroxypropan-2-yl, 1,3-dihydroxy-2-ethylpropan-2-yl, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl, and pentahydroxyhexan-1-yl groups are preferred.

[0045] Examples of the carboxy hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups having one or more carboxy groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and hydrocarbon groups that are combinations thereof. Monocarboxyalkyl groups and polycarboxyalkyl groups in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (alkyl group) are preferred. Specific examples of these include those in which the hydroxyl groups of the mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octahydroxyalkyl groups exemplified above have been substituted with carboxy groups (the alkyl moiety may contain an oxygen atom).

[0046] The monocarboxyalkyl group and polycarboxyalkyl group preferably have an alkyl moiety of 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0047] The hydroxycarboxy hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group that is a combination thereof, each having one or more hydroxy groups and one or more carboxy groups. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). Examples of the hydrocarbon group include, but are not limited to, the di-, tri-, tetra-, penta-, hexa-, hepta-, or octahydroxyalkyl groups exemplified above, in which some of the hydroxyl groups have been substituted with carboxy groups (the alkyl moiety may contain an oxygen atom). The alkyl moiety of the hydroxycarboxyalkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

[0048] In the above formula (I), R 2 When the hydrocarbon moiety contains an oxygen atom, the oxygen atom forms, for example, an ether bond, a carboxyl group, a carbonyl group, an ester bond, an amide bond, a urea bond, or a urethane bond in the hydrocarbon moiety. Therefore, in the present invention, the phrase "the hydrocarbon moiety contains an oxygen atom" includes cases where the hydrocarbon moiety is interrupted by a group that may also contain a heteroatom such as a nitrogen atom as an atomic group containing an oxygen atom, where such a group is contained at the base end, or where a hydrogen atom is substituted by such a group. Specific examples of these include, but are not limited to, saturated aliphatic hydrocarbon groups containing a hydroxyalkoxy group (hydroxyalkoxyalkyl group), saturated aliphatic hydrocarbon groups containing an alkoxyhydroxy group (alkoxyhydroxyalkyl group), saturated aliphatic hydrocarbon groups containing a hydroxypolyalkyleneoxy group (hydroxypolyalkyleneoxyalkyl group), etc.

[0049] In the ammonium cation represented by the above formula (I), l, m, and n each represent an integer of 0 to 4, and the sum of l, m, and n is 4.

[0050] The raw material for the ammonium cation represented by the above formula (I) can be an amine compound obtained by removing one hydrogen ion from an ammonium cation, or a salt of an ammonium cation and a hydroxide anion.

[0051] In the organic ammonium salt of the present invention, the anion is a phosphonate ion or a phosphinate ion. Among these, the phosphonate ion and the phosphinate ion are preferred because they exhibit excellent freezing point depression, while the phosphinate ion is preferred because it can provide an organic ammonium salt with low viscosity.

[0052] The phosphonate ions and phosphinate ions of the anions of the present invention also include alkylphosphonic acids and alkylphosphinic acids containing an alkyl group in the structure. The alkyl moiety may have 1 to 18 carbon atoms or 1 to 10 carbon atoms.

[0053] The organic ammonium salt of the present invention preferably has a hydrogen-bonding functional group in the cation. The hydrogen-bonding functional group is not particularly limited, but examples thereof include an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, and a hydrogen atom directly bonded to the nitrogen of the cation. For the oxygen-containing group, the nitrogen-containing group, the sulfur-containing group, and the phosphorus-containing group, see those listed above under [Substituents]. Among these, an oxygen-containing group and a hydrogen atom are preferred, and a hydroxyl group, a carboxyl group, and a hydrogen atom are more preferred. The hydrogen-bonding functional group is represented by R in formula (I). 2 The hydroxy hydrocarbon group, carboxy hydrocarbon group, or hydroxycarboxy hydrocarbon group may be a hydroxyl group or a carboxyl group, and R 1 The organic group may have the above structure.

[0054] In the formula (I), preferred examples from the viewpoint of freezing point depressing effect and low viscosity are as follows:

[0055] [1] In a preferred example of formula (I), l is an integer of 0 to 3, m is 0, n is an integer of 1 to 4, and R 2is a linear monohydroxy hydrocarbon group having 1 to 18 carbon atoms. The combination of l, m, and n is more preferably l is an integer of 1 to 3, m is 0, and n is an integer of 1 to 3, even more preferably l is 2 or 3, m is 0, and n is 1 or 2, and particularly preferably l is 3, m is 0, and n is 1. R 2 The number of carbon atoms is more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. The monohydroxy hydrocarbon group is preferably a monohydroxyalkyl group. More specific examples of preferred cation structures are not particularly limited, but include, for example, monomethanolammonium cation, monoethanolammonium cation, monopropanolammonium cation, monoisopropanolammonium cation, monobutanolammonium cation, dimethanolammonium cation, diethanolammonium cation, dipropanolammonium cation, diisopropanolammonium cation, dibutanolammonium cation, trimethanolammonium cation, triethanolammonium cation, tripropanolammonium cation, triisopropanolammonium cation, tributanolammonium cation, tetramethanolammonium cation, tetraethanolammonium cation, tetrapropanolammonium cation, tetraisopropanolammonium cation, tetrabutanolammonium cation, etc. Among these, monoalkanolammonium cations, trialkanolammonium cations, and tetraalkanolammonium cations are preferred because they pose less risk of toxicity during production and use than dialkanolammonium cations, which are subject to such concerns.

[0056] [2] In a preferred example of formula (I), l is an integer of 0 to 3, m is 0, n is an integer of 1 to 4, and R 2 is a branched hydroxy hydrocarbon group having one or more hydroxyl groups and having 1 to 18 carbon atoms. A preferred example of the combination of l, m, and n is that l, m, and n are 3, 0, and 1. 2The number of hydroxyl groups in R is preferably 3 or less. 2 More preferably, R 2 There is one hydroxyl group in R. 2 The number of carbon atoms is more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. The hydroxy hydrocarbon group is preferably a hydroxy alkyl group. More specific preferred examples of cation structures include, but are not limited to, 2-amino-2-methyl-1-propanol ammonium cation, 2-amino-1,3-propanediol ammonium cation, 2-amino-2-methyl-1,3-propanediol ammonium cation, 2-amino-2-ethyl-1,3-propanediol ammonium cation, and 2-amino-2-hydroxymethyl-1,3-propanediol ammonium cation.

[0057] [3] In a preferred example of formula (I), l is an integer of 0 to 2, m is an integer of 1 to 3, n is an integer of 1 to 3, and R 1 is a linear or branched hydrocarbon group having 1 to 18 carbon atoms, and R 2 is a linear or branched hydroxy hydrocarbon group having one or more hydroxyl groups and having 1 to 18 carbon atoms. The combination of l, m, and n is more preferably l is 0 or 1, m is an integer of 2 to 3, and n is 1 or 2, and even more preferably l is 0, m is 3, and n is 1. R 1 R preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and the hydrocarbon group is preferably an alkyl group. 2 The number of carbon atoms is more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. The hydroxy hydrocarbon group is preferably a hydroxy alkyl group.

[0058] [4] In a preferred example of formula (I), l is an integer of 0 to 3, m is an integer of 0 to 3, n is an integer of 1 to 3, and R 1 is a linear or branched hydrocarbon group having 1 to 18 carbon atoms, and R 2is a linear or branched carboxy hydrocarbon group having 1 to 18 carbon atoms. The combination of l, m, and n is more preferably l is 1 or 2, m is 1 or 2, and n is 1 or 2, and even more preferably l is 1 or 2, m is 1 or 2, and n is 1. R 2 is preferably a carboxyalkyl group.

[0059] [5] In a preferred example of formula (I), l is an integer of 4.

[0060] [6] In a preferred example of formula (I), l is an integer of 1 to 3, m is an integer of 1 to 3, n is 0, and R 1 is a linear or branched hydrocarbon group having 1 to 18 carbon atoms. The combination of l, m, and n is more preferably l is 1 or 2, m is 2 or 3, and n is 0, and even more preferably l is 1, m is 3, and n is 0. R 1 The number of carbon atoms is more preferably 1 to 12, still more preferably 1 to 8, and particularly preferably 1 to 6. The hydrocarbon group is preferably an alkyl group.

[0061] [7] In a preferred example of formula (I), l and n are 0, m is 4, and R 1 is a linear or branched hydrocarbon group having 1 to 18 carbon atoms. R 1 The number of carbon atoms is more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. The hydrocarbon group is preferably an alkyl group.

[0062] In the above [1] and [2], a preferred example is a structure in which the substituent or atom bonded to the nitrogen of the ammonium cation has two or more different types of substituent or atom. More preferably, in [1] and [2], the substituent or atom bonded to the nitrogen of the cation is two types: a hydroxy hydrocarbon group and a hydrogen atom.

[0063] More specific preferred examples of cation structures include, but are not limited to, monomethanol ammonium cation, monoethanol ammonium cation, monopropanol ammonium cation, monoisopropanol ammonium cation, monobutanol ammonium cation, monopentanol ammonium cation, dimethanol ammonium cation, diethanol ammonium cation, dipropanol ammonium cation, diisopropanol ammonium cation, dibutanol ammonium cation, dipentanol ammonium cation, trimethanol ammonium cation, triethanol ammonium cation, tripropanol ammonium cation, triisopropanol ammonium cation, tripunol ammonium cation, tripentanol ammonium cation, 2-amino-2-methyl-1-propanol ammonium cation, 2-amino-1,3-propanediol ammonium cation, 2-amino-2-methyl-1,3-propanediol ammonium cation, 2-amino-2-ethyl-1,3-propanediol ammonium cation, and 2-amino-2-hydroxymethyl-1,3-propanediol ammonium cation. Among these, monoethanolammonium cation, diethanolammonium cation, triethanolammonium cation, 2-amino-2-methyl-1-propanolammonium cation, 2-amino-1,3-propanediolammonium cation, 2-amino-2-methyl-1,3-propanediolammonium cation, 2-amino-2-ethyl-1,3-propanediolammonium cation, and 2-amino-2-hydroxymethyl-1,3-propanediolammonium cation are preferred.

[0064] In the organic ammonium salt of the present invention, the cationicity of the ammonium cation as a whole is weakened due to the presence of a hydroxyl group, which is an anionic electron-donating group, in the cation, and on the other hand, the pKa of the anion is larger than that of common anions such as halogen anions and sulfonate anions, and the anion tends to be weakly acidic. Therefore, the interaction between the anion and the cation is weakened, reducing crystallinity, and as a result, the salt tends to become more liquid, resulting in an organic ammonium salt with a low melting point and low viscosity.

[0065] The organic ammonium salt of the present invention may be either a liquid or a solid at 25°C, but when the anhydride and hydrate are liquid or gel at 25°C, they can be uniformly coated on an object without volatilizing, and can be used as a solvent or base when used in combination with other additives, etc. In particular, the phosphonate anion, phosphinate anion, and / or hydrogen-bonding functional groups of the cation in the anion have coordination and bonding properties, and therefore have excellent solubility and dispersibility in organic compounds, as well as excellent adhesion and penetration into objects (e.g., resins, paper, and biomaterials), making them highly industrially useful.

[0066] In the present invention, a hydrate refers to a compound that absorbs water and reaches a saturated moisture content when left in air at 25° C. A compound that does not absorb water when left in air at 25° C. does not have a hydrate and is an anhydrous compound.

[0067] The organic ammonium salt of the present invention exhibits an excellent freezing point depressing effect by having a phosphonate ion or a phosphinate ion as the anion. For example, when mixed with water, it can lower the freezing point of water, for example, to -10°C or below, and even to -20°C or below, or even to -40°C or below, of a 50% by mass aqueous solution. From the viewpoint of the freezing point depressing effect, organic ammonium salts whose anhydrides and hydrates are liquid at 25°C are preferred.

[0068] The organic ammonium salt of the present invention has a phosphonate ion or phosphinate ion as the anion, and when the anhydride and hydrate are liquid at 25°C, the organic ammonium salt can have a low viscosity. The viscosity of the anhydride and hydrate is not particularly limited, but for example, the kinematic viscosity at 25°C can be 1000 mP·s or less. The viscosity of the organic ammonium salt of the present invention is suitable for use as, for example, an electrolyte, electrolytic solution, or heat transfer medium, and also as a reaction solvent, from the viewpoints of ease of handling, electrical conductivity, and thermal conductivity in various liquid applications. However, a kinematic viscosity at 25°C of 250 mP·s or less is preferred from the viewpoints of ease of stirring and uniform mixing. The anion is preferably a phosphinate anion, since the anhydride and hydrate are liquid at 25°C.

[0069] When the anion raw material of the organic ammonium salt of the present invention is a polybasic acid, the anion raw material may be reacted with an amine compound as a cation raw material in an amount ranging from equimolar to a molar amount sufficient to form a completely neutralized salt. For example, when the anion is a phosphonate ion of a dibasic acid, an organic ammonium salt can be prepared by reacting the cation and phosphonate ion in a molar ratio of 1:1 to 2:1. Two or more types of cations may be used. When the cation raw material has two or more nitrogen atoms, the anion raw material may be reacted with a phosphonic acid or phosphinic acid as an anion raw material in an amount ranging from equimolar to a molar amount sufficient to form a completely neutralized salt.

[0070] The organic ammonium salt of the present invention, having phosphonate ions and phosphinate ions, is expected to be advantageously utilized in a variety of applications, including, but not limited to, fields requiring properties such as affinity with inorganic and organic substances and biomaterials, solubility, dispersion, low viscosity, high specific heat, high thermal conductivity, high electrical conductivity, lubricity, freezing point depression, boiling point elevation, vapor pressure depression, permeability, hydrophilicity, adsorption, reactivity, water retention and moisture retention, and safety.

[0071] Specifically, the material is not particularly limited, but examples thereof include organic materials or inorganic materials (including, but not limited to, proteins, enzymes, amino acids and their salts, nucleic acids, antibodies and antigens, biological tissues such as cells, animals, plants and organs, biological and natural materials such as cellulose, and poorly soluble components such as substrates for enzyme reactions; metals, metal oxides (including, but not limited to, silica, aluminum oxide (alumina), zirconia, titanium oxide, magnesium oxide, indium tin oxide (ITO), cobalt blue (CoO·Al2O3), antimony oxide, zinc oxide, cesium oxide, zirconium oxide, yttrium oxide, tungsten oxide, vanadium oxide, cadmium oxide, tantalum oxide, niobium oxide, and oxides); and the like. The compound can be used as a reaction solvent, dissolution solvent, preservation solvent, dispersion solvent or additive for compounds such as tin oxide, bismuth oxide, cerium oxide, copper oxide, iron oxide, indium oxide, boron oxide, calcium oxide, barium oxide, thorium oxide, indium tin oxide, ferrite, and carbon materials, pigments, dyes, pharmaceuticals, culture media, feed, fertilizers, functional materials, abrasives, chelating agents, cleaning agents, heat transfer media, refrigerants, emulsifiers, electrolyte materials, antistatic agents, lubricants or additives thereof, surface treatment agents for organic or inorganic materials, freezing point depressants, snow melting agents, antifreezing agents, antifreeze solutions, antifogging agents, adsorbents, extractants, adhesives, topical agents, transdermal absorbents, cosmetics, fragrances, liquid moisture-absorbing materials, water-retaining and moisturizing agents, insecticides, herbicides, pesticides, etc.

[0072] Among the above-mentioned applications, in applications where the freezing point depressing effect of the organic ammonium salt of the present invention is utilized, the organic ammonium salt of the present invention may be used alone, or may be used as a composition further containing other optional components. The type and amount of optional components added to the composition are not particularly limited as long as they do not impair the effects of the present invention. Such optional components are not particularly limited, but examples thereof include solvents, pH adjusters, detergents and dispersants, antioxidants, load-bearing additives, corrosion inhibitors, viscosity index improvers, antifoaming agents, emulsifiers, etc.

[0073] The organic ammonium salt of the present invention has an especially excellent freezing point depressing effect, and has a higher freezing point depressing effect than when phosphate anion or the like is used. Therefore, it is expected to be applicable to various fields requiring freezing point depressing, such as, but not limited to, the preservation of animals and plants at low temperatures, the preservation of biological materials such as enzymes and proteins at low temperatures, the preservation of biological tissues such as organs at low temperatures, food preservation, refrigerant solvents, low-temperature thermometers, low-temperature resistance of plants, snowfall regulators, and antifreezing by coating of material surfaces (antifrosting agents, antifogging agents, antifrosting agents, anticondensation agents).

[0074] The organic ammonium salt of the present invention has a phosphonate ion or a phosphinate ion as the anion, and has excellent affinity with organic and inorganic materials having hydrogen-bonding functional groups, as well as with organic and inorganic materials having affinity for hydrogen-bonding functional groups, and exhibits excellent solubility and dispersibility therein. For example, it exhibits excellent affinity with nitrogen-containing compounds and their salts, and exhibits excellent solubility and dispersibility therein. It also exhibits excellent affinity, solubility, and dispersibility with complexes containing nitrogen-containing compounds and their salts. Furthermore, the presence of a hydroxyl group or a carboxyl group in the cation can enhance these effects. Examples of nitrogen-containing compounds include, but are not limited to, nitrogen-containing compounds having a carboxyl group, and their salts include, but are not limited to, inorganic acid salts, organic acid salts, salts of metals of Groups 1 to 12, ammonium salts, and salts with nitrogen-containing compounds. The organic ammonium salt of the present invention exhibits excellent solubility with amino acids and their salts, and is useful as a solvent for dissolving amino acids. The amino acid is not particularly limited, but examples thereof include glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, threonine, tyrosine, cysteine, cystine, methionine, asparagine, glutamine, aspartic acid, glutamic acid, histidine, lysine, arginine, theanine, aminobutyric acid, sarcosine, methylleucine, aminocaprylic acid, aminohexanoic acid, aminocapric acid, aminolauric acid, and Examples of the amino acid esters include aminomyristic acid, aminopalmitic acid, aminostearic acid, norvaline, aminovaleric acid, aminoisobutyric acid, thyroxine, creatine, ornithine, opine, theanine, tricholamine, kainic acid, domoic acid, ibotenic acid, acromelic acid, cystine, hydroxyproline, hydroxylysine, thyroxine, phosphoserine, desmosine, β-alanine, citrulline, creatine, trimethylglycine, and the salts thereof include the above-mentioned salts. For example, in the case of aspartic acid, examples include sodium aspartate, potassium aspartate, magnesium aspartate, calcium aspartate, zinc aspartate, and iron aspartate.

[0075] (compound) The formulation of the present invention is a blend of the following components (A) and (B): (A) Amine or ammonium compound (B) Phosphonic acid or phosphinic acid or its salt

[0076] Components (A) and (B) can form an organic ammonium salt of the cation represented by formula (I) described above and a phosphonate ion or a phosphinate ion. That is, components (A) and (B) can form an organic ammonium salt in which the cation is an ammonium cation of the amine of component (A) and a proton derived from component (B), or an ammonium cation derived from the ammonium compound of component (A), which is the ammonium cation represented by formula (I), and the anion is a phosphonate ion or phosphinate ion derived from component (B).

[0077] In the present invention, the term "blend" includes the blending of components (A) and (B) before preparing the final target blend, the addition of components (A) and (B) separately, the synthesis of an organic ammonium salt formed by components (A) and (B) using components (A) and (B) as starting materials, the synthesis of the salt as a blend, and the mixing of the salt with other components such as water as necessary to form a blend. The blend of the present invention may be a mixture consisting of only components (A) and (B) (including the case of their salts), or it may be a composition containing components other than components (A) and (B) or their salts, such as a composition containing water, a composition that is an additive added during the production of a product, or a composition that is a product.

[0078] Examples of the amine compound of component (A) include amine compounds having a structure in which one proton has been removed from an ammonium cation represented by formula (I), where l is an integer of 1 to 4. When component (A) is an amine compound, the organic ammonium salt is one in which l in formula (I) is an integer of 1 to 4.

[0079] The ammonium compound of component (A) includes an ammonium compound having the same ammonium cation as the ammonium cation represented by formula (I). The anion of the ammonium compound is not particularly limited, but examples thereof include hydroxide anions, halogen-based anions, sulfur-based anions, phosphorus-based anions, cyanide-based anions, boron-based anions, fluorine-based anions, nitrogen oxide-based anions, and carboxylate-based anions, with hydroxide anions being preferred.

[0080] In the formulations of the present invention, the ammonium cation represented by formula (I) refers to all of the descriptions given above for organic ammonium salts, including preferred embodiments and specific examples.

[0081] The phosphonic acid or phosphinic acid or salt thereof of component (B) is composed of a phosphonate ion or phosphinate ion in the organic ammonium salt of the present invention described above and a proton or other cation, and all of the descriptions regarding the phosphonate ion or phosphinate ion in the organic ammonium salt, including preferred embodiments and specific examples, are incorporated herein by reference.

[0082] Examples of the salt of component (B) include salts of phosphonate ions or phosphinate ions with cations (alkali metal cations, alkaline earth metal cations, ammonium cations, etc.).

[0083] In the blend of the present invention, the blending molar ratio of component (A) to component (B) is not particularly limited and can be 1:99 to 99:1, preferably 1:9 to 9:1, more preferably 1:5 to 5:1, and even more preferably 1:2 to 2:1.

[0084] When the blend of the present invention is a composition, the type and amount of optional components added to the composition are not particularly limited as long as the effects of the present invention are not impaired. Examples of such optional components include, but are not limited to, solvents, pH adjusters, detergent dispersants, antioxidants, load-bearing additives, corrosion inhibitors, viscosity index improvers, antifoaming agents, emulsifiers, etc.

[0085] The blend of the present invention can form the organic ammonium salt of the present invention described above, and therefore exhibits the same effects as the organic ammonium salt of the present invention, and has an excellent freezing point depressing effect.When used as a solution, the organic ammonium salt of the present invention remains even after the solvent evaporates because it is nonvolatile.

[0086] In the blend of the present invention, the mixture of components (A) and (B) or the salt of (A) and (B) may be either a liquid or a solid at 25°C, but if the anhydride or hydrate is a liquid or gel at 25°C, it can be uniformly coated on the target object without volatilizing, and can be used as a solvent or base when used in combination with other additives, etc. If the anhydride or hydrate is a liquid at 25°C, it can be made into an organic ammonium salt with a low viscosity, which, for example, improves ease of handling, such as handleability in various liquid applications, as well as electrical conductivity and thermal conductivity. [Example]

[0087] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples. The compounds of Examples 1 to 32 shown in Tables 1 to 3 were synthesized as follows. Example 1: Synthesis of Compound 1 The compound represented by the following formula was synthesized.

[0088] [ka]

[0089] Monoethanolamine (50.0 g, 0.82 mol) and 30% phosphinic acid (223.8 g, 0.82 mmol) were reacted in 50 mL of water at room temperature for 3 hours, and the water was then distilled off under reduced pressure to obtain a colorless, transparent liquid. The resulting liquid was washed to obtain Compound 1 (monoethanolamine phosphinate) as a colorless, transparent liquid. 1 H-NMR (D2O 400MHz):δ 3.04 (t, 2H, N + C H 2CH2OH), δ 3.72 (t, 2H, N + CH2C H 2OH), δ 6.29, 7.58 (s, 2H, H 2PO2 - ). 13 C-NMR (DO 100MHz): δ 41.2 (N + C H2CH2OH), δ 57.5 (N + CH2 C H2OH).

[0090] <Examples 2 to 32> Compounds 2 to 32 of Examples 2 to 32 shown in Tables 1 to 3 were synthesized by the same synthesis method as in Example 1 and in the blending molar ratios shown in Tables 4 to 6. The physical property values ​​are shown below.

[0091] Example 2: Synthesis of Compound 2

[0092] [ka]

[0093] 1 H-NMR (D2O 400MHz):δ 3.15 (t, 4H, N + C H 2CH2OH), δ 3.78 (t, 4H, N + CH2C H 2OH), δ 6.29, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 48.9 (N + C H₂CH₂OH), δ 56.5 (N + CH2 C H2OH).

[0094] <Example 3> Synthesis of Compound 3

[0095]

change

[0096] 1 H-NMR (D2O 400MHz): δ 3.40 (t, 6H, N + C H 2CH2OH), δ 3.87 (t, 6H, N + CH2C H 2OH), δ 6.30, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 55.0 (N + C H₂CH₂OH), δ 55.3 (N + CH2 C H2OH).

[0097] <Example 4> Synthesis of Compound 4

[0098]

change

[0099] 1 H-NMR (D2O 400MHz): δ 2.87 (t, 8H, N + C H 2CH2OH), δ 3.97 (t, 8H, N + CH2C H 2OH), δ 6.30, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 55.0 (N + C H₂CH₂OH), δ 57.8 (N + CH2 C H2OH).

[0100] <Example 5> Synthesis of Compound 5

[0101]

change

[0102] 1 H-NMR (D2O 400MHz): δ 1.21 (s, 6H, N + CC H 3), δ 3.45 (s, 2H, N + CC H 2OH), δ 6.30, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 21.5 (N + C C H3), δ 55.1 (N + C C H2OH), δ 66.5 (N + C CH2OH).

[0103] <Example 6> Synthesis of Compound 6

[0104]

change

[0105] 1 H-NMR (D2O 400MHz): δ 3.30-3.40 (m, 1H, HOCH2C H N + ), δ 3.61-3.77 (m, 4H, HOC H 2CHN +), δ 6.29, 7.60 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 54.1 (HOCH2 C N + ), δ 58.6 (HO C H2CN + ).

[0106] <Example 7> Synthesis of Compound 7

[0107]

change

[0108] 1 H-NMR (D2O 400MHz): δ 1.18 (s, 3H, N + CC H 3), δ 3.49-3.61 (m, 4H, N + CC H 2OH), δ 6.29, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 16.9 (N + C C H3), δ 58.4 (N + C CH2OH), δ 62.9 (N + C C H2OH).

[0109] <Example 8> Synthesis of Compound 8

[0110]

change

[0111] 1 H-NMR (D2O 400MHz): δ 0.84 (t, 3H, N + CCH2C H3), δ 1.63 (q, 2H, N + CC H 2CH3), δ 3.59 (m, 4H, N + CC H 2OH), δ 6.29, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 6.3 (N + CCH2 C H3), δ 23.3 (N + C C H2CH3), δ 60.6 (N + C C H2OH), δ 61.1 (N + C CH2OH).

[0112] <Example 9> Synthesis of Compound 9

[0113]

change

[0114] 1 H-NMR (D2O 400MHz): δ 3.64 (s, 6H, N + CC H 2OH), δ 6.29, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 59.3 (N + C C H2OH), δ 61.4 (N + C CH2OH).

[0115] <Example 10> Synthesis of Compound 10

[0116]

change

[0117] 1 H-NMR (D2O 400 MHz): δ 0.89 (m, 9H, C H 3CH2CH2CH2, N + C H 3), δ 1.28 (m, 2H, CH3C H 2CH2CH2), δ 1.58 (m, 2H, CH3CH2C H 2CH2), δ 3.02 (m, 2H, CH3CH2CH2C H 2), δ 6.29, 7.61 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100 MHz): δ 12.7 ( C H3CH2CH2CH2), δ 19.0 (CH3 C H2CH2CH2), δ 25.9 (CH3CH2 C H2CH2), δ 42.5 (CH3CH2CH2 C H2), δ 57.6 (N + C H3).

[0118] Synthesis of Compound 11 in <Example 11>

[0119]

Chemical Structure

[0120] 1 H-NMR (D2O 400 MHz): δ 0.85 (t, 3H, C H 3CH2CH2CH2), δ 1.28 (m, 2H, CH3C H 2CH2CH2), δ 1.56 (m, 2H, CH3CH2C H 2CH2), δ 2.90 (m, 2H, CH3CH2CH2C H 2), δ 6.29, 7.59 (s, 2H, H 2PO2 - ). 13C-NMR (D2O 100MHz): δ 12.7 ( C H3CH2CH2CH2), δ 18.9 (CH3 C H2CH2CH2), δ 28.1 (CH3CH2 C H2CH2), δ 39.2 (CH3CH2CH2 C H2).

[0121] <Example 12> Synthesis of Compound 12

[0122]

change

[0123] 1 H-NMR (D2O 400MHz): δ 3.11 (s, 9H, C H 3N + ), δ 3.43 (t, 2H, C H 2N + ), δ 3.98 (t, 2H, N + CH2C H 2OH), δ 6.30, 7.60 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 53.9 ( C H3N + )δ 55.6 (N + C H₂CH₂OH), δ 67.4 (N + CH2 C H2OH).

[0124] <Example 13> Synthesis of Compound 13

[0125]

change

[0126] 1 H-NMR (D2O 400MHz): δ 2.83 (s, 6H, C H 3N+ ), δ 3.20 (t, 2H, C H 2N + ), δ 3.81 (t, 2H, N + CH2C H 2OH), δ 6.30, 7.59 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz):δ 42.6 ( C H3N + )δ 55.1 (N + C H2CH2OH), δ 58.7 (N + CH2 C H2OH).

[0127] Synthesis of Compound 14 in <Example 14>

[0128]

Chemical Structure

[0129] 1 H-NMR (D2O 400MHz): δ 0.89 (m, 12H, C H 3CH2CH2CH, N + C H 3), δ 1.28 (m, 2H, CH3C H 2CH2CH2), δ 1.58 (m, 2H, CH3CH2C H 2CH2), δ 3.16 (m, 2H, CH3CH2CH2C H 2), δ 6.31, 7.61 (s, 2H, H 2PO2 - ).<000086​​​​​​​​​H2), δ 61.3 (N + C H3).

[0130] <Example 15> Synthesis of Compound 15

[0131]

change

[0132] 1 H-NMR (D2O 400MHz): δ 6.29, 7.58 (s, 2H, H 2PO2 - ).

[0133] <Example 16> Synthesis of Compound 16

[0134]

change

[0135] H-NMR (D2O 400MHz): δ 2.67 (m, 3H, N + C H 3), δ 3.79 (m, 2H, N + C H 2COOH), δ 6.27, 7.60 (s, 2H, H 2PO2 - ). 13 C-NMR (D2O 100MHz): δ 32.6 (N + C H3), δ 49.0 (N + C H2COOH), δ 169.3 (N + CH2 C OOH) .

[0136] <Example 17> Synthesis of Compound 17

[0137]

change

[0138] 1 H-NMR (D2O 400MHz): δ 3.04 (t, 2H, N + C H 2CH2OH), δ 3.72 (t, 2H, N + CH2C H 2OH), δ 5.94, 7.51 (s, 2H, H 2PO3 - ). 13 C-NMR (D2O 100MHz): δ 41.2 (N + C H₂CH₂OH), δ 57.5 (N + CH2 C H2OH).

[0139] <Example 18> Synthesis of Compound 18

[0140]

change

[0141] 1 H-NMR (D2O 400MHz): δ 1.21 (s, 6H, N + CC H 3), δ 3.45 (s, 2H, N + CC H 2OH), δ 5.94, 7.51 (s, 2H, H 2PO3 - ). 13 C-NMR (D2O 100MHz): δ 21.5 (N + C C H3), δ 55.1 (N + C C H2OH), δ 66.5 (N + C CH2OH).

[0142] <Example 19> Synthesis of Compound 19

[0143]

change

[0144] 1 H-NMR (D2O 400MHz): δ 1.18 (s, 3H, N + CC H 3), δ 3.49-3.61 (m, 4H, N + CC H 2OH), δ 5.94, 7.51 (s, 2H, H 2PO3 - ). 13 C-NMR (D2O 100MHz): δ 16.9 (N + C C H3), δ 58.4 (N + C CH2OH), δ 62.9 (N + C C H2OH).

[0145] <Example 20> Synthesis of Compound 20

[0146]

change

[0147] 1 H-NMR (D2O 400MHz): δ 3.64 (s, 6H, N + CC H 2OH), δ 5.94, 7.51 (s, 2H, H 2PO3 - ). 13 C-NMR (D2O 100MHz): δ 59.3 (N + C C H2OH), δ 61.4 (N + C CH2OH).

[0148] <Example 21> Synthesis of Compound 21

[0149]

Chem.

[0150] 1 H-NMR (D2O 400 MHz): δ 0.89 (m, 9H, C H 3CH2CH2CH2, N + C H 3), δ 1.28 (m, 2H, CH3C H 2CH2CH2), δ 1.58 (m, 2H, CH3CH2C H 2CH2), δ 3.02 (m, 2H, CH3CH2CH2C H 2), δ 5.94, 7.53 (s, 2H, H 2PO3 - ). 13 C-NMR (D2O 100 MHz): δ 12.7 ( C H3CH2CH2CH2), δ 19.0 (CH3 C H2CH2CH2), δ 25.9 (CH3CH2 C H2CH2), δ 42.5 (CH3CH2CH2 C H2), δ 57.6 (N + <00XX1003>H(CH3)2).

[0151] <Example 22> Synthesis of Compound 22 [[ID=4Z]]

[0152]

Chem.

[0153] 1 H-NMR (D2O 400 MHz): δ 2.83 (s, 6H, C H 3N + ), δ 3.20 (t, 2H, C H 2N + ), δ 3.81 (t, 2H, N + CH2C H 2OH), δ 5.95, 7.52 (s, 2H,H 2PO3 - ). 13 C-NMR (D2O 100MHz): δ 42.6 ( C H3N + ), δ 55.1 (N + C H₂CH₂OH), δ 58.7 (N + CH2 C H2OH).

[0154] <Example 23> Synthesis of Compound 23

[0155]

change

[0156] 1 H-NMR (D2O 400MHz): δ 5.94, 7.51 (s, 2H, H 2PO3 - ).

[0157] <Example 24> Synthesis of Compound 24

[0158]

change

[0159] 1 H-NMR (D2O 400MHz): δ 3.04 (t, 4H, N + C H 2CH2OH), δ 3.72 (t, 4H, N + CH2C H 2OH), δ 7.51 (s, 1H, H PO3 2- ). 13 C-NMR (D2O 100MHz): δ 41.2 (N + C H₂CH₂OH), δ 57.5 (N + CH2 C H2OH).

[0160] <Example 25> Synthesis of Compound 25

[0161]

change

[0162] 1 H-NMR (D2O 400MHz): δ 1.21 (s, 12H, N + CC H 3), δ 3.45 (s, 4H, N + CC H 2OH), δ 7.51 (s, 1H, H PO3 2- ). 13 C-NMR (D2O 100MHz): δ 21.5 (N + C C H3), δ 55.1 (N + C C H2OH), δ 66.5 (N + C CH2OH).

[0163] <Example 26> Synthesis of Compound 26

[0164]

change

[0165] 1 H-NMR (D2O 400MHz): δ 2.83 (s, 12H, C H 3N + ), δ 3.20 (t, 4H, C H 2N + ), δ 3.81 (t, 4H, N + CH2C H 2OH), δ 7.52 (s, 1H, H PO3 2- ). 13 C-NMR (D2O 100MHz): δ 42.6 ( C H3N+ ), δ 55.1 (N + C H₂CH₂OH), δ 58.7 (N + CH2 C H2OH).

[0166] <Example 27> Synthesis of Compound 27

[0167]

change

[0168] 1 H-NMR (D2O 400MHz): δ 0.96 (t, 3H, C H 3(CH2)9), δ 1.29 (m, 12H, CH3CH2(C H 2)6), δ 1.33 (m, 6H, CH3C H 2(CH2)6(C H 2)2), δ 3.04 (t, 2H, N + C H 2CH2OH), δ 3.72 (t, 2H, N + CH2C H 2OH). 13 C-NMR (D2O 100MHz): δ 14.0 ( C H3(CH2)9), δ 14.4 (CH3CH2(CH2)6 C H2CH2), δ 23.1 (CH3 C H2(CH2)8), δ 30.0 (CH3CH2CH2( C H2)4), δ 30.3 (CH3(CH2)8 C H2), δ 31.6 (CH3CH2 C H2(CH2)4 C H2(CH2)2), δ 41.2 (N + C H₂CH₂OH), δ 57.5 (N + CH2 C H2OH).

[0169] <Example 28> Synthesis of Compound 28

[0170]

Chem.

[0171] 1 H-NMR (D2O 400 MHz): δ 0.96 (t, 3H, C H 3(CH2)9), δ 1.21 (s, 6H, N + CC H 3), δ 1.29 (m, 12H, CH3CH2(C H 2)6), δ 1.33 (m, 6H, CH3C H 2(CH2)6(C H 2)2), δ 3.45 (s, 2H, N + CC H 2OH). 13 C-NMR (D2O 100 MHz): δ 14.0 ( C H3(CH2)9), δ 14.4 (CH3CH2(CH2)6 C H2CH2), δ 21.5 (N + C C H3), δ 23.1 (CH3 C H2(CH2)S), δ 30.0 (CH3CH2CH2( C H2)4), δ 30.3 (CH3(CH2)8 C H2), δ 31.6 (CH3CH2 C H2(CH2)4 C H2(CH2)2), δ 55.1 (N + C C H2OH), δ 66.5 (N + C CH2OH).

[0172] <Example 29> Synthesis of Compound No.

[0173]

Chem.

[0174] 1 H-NMR (D2O 400 MHz): δ 0.96 (t, 3H, C H 3(CH2)9), δ 1.29 (m, 12H, CH3CH2(C H 2)6), δ 1.33 (m, 6H, CH3C H 2(CH2)6(C H 2)2), δ 2.83 (s, 6H, C H 3N + ), δ 3.20 (t, 2H, C H 2N + ), δ 3.81 (t, 2H, N + CH2C H 2OH). 13 C-NMR (D2O 100 MHz): δ 14.0 ( C H3(CH2)9), δ 14.4 (CH3CH2(CH2)6 C H2CH2), δ 23.1 (CH3 C H2(CH2)8), δ 30.0 (CH3CH2CH2( C H2)4), δ 30.3 (CH3(CH2)8 C H2), δ 31.6 (CH3CH2 C H2(CH2)4 C H2(CH2)2), δ 42.6 ( C H3N + ), δ 55.1 (N + C H2CH2OH), δ 58.7 (N + CH2 C H2OH).

[0175] <Example 30> Synthesis of Compound 30

[0176]

Chem.

[0177] 1 H-NMR (D2O 400 MHz): δ 0.96 (t, 3H, C H3(CH2)9), δ 1.29 (m, 12H, CH3CH2(C H 2)6), δ 1.33 (m, 6H, CH3C H 2(CH2)6(C H 2)2), δ 3.04 (t, 4H, N + C H 2CH2OH), δ 3.72 (t, 4H, N + CH2C H 2OH). 13 C-NMR (D2O 100MHz):δ 14.0 ( C H3(CH2)9), δ 14.4 (CH3CH2(CH2)6 C H2CH2), δ 23.1 (CH3 C H2(CH2)8), δ 30.0 (CH3CH2CH2( C H2)4), δ 30.3 (CH3(CH2)8 C H2), δ 31.6 (CH3CH2 C H2(CH2)4 C H2(CH2)2), δ 41.2 (N + C H2CH2OH), δ 57.5 (N + CH2 C H2OH).

[0178] <Example 31> Synthesis of Compound 31

[0179]

Chem.

[0180] 1 H-NMR (D2O 400MHz): δ 0.96 (t, 3H, C H 3(CH2)9), δ 1.21 (s, 12H, N + CC H 3), δ 1.29 (m, 12H, CH^{3}CH^{2}(C H 2)6), δ 1.33 (m, 6H, CH^{3}C H 2(CH2)6(C H2) 2), δ 3.45 (s, 4H, N + CC H 2OH). 13 C-NMR (D2O 100MHz): δ 14.0 ( C H3(CH2)9), δ 14.4 (CH3CH2(CH2)6 C H2CH2), δ 21.5 (N + C C H3), δ 23.1 (CH3 C H2(CH2)8), δ 30.0 (CH3CH2CH2( C H2)4), δ 30.3 (CH3(CH2)8 C H2), δ 31.6 (CH3CH2 C H2(CH2)4<谢001245>H2(CH2)2), δ <谢001246>55.1 (N + C C H2OH), δ <谢001247>66.5 (N + C CH2OH).

[0181] <Example 32> Synthesis of Compound 32

[0182]

Chemical Structure

[0183] 1 H-NMR (D2O 400MHz): δ 0.96 (t, 3H, C[[ID=B50]] H 3(CH2)9), δ 1.29 (m, 12H, CH3CH2(C H 2)6), δ 1.33 (m, 6H, CH3C H 2(CH2)6(C<00B1264>2)2), δ 2.83 (s, 12H, C H 3N + ), δ 3.20 (t, 4H, C H 2N + ), δ 3.81 (t, 4H, N + CH2C H 2OH). 13 It should be noted that there seem to be some incorrect tags in the original text (e.g., "<谢001245>", "<谢001246>", "<谢001247>", "<谢001264>", "<谢001265>", "<谢001266>", "<谢001267>", "<谢001268>", "<谢001269>", "<谢001270>", "<谢001271>", "<B50>", "<B51>", "<B52>", "<B53>", "<B54>", "<B55>", "<B56>", "<B57>", "<B58>", "<B59>", "<B60>", "<B61>", "<B62>", "<B63>", "<B64>", "<B65>", "<B66>", "<B67>", "<B68>", "<B69>", "<B70>", "<B71>"). I have translated them as they are while highlighting the potential issues. If these are not actual tags but errors, they may need to be corrected in the original source for a more accurate translation.C-NMR (DO 100MHz): δ 14.0 ( C H3(CH2)9), δ 14.4 (CH3CH2(CH2)6 C H2CH2), δ 23.1 (CH3 C H2(CH2)8), δ 30.0 (CH3CH2CH2( C H2)4), δ 30.3 (CH3(CH2)8 C H2), δ 31.6 (CH3CH2 C H2(CH2)4 C H2(CH2)2), δ 42.6 ( C H3N + ), δ 55.1 (N + C H2CH2OH), δ 58.7 (N + CH2 C H2OH).

[0184] <Comparative Examples> Compounds 33 to 41, 43 to 45, and 47 to 50 phosphate compounds The synthesis was carried out in the same manner as in Example 1 using the amine compounds and phosphoric acid shown in Tables 4 to 6.

[0185] <Comparative Examples> Compounds 42, 46, and 53 Lactate-based compounds The synthesis was carried out in the same manner as in Example 1 using the amine compounds and lactic acid shown in Tables 4 to 6.

[0186] <Comparative Example> Compound 51 Halogen compounds The synthesis was carried out in the same manner as in Example 1 using the amine compounds shown in Tables 4 to 6 and hydrochloric acid.

[0187] <Comparative Example> Compound 52 Halogen compounds The compounds were synthesized in the same manner as in Example 1 using the amine compounds shown in Tables 4 to 6 and trifluoromethanesulfonic acid.

[0188] The compounds of the above Examples and Comparative Examples were subjected to the following measurements and evaluations. 1. Properties at room temperature (25°C) The moisture content (mass%) of compounds 1 to 32 in the examples was measured using a Karl Fischer moisture meter (KF-100, manufactured by Mitsubishi Chemical Analytech) and confirmed to be hydrates with the moisture content shown in Tables 1 to 3. After confirming the properties of these hydrates at 25°C, they were placed in screw tubes and dried under reduced pressure to form anhydrous compounds, and their properties at 25°C were confirmed. The results are shown in Tables 1 to 3 and Tables 8A and 8B. Among the compounds in the examples, the hydrates and anhydrous compounds 1 to 17, 21, and 22 were liquids at 25°C.

[0189] It was found that the organic ammonium salts of the present invention, which use a phosphinate anion or a phosphonate anion as the anion, have a tendency to become liquid compared to conventional organic ammonium salts containing halogen anions, such as the comparative compounds 51 and 52, because the interaction between the cation and anion molecules is alleviated. In particular, it was confirmed that the phosphinate anions of compounds 1 to 16 are liquid at 25°C and have low melting points, because the interaction between the cation and anion molecules is particularly alleviated.

[0190] 2. Viscosity measurement evaluation The viscosities of the hydrates of the compounds of the Examples and Comparative Examples shown in Tables 7A and 7B were confirmed. The viscosities were measured using a rotational viscometer (BROOK FIELD DIGITAL VISCOMETER MODEL DV-2 Pro).

[0191] The viscosity of the quaternary ammonium salt hydrates of each anion for the same cation species was lower with the phosphonate anion and phosphinate anion of the Examples than with the phosphate anion and lactate anion of the Comparative Examples, regardless of the cation species. It was also confirmed that the phosphinate anion had an even lower viscosity than the phosphonate anion. This suggests that the phosphonate and phosphinate anions had lower viscosities than the phosphate and lactate anions, and that the phosphinate anion had lower viscosities than the phosphonate anion, due to the relaxation of interactions such as hydrogen bonds between cation and anion molecules.

[0192] When comparing compounds whose anion is phosphinate anion, the following trends were observed.

[0193] When comparing compounds with hydroxyalkyl groups in the cation, the viscosity was lower in compounds 1 to 3 and 5 to 9 with different substituents (two types of groups bonded to the nitrogen of the cation: a hydrogen atom and a hydroxyalkyl group) than in compound 4, which has the same substituent but all four groups bonded to the nitrogen of the cation are hydroxyalkyl groups.

[0194] When comparing compounds containing cations consisting of linear hydroxy hydrocarbon groups (1-hydroxyethyl groups) and hydrogen atoms, the viscosity of Compound 4 (Example 37), which contains four 1-hydroxyethyl groups, was 981 mPa·s; Compound 3 (Example 36), which contains three hydroxyl groups, was 656 mPa·s; Compound 2 (Example 35), which contains two hydroxyl groups, was 69 mPa·s; and Compound 1 (Example 31), which contains one hydroxyl group, was 17 mPa·s. Furthermore, when comparing compounds containing branched hydroxy hydrocarbon groups, the viscosity of Compound 9 (Example 42), which contains three hydroxyl groups in the hydroxy hydrocarbon group, was 375 mPa·s; Compounds 6–8 (Examples 39–41), which contain two hydroxyl groups, were 269–288 mPa·s; and Compound 5 (Example 38), which contains one hydroxyl group, was 250 mPa·s. The viscosity of the compound decreased with the number of branched hydroxy hydrocarbon groups or hydroxyl groups in the structure. These results suggest that the viscosity decreased due to reduced hydrogen bonding interactions between molecules and with hydration water, which are caused by hydroxyl groups.

[0195] When comparing cations consisting of hydrogen atoms and hydrocarbon groups (alkyl groups), compound 11 (Example 45), which has three hydrogen atoms, had a viscosity of 113 mPa·s, while compound 10 (Example 43), which has one hydrogen atom, had a viscosity of 13 mPa·s. When comparing cations consisting of substituents selected from hydrogen atoms, hydrocarbon groups (alkyl groups), and linear hydroxy hydrocarbon groups, compound 13 (Example 47), which has one hydrogen atom, had a viscosity of 63 mPa·s, while compound 12 (Example 46), which has no hydrogen atoms, had a viscosity of 31 mPa·s. The fewer the number of hydrogen atoms in the structure, the lower the viscosity of the compound. These results suggest that the viscosity decrease is due to a decrease in the water of hydration resulting from hydrogen atoms or hydrogen bonding interactions with hydroxyl groups.

[0196] 3. Freezing point measurement evaluation A 50% by mass aqueous solution of the compounds of the Examples and Comparative Examples shown in Tables 8A and 8B was prepared and its freezing point was measured in accordance with JIS K0065 (Method for measuring the freezing point of chemical products).

[0197] The freezing points of 50% by mass aqueous solutions of quaternary ammonium salts of each anion for the same cation species were lower for the phosphonate and phosphinate anions of the Examples than for the phosphate, carboxylate, and halogen anions of the Comparative Examples, confirming their effect of depressing the freezing point of water. Furthermore, the freezing point of the phosphinate anion was lower than that of the phosphonate anion, demonstrating a greater effect of depressing the freezing point. When comparing compounds whose anion is phosphinate anion, the following trends were observed.

[0198] When comparing compounds with hydroxyalkyl groups in the cation, the freezing points of compounds 1 to 3 and 5 to 9 with different substituents (two types of groups bonded to the nitrogen of the cation: a hydrogen atom and a hydroxyalkyl group) were lower than those of compound 4 with the same substituent (all four groups bonded to the nitrogen of the cation are hydroxyalkyl groups).

[0199] When comparing cations containing a linear hydroxy hydrocarbon group (1-hydroxyethyl group) and hydrogen atoms, the freezing point of compound 4 (Example 57), which has four linear hydroxy hydrocarbon groups, was -22°C; compound 3 (Example 56), which has three linear hydroxy hydrocarbon groups, was -24°C; compound 2 (Example 55), which has two hydroxy groups, was -35°C; and compound 1 (Example 52), which has one hydroxyl group, was less than -40°C. Furthermore, when comparing cations containing branched hydroxy hydrocarbon groups, compound 9 (Example 65), which has three hydroxyl groups in the branched hydroxy hydrocarbon group, was -24°C; compounds 6 to 8 (Examples 61, 62, and 64), which have three hydroxyl groups, were -30 to -32°C; and compound 5 (Example 58), which has one hydroxyl group, was -40°C. The fewer the number of hydroxy hydrocarbon groups or hydroxyl groups in the structure, the lower the freezing point of the compound. These results suggest that the lower the freezing point is due to the reduced hydrogen bonding strength with water as the number of hydroxyl groups in the structure decreases.

[0200] When comparing cations consisting of hydrogen atoms and hydrocarbon groups (alkyl groups), the freezing point of compound 11 (Example 69), which has three hydrogen atoms, was -33 ° C, while the freezing point of compound 10 (Example 67), which has one hydrogen atom, was less than -40 ° C. Furthermore, when comparing cations consisting of a substituent selected from hydrogen atoms, hydrocarbon groups (alkyl groups), and linear hydroxy hydrocarbon groups, the freezing point of compound 13 (Example 71), which has one hydrogen atom, was -40 ° C, while the freezing point of compound 12 (Example 70), which has zero hydrogen atoms, was less than -40 ° C. The fewer the number of hydrogen atoms in the structure, the lower the freezing point of the compound. This result suggests that the fewer the number of hydrogen atoms in the structure, the lower the freezing point due to the reduced hydrogen bonding with water.

[0201] 4. Amino Acid Solubility Assessment To the compounds of the Examples and Comparative Examples shown in Table 9, 1 wt% of L-tryptophan, L-aspartic acid, L-arginine (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and zinc aspartate (synthesized by the method described in JP-A-2006-503092) were added, and the mixture was heated and stirred at 50°C for 1 hour, after which the solubility at 25°C was evaluated. Those that dissolved are indicated by ◯, and those that did not dissolve are indicated by ×.

[0202] Regarding solubility, the phosphate anion compounds of the comparative examples did not dissolve at 1 wt % for any of the cation species, but the phosphinate anions of the examples dissolved at 1 wt % for any of the cation species. These results suggest that the compounds of the present invention are useful as solvents for dissolving amino acids and their salts.

[0203] [Table 1]

[0204] [Table 2]

[0205] [Table 3]

[0206] [Table 4]

[0207] [Table 5]

[0208] [Table 6]

[0209] [Table 7A]

[0210] [Table 7B]

[0211] [Table 8A]

[0212] Table 8B

[0213] Table 9

Claims

1. An organic ammonium salt comprising a cation and an anion, wherein the cation is of the following formula (I): 【Chemistry 1】 (In the formula, R 1 each independently represents a methyl group, R 2 each independently represent a hydroxyalkyl group having one or more hydroxyl groups and having 1 to 22 carbon atoms, l and m each represent an integer of 0 to 3, n represents an integer of 1 to 4, and the sum of l, m, and n is 4, and the anion is a phosphonate ion or a phosphinate ion, the phosphonate ion being an anion of a phosphonic acid or an alkylphosphonic acid that does not contain an alkyl group, and the phosphinate ion being an anion of a phosphinic acid or an alkylphosphinic acid that does not contain an alkyl group, and the alkyl group in the alkylphosphonic acid or alkylphosphinic acid has 1 to 10 carbon atoms.

2. In the formula (I), l is an integer of 0 to 3, m is 0, n is an integer of 1 to 4, and R 2 2. The organic ammonium salt according to claim 1, wherein is a linear monohydroxyalkyl group.

3. In the formula (I), l is an integer of 0 to 3, m is 0, n is an integer of 1 to 4, and R 2 2. The organic ammonium salt according to claim 1, wherein is a branched hydroxyalkyl group having one or more hydroxyl groups.

4. 2. The organic ammonium salt according to claim 1, wherein, in formula (I), l is an integer of 0 to 2, m is an integer of 1 to 3, and n is an integer of 1 to 3.

5. 5. The organic ammonium salt according to claim 1, wherein the anion is a phosphinate anion.

6. The organic ammonium salt according to any one of claims 1 to 5, wherein the anhydride and hydrate of the organic ammonium salt are liquid at 25°C.

7. 2. A method for producing the organic ammonium salt according to claim 1, comprising the steps of: (A) Amine or ammonium compound (B) Phosphonic acid or phosphinic acid or a salt thereof Formulated with The cation of the formula (I) is an ammonium cation of the amine of the component (A) and a proton derived from the component (B), or an ammonium cation derived from the ammonium compound of the component (A), and is represented by the following formula (I): 【Chemistry 2】 (In the formula, R 1 each independently represents a methyl group, R 2 each independently represent a hydroxyalkyl group having one or more hydroxyl groups and having 1 to 22 carbon atoms, l and m each represent an integer of 0 to 3, n represents an integer of 1 to 4, and the sum of l, m, and n is 4), and the organic ammonium salt is formed in which the anion is a phosphonate ion or phosphinate ion derived from component (B).

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