Onium salt, onium salt composition, liquid composition containing onium salt and polysaccharide, preparation method thereof, and polysaccharide recovery method

Abstract

The present invention relates to an onium salt, a liquid composition comprising the onium salt and a polysaccharide, and a method for recovering the polysaccharide. The present invention can provide onium salts having very high polysaccharide solubility at 10 to 50 DEG C, in particular at temperatures of about room temperature (25 DEG C). The present invention may also provide a liquid composition comprising the onium salt and a polysaccharide as a composition suitable for polysaccharide recovery, and a method for efficiently recovering a polysaccharide using such a liquid composition comprising the onium salt and a polysaccharide.

Description

Technical Field

[0001] The present invention relates to an onium salt, an onium salt composition, a liquid composition comprising the onium salt and polysaccharide and a preparation method thereof, and a polysaccharide recovery method. Background Art

[0002] Polysaccharides are substances composed of a large number of monosaccharide molecules polymerized by glycosidic bonds. Among them, cellulose is a polysaccharide composed of β-glucose molecules, which is the most abundant biomass resource on the earth. Its dissolution and molding as an environmentally friendly material have been widely studied. In addition, chitin and chitosan are polysaccharides (whose main sugar components are N-acetylglucosamine and glucosamine) obtained from crustacean shells and used as materials with excellent biocompatibility and biodegradability in various technical fields. However, these polysaccharides have strong hydrogen bonds between or within the molecular chains, making them difficult to dissolve in common solvents.

[0003] Onium salts have been proposed as solvents for dissolving cellulose. PTL 1 discloses 1-butyl-3-methylimidazolium chloride and the like, and NPL 1 discloses 1-ethyl-3-methylimidazolium acetate and the like.

[0004] In order to dissolve various polysaccharides such as cellulose at around room temperature, PTL 2 discloses 1-ethyl-3-methylimidazolium dimethyl phosphate, etc. In addition, PTL 3 discloses N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium 3-(2-methoxyethoxy)propionate, etc. as onium salts for dissolving cellulose.

[0005] Onium salts are also proposed as solvents for dissolving chitin. NPL 2 discloses 1-butyl-3-methylimidazolium acetate and the like. Reference List Patent Literature

[0006] PTL 1: JP2005-506401A PTL 2: JP2010-132558A PTL 3: WO2014 / 087646 Non-patent literature

[0007] NPL 1: Green Chemistry, 2009, vol.11, pp.417-424. NPL 2: Polymer, 2008, vol.49, pp.2321-2327. Summary of the invention Technical issues

[0008] Various onium salts have been proposed in the prior art; however, most of the onium salts have a cellulose solubility as low as 5% or less at about 25°C. Therefore, in order to use these onium salts as solvents for dissolving cellulose, they must be heated. For chitosan, sufficient solubility cannot be obtained unless the onium salt is heated to about 100°C. An object of the present invention is to provide an onium salt having a high polysaccharide solubility at a temperature of 10 to 50°C, particularly at about room temperature (25°C). In addition, an object of the present invention is to provide a liquid composition comprising the onium salt and a polysaccharide as a composition suitable for recovering polysaccharides, and a method for effectively recovering polysaccharides using such a liquid composition comprising the onium salt and a polysaccharide. Solution

[0009] The present inventors have conducted extensive studies on substances that can be used as solvents to sufficiently dissolve polysaccharides at 10 to 50° C., particularly at about room temperature (25° C.). As a result, the present invention has been completed.

[0010] More specifically, the present invention provides the following [1] to

[20] . [1] An onium salt represented by the following formula (1): Formula (1): wherein R1 and R2 are the same or different and each represents a C2-C12 hydrocarbon group containing 1 to 5 heteroatoms or a group represented by the following formula (1a): -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 Represents a hydrocarbon group, when R 1 and R 2 is methoxyethyl and R 3 When it is a hydrogen atom, R 4 Represents C 2 or more carbon atoms. [2] The onium salt according to [1], wherein R in the formula (1) 3 It is a hydrogen atom or a methyl group. [3] The onium salt according to [1] or [2], wherein R in the formula (1) 1 and R2 are the same or different, and each is represented by the formula (2): Formula (2): -R 5 -XR 6 (2) Among them, R 5 Represents C 2 -C 5 Divalent hydrocarbon group, R 6 It represents a C that can contain 1 to 4 heteroatoms 1 -C 10 Hydrocarbon, R 5 and R 6 The total number of carbon atoms in is 3 to 12, the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and X represents an oxygen atom or a sulfur atom. [4] The onium salt according to [3], wherein in formula (2), R 5 is propane-1,3-diyl, R 6 is a C which can contain 1 to 4 heteroatoms 1 -C 9 A hydrocarbon group, and X is an oxygen atom. [5] The onium salt according to any one of [1] to [4], wherein R in the formula (1) 1 and R 2 same. [6] The onium salt according to any one of [1] to [5], wherein R in the formula (1) 4 Methyl, CH 2 =CH-, or CH 2 =C(CH 3 )-. [7] An onium salt composition comprising two or more onium salts represented by the following formula (1): Formula (1): wherein R1 and R2 are the same or different and each represents a C2-C12 hydrocarbon group containing 1 to 5 heteroatoms or a group represented by the following formula (1a): -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 Hydrocarbon; R 3represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 It represents a hydrocarbon group. [8] An onium hydroxide salt represented by the following formula (3): Formula (3): wherein R1 and R2 are the same or different and each represents a C2-C12 hydrocarbon group containing 1 to 5 heteroatoms or a group represented by the following formula (1a): -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 a hydrocarbon group; and R 3 represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, But not including R 1 and R 2 is methoxyethyl and R 3 For the case of hydrogen atoms. [9] A method for preparing an onium salt represented by formula (1), comprising reacting glyoxal, an amine compound represented by formula (6a), an amine compound represented by formula (6b), an aldehyde compound represented by formula (7), and a carboxylic acid represented by formula (4): Formula (6a): R 1 -NH 2 (6a) Formula (6b): R 2 -NH 2 (6b) In formulas (6a) and (6b), R 1 and R 2 are the same or different and each represents a C 2 -C 12 A hydrocarbon group or a group represented by the following formula (1a); -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 Hydrocarbon; Formula (7): R 3 -CHO (7) Among them, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; Formula (4): R 4 -COOH (4) Among them, R 4 represents a hydrocarbon group; and Formula (1): Among them, R 1 To R 4 As defined above.

[10] A method for preparing a composition represented by formula (1), comprising ion-exchanging a compound represented by formula (3) with a compound represented by formula (4): Formula (3): wherein R1 and R2 are the same or different and each represents a C2-C12 hydrocarbon group containing 1 to 5 heteroatoms or a group represented by the following formula (1a): -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; Formula (4): R 4 -COOH (4) Among them, R 4 represents a hydrocarbon group; and Formula (1): Among them, R 1 To R 4 As defined above.

[11] A polysaccharide-containing liquid composition comprising at least one polysaccharide and an onium salt represented by the following formula (1) or the onium salt composition according to [7], wherein the polysaccharide is dissolved in the onium salt: Formula (1): wherein R1 and R2 are the same or different and each represents a C2-C12 hydrocarbon group containing 1 to 5 heteroatoms or a group represented by the following formula (1a): -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 Represents a hydrocarbon group, when R 1 is (2-methoxyethoxy)methyl, R 2 is 2-[2-(2-methoxyethoxy)ethoxy]ethyl, and R 3 When it is a hydrogen atom, R 4 Represents C 2 or more carbon atoms.

[12] The polysaccharide-containing liquid composition according to

[11] , further comprising at least one organic solvent, wherein the polysaccharide is dissolved in a medium containing the onium salt or the onium salt composition and the organic solvent.

[13] The polysaccharide-containing liquid composition according to

[12] , wherein the organic solvent is at least one organic solvent selected from the group consisting of dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

[14] The polysaccharide-containing liquid composition according to

[11] , wherein the polysaccharide is cellulose.

[15] A method for preparing a polysaccharide-containing liquid composition according to any one of

[11] to

[14] , comprising dissolving a polysaccharide using an onium salt represented by the following formula (1) or an onium salt composition according to [7]: Formula (1): wherein R1 and R2 are the same or different and each represents a C2-C12 hydrocarbon group containing 1 to 5 heteroatoms or a group represented by the following formula (1a): -OR a (1a) Among them, R a It represents a C that can contain 1 to 4 heteroatoms1 -C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 It represents a hydrocarbon group.

[16] The method for preparing a polysaccharide-containing liquid composition according to

[15] , wherein a temperature for dissolving the polysaccharide is 50° C. or lower.

[17] The method for preparing a polysaccharide-containing liquid composition according to

[15] or

[16] , wherein the polysaccharide is cellulose.

[18] A polysaccharide recovery method comprising contacting the polysaccharide-containing liquid composition according to any one of

[11] to

[14] with at least one poor solvent.

[19] The polysaccharide recovery method according to

[18] , wherein the poor solvent is selected from the group consisting of water, methanol, ethanol, acetone and mixed solvents thereof.

[20] The polysaccharide recovery method according to

[18] or

[19] , wherein the polysaccharide is cellulose. Beneficial effects of the present invention

[0011] According to the present invention, an onium salt having a very high polysaccharide solubility at a temperature of 10 to 50° C., particularly at about room temperature (25° C.), can be provided. A liquid composition comprising the onium salt and polysaccharide as a composition suitable for recovering polysaccharide can also be provided. In addition, a method for effectively recovering polysaccharide using such a liquid composition comprising the onium salt and polysaccharide can be provided. DETAILED DESCRIPTION

[0012] The present invention is described in detail below. The present invention relates to an onium salt represented by the following formula (1) (hereinafter referred to as onium salt (1)).

[0013] Formula (1): Among them, R 1 and R 2 are the same or different and each represents a C 2 -C 12 A hydrocarbon group or a group represented by the following formula (1a): -OR a (1a) Among them, R aIt represents a C that can contain 1 to 4 heteroatoms 1 -C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 It represents a hydrocarbon group.

[0014] In formula (1), R 1 and R 2 The "C containing 1 to 5 heteroatoms" 2 -C 12 The "hydrocarbon group" can be linear, branched or cyclic, or can contain double bonds or triple bonds. The number of heteroatoms is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms in the hydrocarbon group is preferably 3 to 10, more preferably 4 to 7.

[0015] In formula (1), R 1 and R 2 Examples of the "hetero atom" described in the formula include a nitrogen atom, an oxygen atom and a sulfur atom.

[0016] In formula (1), R 1 and R 2 The "C containing 1 to 5 heteroatoms" 2 -C 12 A "hydrocarbon group" is a C 2 -C 12 Hydrocarbyl groups, which are structured, for example, -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-C(=O)-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O) 2 -、-S(=O) 2 -O-, -OS(=O) 2 -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)-. 1 and R 2 The number of heteroatoms in the structure is 1 to 5, and the number or combination of interruptions or substitutions of the structure is not particularly limited.

[0017] It is preferably a hydrocarbon group interrupted or substituted by a structure -O- or -S-, and more preferably a hydrocarbon group interrupted or substituted by a structure -O-.

[0018] In the present invention, the hydrocarbon structure interrupted or substituted by the structure -O- or -S- can be an ether structure or a thioether structure, and can also be, for example, an epoxy structure or a thioepoxy structure, such as an epoxy group, a thioepoxy group, a glycidyl ether group or an epoxycyclohexyl group. In this case, R 1 or R 2 It may be an epoxy group, a thioepoxy group, or the like.

[0019] When R 1 and R 2 When two or more structures -O- or / and -S- are included, the number of carbon atoms between the structures -O- or / and -S- is desirably 2 or more.

[0020] More ideally, R 1 and R 2 The nitrogen atom on the imidazole ring to which they are bonded is R closest to the nitrogen atom on the imidazole ring. 1 or R 2 The number of carbon atoms between the heteroatoms in the is 2 or more.

[0021] In formula (1), R 1 and R 2 The "C without heteroatoms" 2 -C 12 The "hydrocarbon group" can be straight chain, branched or cyclic, or can contain double bonds or triple bonds. 2 -C 12 The hydrocarbon group includes an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group, but is not particularly limited thereto.

[0022] In formula (1), R 1 and R 2 The "C containing 1 to 5 heteroatoms" 2 -C 12 Examples of " include C containing 1 to 5 heteroatoms 2 -C 12 Straight or branched alkyl, C containing 1 to 5 heteroatoms 2 -C 12 Straight or branched alkenyl, C containing 1 to 5 heteroatoms 2 -C 12 Straight or branched chain alkynyl, C 3 -C 12 Optionally branched cycloalkyl, C 3 -C 12 Optionally branched cycloalkenyl, C6 -C 12 An optionally branched aromatic group, a C 7 -C 12 Optional branched aralkyl, etc. Preferably, it is a C 2 -C 12 Straight or branched chain alkyl, containing 1 to 5 heteroatoms C 2 -C 12 Straight or branched alkenyl, and containing 1 to 5 heteroatoms C 3 -C 12 Optionally branched cycloalkyl. The "C containing 1 to 5 heteroatoms" 2 -C 12 The "straight or branched alkyl" is preferably a C 3 -C 10 In another embodiment, preferably C 3 -C 10 A straight or branched chain alkyl group, more preferably a C 4 -C 7 Straight chain or branched chain alkyl. The "C containing 1 to 5 heteroatoms" 2 -C 12 The straight chain or branched chain alkenyl group is preferably a C 3 -C 10 In another embodiment, preferably C 3 -C 10 A straight chain or branched alkenyl group, more preferably a C 4 -C 7 Straight-chain or branched alkenyl. The "C containing 1 to 5 heteroatoms" 3 -C 12 The "optionally branched cycloalkyl" is preferably a C 3 -C 10 In another embodiment, preferably a C 3 -C 10 Optionally branched cycloalkyl, more preferably C 4 -C 7 Optionally branched cycloalkyl.

[0023] In formula (1), R 1 and R 2 The C 2 -C 12Specific examples of the hydrocarbon group include ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, propenyl, isopropenyl, allyl, propargyl, butenyl, crotyl, butadienyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl, tolyl, and 2,4,6-trimethylphenyl, but are not particularly limited thereto. When the C group does not contain hetero atoms, 2 -C 12 The hydrocarbon group may be a structure such as -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-N<, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-C(=O)-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O) 2 -O-, -OS(=O) 2 When -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)- is interrupted or substituted, it becomes a "C containing 1 to 5 heteroatoms" 2 -C 12 Hydrocarbon".

[0024] In formula (1a), R a It represents a C that can contain 1 to 4 heteroatoms 1 -C 12 The "C hydrocarbon group which may contain 1 to 4 heteroatoms" 1 -C 12 The "hydrocarbyl" group can be straight chain, branched or cyclic, or can contain double or triple bonds. In R a In the embodiment, the hydrocarbon group may contain no heteroatoms or may contain 1 to 4 heteroatoms. a When no heteroatoms are present, the number of carbon atoms in the hydrocarbon group is 1 to 12, preferably 1 to 6, and more preferably 1 to 3. a When containing heteroatoms, the number of heteroatoms is preferably 1 or 2. a The number of carbon atoms in the hydrocarbon group is 2 to 12, and preferably 2 to 6, when containing heteroatoms.

[0025] In formula (1a), when R a It is a C with 1 to 4 heteroatoms 2 -C 12 In the case of a hydrocarbon group, examples of the "heteroatom" include a nitrogen atom, an oxygen atom and a sulfur atom.

[0026] In formula (1a), R a The "C containing 1 to 4 heteroatoms" 2 -C 12 A "hydrocarbon group" is a C 2 -C 12 Hydrocarbyl groups, which are structured, for example, -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-C(=O)-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O) 2 -、-S(=O) 2 -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)-. a The number of heteroatoms in the structure is 1 to 4, and the number or combination of interruptions or substitutions of the structure is not particularly limited.

[0027] It is preferably a hydrocarbon group interrupted or substituted by a structure -O- or -S-, and more preferably a hydrocarbon group interrupted or substituted by a structure -O-.

[0028] In the present invention, the hydrocarbon structure interrupted or substituted by the structure -O- or -S- can be an ether structure or a thioether structure, and can also be, for example, an epoxy structure or a thioepoxy structure, such as an epoxy group, a thioepoxy group, a glycidyl ether group or an epoxycyclohexyl group. In this case, R a It may be an epoxy group, a thioepoxy group, or the like.

[0029] In formula (1a), when R a When two or more structures -O- or / and -S- are included, the number of carbon atoms between the structures -O- or / and -S- is desirably 2 or more. More desirably, R a The oxygen atom bonded to R a The number of carbon atoms between the heteroatoms closest to the oxygen atom is 2 or more.

[0030] In formula (1a), R a The "C without heteroatoms" 1 -C 12 Hydrocarbon" and "C 2 -C 12 The "hydrocarbon group" can be straight chain, branched or cyclic, or can contain double bonds or triple bonds. The "C1 -C 12 Hydrocarbon" and "C 2 -C 12 Examples of the "hydrocarbon group" include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group, but are not particularly limited thereto.

[0031] In formula (1a), R a The "C which may contain 1 to 4 heteroatoms" 1 -C 12 Examples of "hydrocarbon groups" include C 1 -C 12 Straight or branched alkyl, C 2 -C 12 Straight or branched alkenyl, C 2 -C 12 Straight or branched chain alkynyl, C 3 -C 12 Optionally branched cycloalkyl, C 3 -C 12 The optionally branched cycloalkenyl group may contain 1 to 5 heteroatoms. 6 -C 12 The optionally branched aromatic group may contain 1 to 4 heteroatoms. 7 -C 12 Optional branched aralkyl, etc. Preferably, it can contain 1 to 4 hetero atoms. 1 -C 12 Straight or branched alkyl, which may contain 1 to 4 heteroatoms 2 -C 12 A straight chain or branched alkenyl group, and a C 3 -C 12 Optionally branched cycloalkyl. The "C 1 -C 12 The "straight or branched alkyl" is preferably a C 1 -C 6 In another embodiment, it is preferably a C 2 -C 12 A straight chain or branched chain alkyl group, more preferably a C 1 -C 6 In another embodiment, preferably C 1 -C 12 Straight or branched chain alkyl, more preferably C 1 -C6 Straight or branched alkyl, even more preferably C 1 -C 3 Straight chain or branched chain alkyl. The "C 2 -C 12 The "straight or branched alkenyl" is preferably a C 2 -C 6 In another embodiment, it is preferably a C 2 -C 12 Straight or branched alkenyl, more preferably C 2 -C 6 In another embodiment, preferably C 2 -C 12 Straight or branched alkenyl, more preferably C 2 -C 6 Straight or branched alkenyl, even more preferably C 2 or C 3 Straight-chain or branched alkenyl. The "C 3 -C 12 The "optionally branched cycloalkyl" is preferably a C 3 -C 6 In another embodiment, it is preferred that the C 3 -C 12 Optionally branched cycloalkyl, more preferably C 3 -C 6 In another embodiment, preferably C 3 -C 12 Optionally branched cycloalkyl, more preferably C 3 -C 6 Optionally branched cycloalkyl, even more preferably C 3 Optionally branched cycloalkyl.

[0032] In formula (1), when R a It is C without heteroatom 1 -C 12 When the hydrocarbon group 1 -C 12Specific examples of the “hydrocarbon group” include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, vinyl, ethynyl, propenyl, isopropenyl, allyl, propargyl, butenyl, crotyl, butadienyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl, tolyl and 2,4,6-trimethylphenyl, but are not particularly limited thereto.

[0033] In formula (1), R a C without heteroatom 2 -C 12 Examples of the hydrocarbon group include ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, propenyl, isopropenyl, allyl, propargyl, butenyl, crotyl, butadienyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl, tolyl, and 2,4,6-trimethylphenyl, but are not particularly limited thereto. When the C group does not contain hetero atoms, 2 -C 12 The hydrocarbon group may be a structure such as -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-N<, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-C(=O)-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O) 2 When -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)- is interrupted or substituted, it becomes a "C containing 1 to 4 heteroatoms" 2 -C 12 Hydrocarbon".

[0034] R shown in formula (1) 1 and R 2Specific examples of the structure include 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-phenoxyethyl, 2-(benzyloxy)ethyl, 2-(p-methoxybenzyloxy)ethyl, 2-(2-methoxyethoxymethoxy)ethyl, 2-(2-benzyloxyethoxy)ethyl, 2-(dimethylamino)ethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-allyloxypropyl, 3-isopropoxypropyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 3-butoxypropyl, 3-pentyloxypropyl, 3-neopentyloxypropyl, 3-hexyloxypropyl, 3-cyclohexyloxypropyl, 3-(2-ethylhex-1-yl)oxypropyl, 3-(2,4,6-trimethylphenoxy)propyl, 3-(2-methoxyethoxy)propyl, 3-(dimethylamino)propyl, 4-methoxybutyl, 4-ethoxybutyl, 4-propoxybutyl, 4-isopropoxybutyl, 4-allyloxybutyl, 4-butoxybutyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl, 4-(1,1-dimethylethoxy)butyl, 4-pentyloxybutyl, 4-neopentyloxybutyl, 4-hexyloxybutyl 4-(2-ethylhexyl)oxybutyl, 4-(2-ethylhexyl)oxybutyl, 5-methoxypentyl, 5-ethoxypentyl, 5-propoxypentyl, 5-isopropoxypentyl, 5-allyloxypentyl, 5-butoxypentyl, 5-(1-methylpropoxy)pentyl, 5-(2-methylpropoxy)pentyl, 5-(1,1-dimethylethoxy)pentyl, 5-pentyloxypentyl, 5-neopentyloxypentyl, 5-hexyloxypentyl, 5-cyclohexyloxypentyl, 5-heptyloxypentyl, 6-methoxyhexyl, 6-ethoxyhexyl, 6-propoxyhexyl, 6-isopropoxyhexyl, 6 -(1-methylpropoxy)hexyl, 6-(2-methylpropoxy)hexyl, 6-(1,1-dimethylethoxy)hexyl, 6-pentyloxyhexyl, 6-neopentyloxyhexyl, 6-hexyloxyhexyl, 6-cyclohexyloxyhexyl, (2-methoxycyclohexane-1-yl)methyl, (2-ethoxycyclohexane-1-yl)methyl, (2-propoxycyclohexane-1-yl)methyl, (2-isopropoxycyclohexane-1-yl)methyl, (2-butoxycyclohexane-1-yl)methyl, [2-(1-methylpropoxy)cyclohexane-1-yl]methyl, [2-(2-methylpropoxy)cyclohexane-1-yl]methyl, [2-(1,1-dimethylethoxy)hexyl, [2-(1-methylpropoxy)cyclohexane-1-yl]methyl, [2-(2-methylpropoxy)cyclohexane-1-yl]methyl, [2-(1,1-dimethylethoxy)hexyl, [2-(1,1-dimethylethoxy)cyclohexane-1-yl]methyl ...1-(dimethylethoxy)cyclohexane-1-yl]methyl, (2-pentyloxycyclohexane-1-yl)methyl, (2-neopentyloxycyclohexane-1-yl)methyl, 2-methylthioethyl, 3-methylthiopropyl, 1-(methoxymethyl)propyl, (oxolan-2-yl)methyl, (furan-2-yl)methyl, 2-[(furan-2-yl)methylthio]ethyl, 2-(methylsulfonyl)ethyl, (thiophen-2-yl)methyl, p-methoxyphenyl, p-ethoxyphenyl, 3,4-methylene dioxyphenyl, 3,4-methylenedioxybenzyl, (7-oxabicyclo[2,2,1]heptane-2-yl)methyl, etc.; more preferably 2-methoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-isopropoxypropyl, 3-butoxypropyl, 3-(2-methoxyethoxy)propyl, 3-methylthiopropyl and 3-(dimethylamino)propyl; more preferably 2-methoxyethyl, 3-methoxypropyl and 3-(2-methoxyethoxy)propyl; however, the present invention is not limited thereto. ,

[0035] In formula (1), preferably R 1 and R 2 same.

[0036] In formula (1), R 3 represents a hydrogen atom or a hydrocarbon group that can contain heteroatoms. The "hydrocarbon group that can contain heteroatoms" can be linear, branched or cyclic, or can contain double bonds or triple bonds. 3 The hydrocarbon group in may not contain heteroatoms or may contain heteroatoms.

[0037] In formula (1), when R 3 When R is a hydrocarbon group containing no heteroatoms, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 3. 3 In the case of a heteroatom-containing hydrocarbon group, the number of carbon atoms is preferably 2 to 12, more preferably 2 to 8, even more preferably 2 to 4.

[0038] In formula (1), when R 3 When heteroatoms are contained, the number of heteroatoms is preferably 1 to 5, more preferably 1 or 2. The number of carbon atoms in the hydrocarbon group is 2 or more, preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.

[0039] In formula (1), when R 3 In the case of a hydrocarbon group containing a hetero atom, examples of the "hetero atom" include a nitrogen atom, an oxygen atom and a sulfur atom.

[0040] When R 3 In the case of a hydrocarbon group containing a hetero atom, examples of the "hetero atom" include a nitrogen atom, an oxygen atom and a sulfur atom. The number of the hetero atoms is preferably 1 to 5, and more preferably 1 or 2.

[0041] In formula (1), R 3 The "hydrocarbon group containing heteroatoms" in the present invention is a hydrocarbon group containing no heteroatoms, which is a hydrocarbon group having a structure such as -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-N<, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O)- 2 -O-, -OS(=O) 2 -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)-. The number or combination of such structure interruptions or substitutions is not particularly limited; however, R 3 The number of heteroatoms is preferably 1 to 5, more preferably 1 or 2.

[0042] It is preferably a hydrocarbon group interrupted or substituted by a structure -O- or -S-, and more preferably a hydrocarbon group interrupted or substituted by a structure -O-.

[0043] In the present invention, the hydrocarbon structure interrupted or substituted by the structure -O- or -S- can be an ether structure or a thioether structure, and can also be, for example, an epoxy structure or a thioepoxy structure, such as an epoxy group, a thioepoxy group, a glycidyl ether group or an epoxycyclohexyl group. In this case, R 3 It may be an epoxy group, a thioepoxy group, or the like.

[0044] When R 3 When two or more structures -O- or / and -S- are included, the number of carbon atoms between the structures -O- or / and -S- is 2 or more.

[0045] In formula (1), R 3 Examples of the "hydrocarbon group capable of containing heteroatoms" described in the above include straight or branched alkyl groups capable of containing heteroatoms, straight or branched alkenyl groups capable of containing heteroatoms, straight or branched alkynyl groups capable of containing heteroatoms, optional branched cycloalkyl groups capable of containing heteroatoms, optional branched cycloalkenyl groups capable of containing heteroatoms, optional branched aryl groups capable of containing heteroatoms, and optional branched aralkyl groups capable of containing heteroatoms. Preferably, straight or branched alkyl groups capable of containing heteroatoms, straight or branched alkenyl groups capable of containing heteroatoms, and optional branched cycloalkyl groups capable of containing heteroatoms are preferred. The "straight or branched alkyl group which may contain a hetero atom" is preferably a C 1 -C 12In another embodiment, it is preferably a C 1 -C 12 A straight chain or branched chain alkyl group, more preferably a C 1 -C 8 Straight or branched alkyl, even more preferably C 1 -C 4 In another embodiment, preferably C 1 -C 12 Straight or branched chain alkyl, more preferably C 1 -C 8 Straight or branched alkyl, even more preferably C 1 -C 3 Straight chain or branched chain alkyl. The “straight or branched alkenyl group which may contain a hetero atom” is preferably a C 2 -C 12 In another embodiment, it is preferably a C 2 -C 12 Straight or branched alkenyl, more preferably C 2 -C 8 Straight or branched alkenyl, even more preferably C which may contain 1 or 2 heteroatoms 2 -C 4 In another embodiment, preferably C 2 -C 12 Straight or branched alkenyl, more preferably C 2 -C 8 Straight or branched alkenyl, even more preferably C 2 or C 3 The "optionally branched cycloalkyl group which may contain heteroatoms" is preferably a C 3 -C 12 In another embodiment, it is preferred that the C 3 -C 12 Optionally branched cycloalkyl, more preferably C 3 -C 8 Optionally branched cycloalkyl, even more preferably C 3 or C 4 In another embodiment, preferably C 3 -C 12 Optionally branched cycloalkyl, more preferably C3 -C 8 Optionally branched cycloalkyl, even more preferably C 3 Cycloalkyl.

[0046] In formula (1), R 3 Specific examples of the "hydrocarbon group not containing hetero atoms" described in the above-mentioned group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, vinyl, ethynyl, propenyl, isopropenyl, allyl, propargyl, butenyl, crotyl, butadienyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl, tolyl, styryl and 2,4,6-trimethylphenyl; preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl and hexyl; more preferably methyl, ethyl, propyl, isopropyl and tert-butyl.

[0047] In formula (1), R 3 The “hydrocarbon group containing heteroatoms” described in the above is preferably 3-indolyl, p-methoxyphenyl, 7-oxabicyclo[2,2,1]hept-5-en-2-yl, 1,2-epoxyethyl, 1-methyl-2-methoxyvinyl, 2-furyl, 2-pyridyl, 4-imidazolyl or benzyloxymethyl; and more preferably 1-methyl-2-methoxyvinyl or 2-furyl; however, the present invention is not limited thereto.

[0048] In formula (1), R 3 Preferred is a hydrogen atom or a methyl group, and more preferred is a hydrogen atom.

[0049] In formula (1), R 1 To R 3 Some or all of can be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. Specific examples of the ring structure include but are not particularly limited to wherein R 1 and R 2 , R 1 and R 3 or R 2 and R 3 bonded together and through C containing 2 to 10 heteroatoms 2 -C 24 Hydrocarbon-bridged ring structure.

[0050] In formula (1), R 4 represents a hydrocarbon group which can be linear, branched or cyclic, or can contain double or triple bonds. 4 Preferably C 1 -C 12 Hydrocarbyl, more preferably C 1 -C8 Hydrocarbyl, even more preferably C 1 -C 3 Hydrocarbon.

[0051] In formula (1), R 4 Examples of the "hydrocarbon group" described in the formula include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and aralkyl. 1 -C 12 Straight or branched alkyl, C 1 -C 12 Straight or branched alkenyl, C 1 -C 12 Straight-chain or branched alkynyl, C 3 -C 12 Optional branched cycloalkyl, C 3 -C 12 Optional branched cycloalkenyl, C 6 -C 12 Optional branched aromatic group and C 7 -C 12 Optionally branched aralkyl; more preferably C 1 -C 3 Straight or branched alkyl and C 1 -C 3 Straight-chain or branched alkenyl.

[0052] In formula (1), R 4 Specific examples of the “hydrocarbon group” described in the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, vinyl, ethynyl, propenyl, isopropenyl, allyl, propargyl, 1-propynyl, butenyl, crotyl, butadienyl, pentadienyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl, tolyl, styryl, 2,4,6-trimethylphenyl, naphthyl and 2,6-dimethyl-1,5-heptadienyl, but are not particularly limited thereto.

[0053] In formula (1), R 4 -CO-O -Specific examples of the anions represented by include acetate ion, propionate ion, acrylate ion, propargyl ion, butyrate ion, isobutyrate ion, methacrylate ion, crotonate ion, tetraformate ion, cyclopropanecarboxylate ion, valerate ion, isovalerate ion, pivalate ion, angelica ion, tetraformate ion, cyclobutanecarboxylate ion, hexanoate ion, cyclopentanecarboxylate ion, xanthate ion, sorbate ion, cyclohexanecarboxylate ion, benzoate ion, octanoate ion, 2-ethylhexylcarboxylate ion, methyl methacrylate ion, octanoate ion, 2-ethylhexylcarboxylate ion, methyl methacrylate ion, propyl ... Benzoate ion, 2-norbornene carboxylate ion, nonyl ion, cinnamate ion, decanoate ion, adamantane carboxylate ion, geranyl ion, laurate ion, naphthalene carboxylate ion, etc. are preferred; acetate ion, propionate ion, acrylate ion, propargyl ion, butyrate ion, isobutyrate ion, methacrylate ion, crotonate ion, tetraformate ion, valerate ion, isovalerate ion and pivalate ion are preferred; and acetate ion, acrylate ion or methacrylate ion is particularly preferred; however, the present invention is not limited thereto.

[0054] In formula (2), R 5 Represents C 2 -C 5 A divalent hydrocarbon group. The "C 2 -C 5 The "divalent hydrocarbon group" can be straight chain, branched or cyclic, or can contain double or triple bonds. Examples include C 2 -C 5 Alkylene, C 2 -C 5 Alkenylene, C 2 -C 5 Alkynylidene, C 3 -C 5 Cycloalkylene and C 3 -C 5 Cycloalkenylene; preferably C 2 or C 3 Alkylene and C 2 or C 3 Alkenylene; and particularly preferably C 3 Alkylene.

[0055] In formula (2), R 5Specific examples include ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, cyclopropane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, cyclobutane-1,3-diyl, cyclobutane-1,2-diyl, 2-methylpropane-1,2-diyl, 2-methylpropane-1,3-diyl, pentane-1,5-diyl, pent ... pentane-1,4-diyl, pentane-1,3-diyl, cyclobutane-1,2-diyl, 2-methylpropane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, pentane-1,4-diyl 1,4-diyl, pentane-1,3-diyl, pentane-1,2-diyl, cyclopentane-1,3-diyl, cyclopentane-1,2-diyl, 2-methylbutane-2,4-diyl, 2-methylbutane-1,3-diyl, 2-methylbutane-1,4-diyl, 2-dimethylpropane-1,3-diyl, 1,3-butadiene-1,4-diyl and 2-propylene-1,3-diyl, but are not particularly limited thereto.

[0056] In formula (2), R 6 It represents a C that can contain 1 to 4 heteroatoms 1 -C 10 Hydrocarbon.

[0057] R 6 The "C which may contain 1 to 4 heteroatoms" 1 -C 10 The "hydrocarbon group" can be straight chain, branched or cyclic, or can contain double bonds or triple bonds. In addition, the group can contain no heteroatoms or can contain 1 to 4 heteroatoms.

[0058] In formula (2), in R 6 The number of carbon atoms in the hydrocarbon group capable of containing heteroatoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 3. 6 When R is a hydrocarbon group containing no heteroatoms, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. 6 In the case of a heteroatom-containing hydrocarbon group, the number of carbon atoms is preferably 2 to 10, more preferably 2 to 7, even more preferably 2 to 4.

[0059] In formula (2), when R 6 In the case of a hydrocarbon group containing 1 to 4 hetero atoms, examples of the "hetero atom" include a nitrogen atom, an oxygen atom and a sulfur atom.

[0060] In formula (2), R 6 The "C containing 1 to 4 heteroatoms" 2 -C 10 A "hydrocarbon group" is a C 2 -C 10Hydrocarbyl groups, which are structured, for example, -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-N<, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-C(=O)-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O) 2 -、-S(=O) 2 -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)-. 6 The number of heteroatoms in the structure is 1 to 4, and the number or combination of interruptions or substitutions of the structure is not particularly limited.

[0061] It is preferably a hydrocarbon group interrupted or substituted by a structure -O- or -S-, and more preferably a hydrocarbon group interrupted or substituted by a structure -O-.

[0062] In the present invention, the hydrocarbon structure interrupted or substituted by the structure -O- or -S- can be an ether structure or a thioether structure, and can also be, for example, an epoxy structure or a thioepoxy structure, such as an epoxy group, a thioepoxy group, a glycidyl ether group or an epoxycyclohexyl group. In this case, R 6 It may be an epoxy group, a thioepoxy group, or the like.

[0063] When R 6 When two or more structures -O- or / and -S- are included, the number of carbon atoms between the structures -O- or / and -S- is 2 or more.

[0064] In formula (2), R 6 The "C without heteroatoms" 2 -C 10 The "hydrocarbon group" can be straight chain, branched or cyclic, or can contain double bonds or triple bonds. Examples of the hydrocarbon group containing no heteroatoms include straight chain or branched alkyl groups, straight chain or branched alkenyl groups, straight chain or branched alkynyl groups, optionally branched cycloalkyl groups, optionally branched cycloalkenyl groups, optionally branched aryl groups and optionally branched aralkyl groups. Preferred are straight chain or branched alkyl groups, straight chain or branched alkenyl groups and optionally branched cycloalkyl groups. The "C 1 -C 10 Examples of "hydrocarbon groups" include C 1 -C 10 Straight or branched alkyl, C 2 -C10 Straight or branched alkenyl, C 2 -C 10 Straight or branched chain alkynyl, C 3 -C 10 Optionally branched cycloalkyl, C 3 -C 10 The optionally branched cycloalkenyl group may contain 1 to 5 heteroatoms. 6 -C 10 The optionally branched aromatic group may contain 1 to 4 heteroatoms. 7 -C 10 Optional branched aralkyl, etc. Preferably, it can contain 1 to 4 hetero atoms. 1 -C 10 Straight or branched alkyl, which may contain 1 to 4 heteroatoms 2 -C 10 A straight chain or branched alkenyl group, and a C 3 -C 10 Optionally branched cycloalkyl. The "C 1 -C 10 The "straight or branched alkyl" is preferably a C 2 -C 10 In another embodiment, it is preferred that the C 2 -C 7 A straight chain or branched chain alkyl group, more preferably a C 2 -C 4 In another embodiment, preferably C 1 -C 7 Straight or branched chain alkyl, more preferably C 1 -C 4 Straight chain or branched chain alkyl. The "C 2 -C 10 The "straight or branched alkenyl" is preferably a C 2 -C 10 In another embodiment, it is preferably a C 2 -C 7 A straight chain or branched alkenyl group, more preferably a C 2 -C 4 In another embodiment, preferably C 2 -C7 Straight or branched alkenyl, more preferably C 2 -C 4 Straight-chain or branched alkenyl. The "C 3 -C 10 The "optionally branched cycloalkyl" is preferably a C 3 -C 10 In another embodiment, it is preferred that the C 3 -C 7 Optionally branched cycloalkyl, more preferably C 3 -C 7 In another embodiment, preferably C 3 -C 7 Optionally branched cycloalkyl, more preferably C 3 or C 4 Optionally branched cycloalkyl.

[0065] In formula (2), when R 6 It is C without heteroatom 1 -C 10 When the hydrocarbon group 1 -C 10 Specific examples of the “hydrocarbon group” include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, propenyl, isopropenyl, allyl, propargyl, butenyl, crotyl, butadienyl, salvinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl and 2,4,6-trimethylphenyl, but are not particularly limited thereto.

[0066] R 6 The C 2 -C 10 The "C 2 -C 10 Examples of the "alkyl" include ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, 2-ethylhexyl, decyl, vinyl, ethynyl, propenyl, isopropenyl, allyl, propargyl, butenyl, crotyl, butadienyl, geranyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, phenyl, benzyl and 2,4,6-trimethylphenyl; preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, neopentyl and hexyl; more preferably methyl, ethyl, propyl and isopropyl. When the C group does not contain heteroatoms, 2 -C 10The hydrocarbon group may be a structure such as -O-, -N<, -NH-, -S-, -C(=O)-O-, -C(=O)-, =N-, -C(=O)-N<, -C(=O)-NH-, -OC(=O)-O-, -OC(=O)-N<, -OC(=O)-NH-, -C(=O)-N[-C(=O)-]-, -C(=O)-NH-C(=O)-, >NC(=O)-N<, >NC(=O)-NH-, -HN-C(=O)-NH-, -S(=O)-, -S(=O) 2 When -O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)- or -C(=NH)- is interrupted or substituted, it becomes a "C containing 1 to 4 heteroatoms" 2 -C 10 Hydrocarbon".

[0067] In formula (2), R 6 The "C without heteroatoms" 2 -C 10 The "hydrocarbon group" is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, more preferably a methyl group.

[0068] In formula (2), R 6 The "C containing heteroatoms" 2 -C 10 The "hydrocarbon group" is preferably a 2-methoxyethyl group, a 2-(2-methoxyethoxy)ethyl group, a furyl group, a thienyl group, a 2-pyridyl group, a (oxolan-2-yl)methyl group, a 2-morpholinylethyl group, a 2-(dimethylamino)ethyl group or a 1,2-epoxypropyl group; more preferably a 2-methoxyethyl group; however, the present invention is not limited thereto.

[0069] In formula (2), R 6 Preferred is methyl, ethyl, propyl or isopropyl; more preferred is methyl.

[0070] In formula (2), R 5 and R 6 The total number of carbon atoms in the molecule is 3 to 12.

[0071] In formula (2), X represents an oxygen atom or a sulfur atom. 5 and R 6 Bonded via an ether group (-O-) or a thioether group (-S-).

[0072] Specific examples of the imidazolium cation of the onium salt represented by formula (1) include 1,3-bis(2-methoxyethyl)imidazolium, 1,3-bis(2-ethoxyethyl)imidazolium, 1,3-bis(2-propoxyethyl)imidazolium, 1,3-bis(2-isopropoxyethyl)imidazolium, 1,3-bis(2-phenoxyethyl)imidazolium, 1,3-bis(2-benzyloxyethyl)imidazolium, 1,3-bis[2-(p-methoxybenzyloxy)ethyl]imidazolium, 1,3-bis[2-(2-methoxyethoxymethoxy)ethyl]imidazolium, 1,3-bis[2-(2-benzyloxyethoxy)ethyl]imidazolium, 1,3-bis(3-methoxypropyl)imidazolium, 1,3-bis(3-ethoxypropyl)imidazolium, 、1,3-bis(3-propoxypropyl)imidazolium、1,3-bis(3-isopropoxypropyl)imidazolium、1,3-bis(3-allyloxypropyl)imidazolium、1,3-bis(3-butoxypropyl)imidazolium、1,3-bis[3-(1-methylpropoxy)propyl]imidazolium、1,3-bis[3-(2-methylpropoxy)propyl]imidazolium、1 ,3-bis[3-(1,1-dimethylethoxy)propyl]imidazolium, 1,3-bis[(oxacyclopentyl-2-yl)methyl]imidazolium, 1,3-bis(3-pentyloxypropyl)imidazolium, 1,3-bis(3-neopentyloxypropyl)imidazolium, 1,3-bis(3-hexyloxypropyl)imidazolium, 1,3-bis(3-cyclohexyloxypropyl)imidazolium, 1 ,3-bis(3-heptyloxypropyl)imidazolium, 1,3-bis(3-octyloxypropyl)imidazolium, 1,3-bis(3-nonyloxypropyl)imidazolium, 1,3-bis{3-[(2-ethylhexyl-1-yl)oxy]propyl}imidazolium, 1,3-bis[3-(2,4,6-trimethylphenoxy)propyl]imidazolium, 1,3-bis[3-(2-methylphenoxy)propyl]imidazolium 1,3-bis[2-(dimethylamino)ethyl]imidazolium, 1,3-bis[3-(dimethylamino)propyl]imidazolium, 1,3-bis(2-methylthioethyl)imidazolium, 1,3-bis{2-[(furan-2-yl)methylthio]ethyl]imidazolium, 1,3-bis[2-(furan-2-yl)methyl]imidazolium imidazolium, 1,3-bis[1-(methoxymethyl)propyl]imidazolium, 1,3-bis(4-methoxybutyl)imidazolium, 1,3-bis(4-ethoxybutyl)imidazolium, 1,3-bis(4-propoxybutyl)imidazolium, 1,3-bis(4-isopropoxybutyl)imidazolium, 1,3-bis(4-allyloxybutyl)imidazolium, 1,3-bis(4- imidazolium, 1,3-bis[4-(1-methylpropoxy)butyl]imidazolium, 1,3-bis[4-(2-methylpropoxy)butyl]imidazolium, 1,3-bis[4-(1,1-dimethylethoxy)butyl]imidazolium, 1,3-bis(4-pentyloxybutyl)imidazolium, 1,3-bis(4-neopentyloxybutyl)imidazolium, 1,3-bis(4-hexyloxybutyl)imidazolium, 1,3-bis(4-cyclohexyloxybutyl)imidazolium, 1,3-bis(4-heptyloxybutyl)imidazolium, 1,3-bis(4-octyloxybutyl)imidazolium, 1,3-bis{4-[(2-ethylhexyl-1-yl)oxy]butyl}imidazolium, 1,3-bis(5-methoxypentyl)imidazolium, 1,3- di(5-ethoxypentyl)imidazolium, 1,3-di(5-propoxypentyl)imidazolium, 1,3-bis(5-isopropoxypentyl)imidazolium, 1,3-bis(5-allyloxypentyl)imidazolium, 1,3-bis(5-butoxypentyl)imidazolium, 1,3-bis[5-(1-methylpropoxy)pentyl]imidazolium, 1,3-bis[5-(2-methylpropoxy)pentyl]imidazolium imidazolium, 1,3-bis[5-(1,1-dimethylethoxy)pentyl]imidazolium, 1,3-bis(5-pentyloxypentyl)imidazolium, 1,3-bis(5-neopentyloxypentyl)imidazolium, 1,3-bis(5-hexyloxypentyl)imidazolium, 1,3-bis(5-cyclohexyloxypentyl)imidazolium, 1,3-bis(5-heptyloxy)imidazolium imidazolium, 1,3-bis(6-methoxyhexyl)imidazolium, 1,3-bis(6-ethoxyhexyl)imidazolium, 1,3-bis(6-propoxyhexyl)imidazolium, 1,3-bis(6-isopropoxyhexyl)imidazolium, 1,3-bis(6-allyloxyhexyl)imidazolium, 1,3-bis(6-butoxyhexyl)imidazolium, 1,3-bis[6- imidazolium, 1,3-bis[6-(2-methylpropoxy)hexyl]imidazolium, 1,3-bis[6-(1,1-dimethylethoxy)hexyl]imidazolium, 1,3-bis(6-pentyloxyhexyl)imidazolium, 1,3-bis(6-neopentyloxyhexyl)imidazolium, 1,3-bis(6-hexyloxyhexyl)imidazolium, 1, 3-bis(6-cyclohexyloxyhexyl)imidazolium, 1,3-bis[(2-methoxycyclohexane-1-yl)methyl]imidazolium, 1,3-bis[(2-ethoxycyclohexane-1-yl)methyl]imidazolium, 1,3-bis[(2-propoxycyclohexane-1-yl)methyl]imidazolium, 1,3-bis[(2-isopropoxycyclohexane-1-yl)methyl]imidazolium imidazolium, 1,3-bis[(2-butoxycyclohexane-1-yl)methyl]imidazolium, 1,3-bis{[2-(1-methylpropoxy)cyclohexane-1-yl]methyl}imidazolium, 1,3-bis{[2-(2-methylpropoxy)cyclohexane-1-yl]methyl}imidazolium, 1,3-bis{[2-(1,1-dimethylethoxy)cyclohexane-1-yl]methyl}imidazolium ] methyl} imidazolium, 1,3-bis[(2-pentyloxycyclohexane-1-yl)methyl]imidazolium, 1,3-bis[(2-neopentyloxycyclohexane-1-yl)methyl]imidazolium, 1,3-bis(3-methylthiopropyl)imidazolium, 1,3-bis[2-(methylsulfonyl)ethyl]imidazolium, 1,3-bis[(thiophen-2-yl)methyl]imidazolium, 1,3-Bis(p-methoxyphenyl)imidazolium, 1,3-bis(p-ethoxyphenyl)imidazolium, 1,3-bis(3,4-methylenedioxyphenyl)imidazolium, 1,3-bis(3,4-methylenedioxybenzyl)imidazolium, 1,3-bis{(7-oxabicyclo[2,2,1]hept-2-yl)methyl}imidazolium, 1-methoxypropyl-3-methylthioimidazolium, 1,3-bis(3-methoxypropyl)-2-methylimidazolium, 1,3-bis(2-methyl 1,3-bis(3-methoxypropyl)imidazolium, 1,3-bis(3-ethoxypropyl)imidazolium, 1,3-bis(3-propoxypropyl)imidazolium, 1,3-bis(3-isopropoxypropyl)imidazolium, 1,3-bis(3-allyloxypropyl)imidazolium, 1,3-bis(3-butoxypropyl)imidazolium, 1,3-bis[3-(1-methylpropoxy)propyl]imidazolium, 1,3-bis[ 3-(2-methylpropoxy)propyl]imidazolium, 1,3-bis[3-(1,1-dimethylethoxy)propyl]imidazolium, 1,3-bis[(oxolan-2-yl)methyl]imidazolium, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium, 1,3-bis(3-methylthiopropyl)imidazolium, 1-methoxypropyl-3-methylthiopropylimidazolium, 1,3-bis(3-methoxypropyl)-2-methylimidazolium and 1,3-bis (2-methoxyethyl)-2-methylimidazolium; more preferably 1,3-bis(3-methoxypropyl)imidazolium, 1,3-bis(3-ethoxypropyl)imidazolium, 1-methoxypropyl-3-methylthioimidazolium, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium, 1,3-bis(2-methoxyethyl)-2-methylimidazolium and 1,3-bis(3-methoxypropyl)-2-methylimidazolium; however, the present invention is not limited thereto. ,

[0073] The onium salt represented by formula (1) is preferably an onium salt formed by a combination of a cation selected from the group consisting of 1,3-bis(2-methoxyethyl)imidazolium, 1,3-bis(3-methoxypropyl)imidazolium, 1,3-bis(3-ethoxypropyl)imidazolium, 1,3-bis(3-methylthiopropyl)imidazolium, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium, 1-methoxypropyl-3-methylthiopropylimidazolium, 1,3-bis(2-methoxyethyl)-2-methylimidazolium and 1,3-bis(3-methoxypropyl)-2-methylimidazolium and an anion selected from the group consisting of acetate ion, methoxyacetate ion, acrylate ion and methacrylate ion.

[0074] More specific examples of the onium salt represented by formula (1) include 1,3-bis(2-methoxyethyl)imidazolium acetate, 1,3-bis(3-methoxypropyl)imidazolium acetate, 1,3-bis(3-methoxypropyl)imidazolium acrylate, 1,3-bis(3-methoxypropyl)imidazolium methacrylate, 1,3-bis(3-ethoxypropyl)imidazolium acetate, 1-methoxypropyl-3-methylthioimidazolium acetate, 1,3-bis(3-methylthiopropyl)imidazolium acetate, 1,3-bis(2-methoxyethyl)-2-methylimidazolium acetate, 1,3-bis(2-methoxyethyl)-2-methylimidazolium acrylate, 1,3-bis(2-methoxyethyl)-2-methylimidazolium methacrylate, 1,3-bis(3-ethoxypropyl)imidazolium acetate, 1-methoxypropyl-3-methylthioimidazolium acetate, 1,3-bis(3-methylthiopropyl)imidazolium acetate. 3-bis(3-methoxypropyl)-2-methylimidazolium acetate, 1,3-bis(3-methoxypropyl)-2-methylimidazolium acrylate, 1,3-bis(3-methoxypropyl)-2-methylimidazolium methacrylate, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium acetate, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium acrylate, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium methacrylate, and the like; and preferably 1,3-bis(3-methoxypropyl)imidazolium acetate, 1,3-bis(3-methoxypropyl)imidazolium acrylate and 1,3-bis(3-methoxypropyl)imidazolium methacrylate; however, the present invention is not limited thereto.

[0075] The onium salt (1) of the present invention can be easily produced by a person skilled in the art according to the method described in the examples. The onium salt (1) can be obtained, for example, by the preparation method shown in the following reaction formula 1 (preparation method 1). Reaction 1:

[0076] In reaction formula 1, R 1 , R 2 , R 3 and R 4 Each is as defined above.

[0077] The preparation method 1 is described. 1 -NH 2 (Formula (6a)) and / or R 2 -NH 2 (Formula (6b)) represented by an amine compound, wherein R 3 -CHO (Formula (7)) and an aldehyde compound represented by R 4 The carboxylic acid represented by -COOH (Formula (4)) is reacted.

[0078] By R 1 -NH2 (Formula (6a)) or R 2 -NH 2Specific examples of the amine compound represented by the formula (6b) include 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-isopropoxyethylamine, 2-allyloxyethylamine, 2-butoxyethylamine, 2-(1-methylpropoxy)ethylamine, 2-(2-methylpropoxy)ethylamine, 2-(1,1-dimethylethoxy)ethylamine, 2-pentyloxyethylamine, 2-neopentyloxyethylamine, 2-hexyloxyethylamine, 2-phenoxyethylamine, 2-heptyloxyethylamine, 2-octyloxyethylamine, 2-nonyloxyethylamine, 2-decyloxyethylamine, 2-cyclopentyloxyethylamine, 2-cyclohexyloxyethylamine, 2-(2-ethylhex-1-yl)oxyethylamine, 2-(2,4,6 2-(benzyloxy)ethylamine, 2-(p-methoxybenzyloxy)ethylamine, 2-(2-methoxyethoxymethoxy)ethylamine, 2-(2-benzyloxyethoxy)ethylamine, 2-(dimethylamino)ethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-allyloxypropylamine, 3-isopropoxypropylamine, 3-(1-methylpropoxy)propylamine, 3-(2-methylpropoxy)propylamine, 3-(1,1-dimethylethoxy)propylamine, 3-butoxypropylamine, 3-pentyloxypropylamine, 3-neopentyloxypropylamine, 3-hexyloxypropylamine, 3-cyclohexyloxypropylamine, 3-heptyloxypropylamine, 3-octyloxypropylamine, 3-nonyloxypropylamine 4-(2-ethylhexyl)oxypropylamine, 3-(2,4,6-trimethylphenoxy)propylamine, 3-(2-methoxyethoxy)propylamine, 3-(dimethylamino)propylamine, 4-methoxybutylamine, 4-ethoxybutylamine, 4-propoxybutylamine, 4-isopropoxybutylamine, 4-allyloxybutylamine, 4-butoxybutylamine, 4-(1-methylpropoxy)butylamine, 4-(2-methylpropoxy)butylamine, 4-(1,1-dimethylethoxy)butylamine, 4-pentyloxybutylamine, 4-neopentyloxybutylamine, 4-hexyloxybutylamine, 4-cyclohexyloxybutylamine, 4-heptyloxybutylamine, 4-octyloxybutylamine, 4-(2-ethylhexyl-1-yl)oxy butylamine, 5-methoxypentylamine, 5-ethoxypentylamine, 5-propoxypentylamine, 5-isopropoxypentylamine, 5-allyloxypentylamine, 5-butoxypentylamine, 5-(1-methylpropoxy)pentylamine, 5-(2-methylpropoxy)pentylamine, 5-(1,1-dimethylethoxy)pentylamine, 5-pentyloxypentylamine, 5-neopentyloxypentylamine, 5-hexyloxypentylamine, 5-cyclohexyloxypentylamine, 5-heptyloxypentylamine, 6-methoxyhexylamine, 6-ethoxyhexylamine, 6-propoxyhexylamine, 6-isopropoxyhexylamine, 6-allyloxyhexylamine, 6-butoxyhexylamine, 6-(1-methylpropoxy)hexylamine, 6-(2-methylpropoxy)hexylamine, 6-(1,1-dimethylethoxy)pentylamine1-dimethylethoxy)hexylamine, 6-pentyloxyhexylamine, 6-neopentyloxyhexylamine, 6-hexyloxyhexylamine, 6-cyclohexyloxyhexylamine, 2-methoxycyclohexyl-1-methylamine, (2-propoxycyclohexane-1-yl)methylamine, (2-isopropoxycyclohexane-1-yl)methylamine, (2-butoxycyclohexyl-1-yl)methylamine, [2-(1-methylpropoxy)cyclohexane-1-yl]methylamine, [2-(2-methylpropoxy)cyclohexane-1-yl]methylamine, [2-(1,1-dimethylethoxy)cyclohexane-1-yl]methylamine, (2-pentyloxycyclohexane-1-yl)methylamine, (2-neopentyloxycyclohexane-1-yl)methylamine, 2-methylthioethylamine, 3-methylthiopropylamine, 1-(methoxymethyl)propylamine, (oxoheterocyclic 2-(pentan-2-yl)methylamine, (furan-2-yl)methylamine, 2-[(furan-2-yl)methylthio]ethylamine, 2-(methylsulfonyl)ethylamine, (thiophen-2-yl)methylamine, p-methoxyaniline, p-ethoxyaniline, 3,4-methylenedioxyaniline, 3,4-methylenedioxybenzylamine, (7-oxabicyclo[2,2,1]heptane-2-yl)methylamine, etc.; preferably 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-(2-methoxyethoxy)propylamine, 3-methylthiopropylamine and 3-(dimethylamino)propylamine; and more preferably 2-methoxyethylamine, 3-methoxypropylamine and 3-(2-methoxyethoxy)propylamine; however, the present invention is not limited thereto. By R, 1 -NH 2 or R 2 -NH 2 The amine compounds represented may be the same or different.

[0079] By R 3 Specific examples of the aldehyde compound represented by -CHO (formula (7)) include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, etc.; preferably formaldehyde and acetaldehyde; however, the present invention is not limited thereto. As formaldehyde, a cyclic oligomer or polymer capable of generating formaldehyde in the reaction system such as paraformaldehyde, trioxane and tetraoxane can be used.

[0080] As R 3 The aldehyde compound represented by -CHO (Formula (7)) can be used as it is in an aqueous solution or an alcohol solution such as methanol, butanol or 2-ethylhexanol.

[0081] By R 4Examples of the carboxylic acid represented by -COOH (formula (4)) include acetic acid, propionic acid, acrylic acid, propiolic acid, butyric acid, isobutyric acid, methacrylic acid, crotonic acid, tetracarboxylic acid, cyclopropylcarboxylic acid, valeric acid, isovaleric acid, pivalic acid, angelic acid, tiglic acid, cyclobutanecarboxylic acid, hexanoic acid, cyclopentanecarboxylic acid, heptanoic acid, sorbic acid, cyclohexanecarboxylic acid, benzoic acid, octanoic acid, 2-ethylhexylcarboxylic acid, toluic acid, 2-norbornylcarboxylic acid, nonanoic acid, cubic carboxylic acid, cinnamic acid, decanoic acid, 3-noradamantanecarboxylic acid, geranic acid, undecanoic acid, 1-naphthoic acid, 2-naphthoic acid, 1-adamantanecarboxylic acid and the like; preferably acetic acid, propionic acid, acrylic acid, propiolic acid, butyric acid, isobutyric acid, methacrylic acid, crotonic acid, tetracarboxylic acid, valeric acid, isovaleric acid and pivalic acid; and particularly preferably acetic acid, acrylic acid or methacrylic acid; however, the present invention is not limited thereto.

[0082] As glyoxal, an aqueous solution or an alcohol solution such as methanol, butanol or 2-ethylhexanol can be used as it is.

[0083] For R 1 -NH 2 (Formula (6a)) and R 2 -NH 2 The amount of the amine compound represented by (formula (6b)) used, R 1 -NH 2 and R 2 -NH 2 The total amount of is usually 0.1 to 10 mol, preferably 0.5 to 3 mol per mol of glyoxal. 1 and R 2 At the same time, the two amine compounds (R 1 -NH 2 and R 2 -NH 2 ) is not particularly limited, and R 1 -NH 2 With R 2 -NH 2 The ratio is 0:100 to 100:0. 1 -NH 2 With R 2 -NH 2 When the ratio is 0:100 or 100:0, R 1 =R 2 When R 1 -NH 2 With R 2 -NH 2When the ratio is not 0:100 or 100:0, the onium salt (1) obtained by the preparation method 1 is a mixture of compounds represented by the following formulae. The compounds represented by the following formulae (1′) and (1″) are both included in the onium salt represented by the formula (1), and the mixture can be used as an onium salt composition described later. If necessary, the mixture can be purified to form a desired single compound, which can then be used as the onium salt (1).

[0084]

[0085] As R 3 The aldehyde compound represented by -CHO (Formula (7)) can be used as it is in an aqueous solution or an alcohol solution such as methanol, butanol or 2-ethylhexanol. The amount of the aldehyde compound used is usually 0.1 to 10 mol, preferably 0.5 to 5 mol / mol of glyoxal.

[0086] R 4 The amount of the carboxylic acid represented by -COOH (Formula (4)) used is usually 0.1 to 10 mol, preferably 0.5 to 2 mol per mol of glyoxal.

[0087] In the preparation method 1, no solvent can be used. When a solvent is used, the solvent used is not particularly limited as long as it does not affect the reaction. Specific examples of the solvent include aromatic hydrocarbon solvents such as toluene, benzene and xylene; hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane and octane; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; alcohol solvents such as methanol, ethanol and 2-propanol; N,N-dimethylformamide, acetonitrile, water, etc.; and preferably alcohol solvents and water.

[0088] Further, the onium salt (1) prepared in advance can be used as a reaction solvent in production method 1. If necessary, two or more solvents can be used as a mixture. The amount of the solvent used is usually 50 parts by mass or less, and preferably 0.1 to 10 parts by mass per part by mass of glyoxal.

[0089] In the production method 1, the reaction can be carried out in an inert gas atmosphere which does not influence the reaction, such as nitrogen, argon or helium, if necessary.

[0090] When the preparation method 1 is carried out, the reaction pressure is generally atmospheric pressure; however, depending on the raw materials and solvent used, the reaction may be carried out by pressurizing the reaction system from atmospheric pressure to 1 MPa.

[0091] The reaction temperature varies depending on the starting material, solvent and the like used, and is usually -10°C or higher, and preferably 0°C to 100°C.

[0092] After completion of the reaction in Preparation Method 1, the onium salt (1) can be purified by a known purification method or can be not purified. Examples of the purification method include concentration, liquid separation, recrystallization, dialysis, adsorption, filtration and the like, but are not particularly limited thereto.

[0093] When the onium salt (1) obtained in the preparation method 1 is composed of R 4 -COO - When the anion represented by formula (2) is not the desired anion, an ion exchange reaction can be further performed to obtain the desired anion, if necessary. In this case, for example, the preparation method 3 described later can be preferably used. When the preparation method 3 is used, the onium salt (1) obtained in the preparation method 1 is used as the onium salt represented by formula (2) in the preparation method 3 to perform ion exchange, thereby producing the onium salt (1) having the desired anion.

[0094] Furthermore, the onium salt (1) can also be prepared by using a desired R 4 -COO - The anion is a cation of Y in the onium salt represented by the following formula (2) (hereinafter referred to as onium salt (2)). - Exchange (ion exchange) to obtain: Formula (2):

[0095] Where R 1 , R 2 and R 3 As defined above, and Y- represents any anion.

[0096] In formula (2), Y - Examples of include halogen anions such as chloride, bromide and iodide; hydroxide anions, carboxylate anions, sulfonate anions, thiocyanate anions, nitrate anions, perchlorate anions, etc., but are not particularly limited thereto. - When it is a carboxylate anion, it reacts with R in the onium salt (1) represented by the formula (1). 4 -COO - The anions are different.

[0097] Examples of the ion exchange method include a direct exchange method (preparation method 2) as shown in the following reaction formula 2. - When the anion is not a hydroxide anion, a method of ion exchange using a hydroxide salt (3) as shown in the following reaction formula 3 can also be used (production method 3). Reaction 2:

[0098] In reaction formula 2, R 1 , R2 , R 3 , R 4 and Y - Each is as defined above, n represents any natural number (preferably a natural number from 1 to 4, more preferably 1, 2 or 3), Z n+ represents any cation. Reaction 3:

[0099] In reaction formula 3, R 1 , R 2 , R 3 , R 4 and Y - As defined above, in reaction formula 3, Y in formula (2) - represents any anion except the hydroxide anion.

[0100] In reaction formula 2, Z n+ Examples of the cation represented by include alkali metal ions such as lithium cation, sodium cation and potassium cation; alkaline earth metal ions such as calcium cation; ammonium cation and the like, but are not particularly limited thereto.

[0101] Preparation method 3 is described. Production method 3 includes a reaction (hereinafter referred to as a first reaction) of subjecting an onium salt (2) represented by formula (2) to ion exchange using an ion exchange resin, silver (I) oxide, an alkali metal hydroxide, or the like to produce an onium hydroxide salt represented by formula (3) (hereinafter referred to as hydroxide salt (3)), and a reaction (hereinafter referred to as a second reaction) of subjecting the obtained hydroxide salt (3) to ion exchange with a carboxylic acid represented by formula (4) to obtain an onium salt (1).

[0102] The case of using an ion exchange resin in the first reaction (reaction 1-1) is described. The ion exchange resin used in reaction 1-1 can be, for example, a commercially available strong basic ion exchange resin (OH type) for water treatment or catalyst use. The amount of the ion exchange resin used is usually 20 molar equivalents or less per mole of the onium salt (2), preferably 1 to 10 molar equivalents.

[0103] Examples of the method of contacting the onium salt (2) with an ion exchange resin include a method of passing the onium salt (2) through a column filled with an ion exchange resin (Reaction 1-1-1), and a method of mixing the onium salt (2) with the ion exchange resin (Reaction 1-1-2).

[0104] In reaction 1-1, the onium salt (2) is usually diluted with a solvent and then contacted with an ion exchange resin. Examples of the solvent include acetone; alcohols such as methanol, ethanol and 2-propanol; acetonitrile, ethyl acetate, water and the like.

[0105] The amount of the solvent is not particularly limited. In the case of reaction 1-1-1, the amount of the solvent is generally 1 to 100 parts by mass, preferably 2 to 20 parts by mass, and more preferably 3 to 10 parts by mass per part by mass of the onium salt (2). In the case of reaction 1-1-2, the amount of the solvent is generally 10 parts by mass or less, preferably 1 to 10 parts by mass per part by mass of the onium salt (2).

[0106] The case of using silver (I) oxide in the first reaction (Reaction 1-2) is explained. The amount of silver (I) oxide used in Reaction 1-2 is usually 10 molar equivalents or less, preferably 0.5 to 2 molar equivalents per mole of the onium salt (2).

[0107] The case of using an alkali metal hydroxide in the first reaction (reaction 1-3) is described. Examples of the alkali metal hydroxide used in reaction 1-3 include sodium hydroxide, potassium hydroxide, etc. The amount of the alkali metal hydroxide used is usually 3 molar equivalents or less per mole of the onium salt (2).

[0108] Reactions 1-2 and 1-3 are usually carried out in a solvent. Examples of the solvent include acetone; alcohols such as methanol, ethanol and 2-propanol; acetonitrile, ethyl acetate, water, etc. The amount of the solvent is not particularly limited, but is usually 10 parts by mass or less, preferably 1 to 10 parts by mass, per part by mass of the onium salt (2).

[0109] The reaction temperature of the first reaction is generally 10°C or higher, preferably 10 to 60°C, and particularly preferably 10 to 30°C.

[0110] The reaction mixture obtained from the first reaction can be directly used in the second reaction, or the reaction solution can be filtered to remove insoluble substances and then used in the second reaction.

[0111] Examples of the hydroxide salt (3) obtained in the first reaction include those in which R of the onium salt represented by the formula (1) is 4 -COO - The anion is OH - Anion-substituted compound (compound represented by formula (3)). Specific examples include 1,3-bis(2-methoxyethyl)imidazolium hydroxide, 1,3-bis(3-methoxypropyl)imidazolium hydroxide, 1,3-bis(3-ethoxypropyl)imidazolium hydroxide, 1,3-bis(3-propoxypropyl)imidazolium hydroxide, 1,3-bis(3-isopropoxypropyl)imidazolium hydroxide, 1,3-bis(3-allyloxypropyl)imidazolium hydroxide, 1,3-bis(3-butyloxypropyl)imidazolium hydroxide, imidazolium hydroxide, 1,3-bis[3-(1-methylpropoxy)propyl]imidazolium hydroxide, 1,3-bis[3-(2-methylpropoxy)propyl]imidazolium hydroxide, 1,3-bis[3-(1,1-dimethylethoxy)propyl]imidazolium hydroxide, 1,3-bis[(oxolan-2-yl)methyl]imidazolium hydroxide, 1,3-bis[3-(2-methoxyethoxy)propyl] imidazolium hydroxide, 1,3-bis(3-methylthiopropyl)imidazolium hydroxide, 1-methoxypropyl-3-methylthiopropylimidazolium hydroxide, 1,3-bis(3-methoxypropyl)-2-methylimidazolium hydroxide, 1,3-bis(2-methoxyethyl)-2-methylimidazolium hydroxide, and the like; and preferably 1,3-bis(2-methoxyethyl)imidazolium hydroxide, 1,3-bis(3-methoxypropyl) imidazolium hydroxide, 1,3-bis(3-ethoxypropyl)imidazolium hydroxide, 1-methoxypropyl-3-methylthioimidazolium hydroxide, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium hydroxide, 1,3-bis(2-methoxyethyl)-2-methylimidazolium hydroxide and 1,3-bis(3-methoxypropyl)-2-methylimidazolium hydroxide; however, the present invention is not limited thereto.

[0112] Next, the second reaction is described. In the second reaction, the carboxylic acid represented by formula (4) can be the same as the carboxylic acid in preparation method 1. The amount of the carboxylic acid represented by formula (4) used in the second reaction is generally 0.8 molar equivalents or more per mole of the hydroxide salt (3) represented by formula (3), preferably 0.8 to 1.2 molar equivalents, particularly preferably 0.9 to 1.1 molar equivalents.

[0113] The second reaction is usually carried out in a solvent. Examples of the solvent include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and 2-propanol; acetonitrile, ethyl acetate, tetrahydrofuran, dimethylformamide, water, etc. The amount of the solvent is not particularly limited, but is usually 10 parts by mass or less, preferably 1 to 10 parts by mass, per part by mass of the hydroxide salt (3).

[0114] The reaction temperature of the second reaction is generally 10°C or higher, preferably 10 to 60°C, and particularly preferably 10 to 30°C.

[0115] After the second reaction is completed, for example, the obtained reaction mixture can be concentrated to obtain an onium salt (1). The obtained onium salt (1) can be purified by a known purification method, or can be not purified. Examples of the purification method include concentration, liquid separation, recrystallization, dialysis, adsorption, filtration, etc., but are not particularly limited thereto.

[0116] The onium salt (2) can be obtained, for example, by the preparation method shown in the following reaction formula 4 (Preparation method 4). Reaction 4:

[0117] In reaction formula 4, R 1 , R 2 , R 3 and Y - Each is as defined above.

[0118] In preparation method 4, glyoxal, R 1 -NH 2 (Formula (6a)) and / or R 2 -NH 2 (Formula (6b)) represented by an amine compound, wherein R 3 -CHO (Formula (7)) and an aldehyde compound represented by H + Y - (Formula (8)) represents the acid reaction. In addition to the use of H + Y - (Formula (8)) represents an acid instead of R 4 Except for the carboxylic acid represented by -COOH (Formula (4)), the preparation method 4 can be carried out in the same manner as the preparation method 1. 1 -NH 2 (Formula (6a)) or R 2 -NH 2 (An amine compound represented by (Formula (6b)), R 3 The aldehyde compound represented by -CHO (Formula (7)), reaction pressure, reaction temperature, post-treatment after the reaction, purification method, etc. are the same as those in Preparation Method 1. In addition, as in Preparation Method 1, if necessary, the reaction can be carried out in an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon or helium.

[0119] By H + Y - Examples of the acid represented by (Formula (8)) include hydrogen halides such as hydrogen chloride, hydrogen bromide and hydrogen iodide; carboxylic acids, sulfonic acids, thiocyanic acid, nitric acid, perchloric acid, etc. Such acids can be used in Preparation Method 4 even in the form of aqueous solutions or organic solvent solutions.

[0120] When Y in the onium salt (2) - When it is a halogen anion, it can also be prepared by the preparation method shown in the following reaction formula 5 (Preparation method 5). Reaction 5:

[0121] In reaction formula 5, R 1 To R 3 As defined above, Y is a halogen atom, Y - It is a halogen anion.

[0122] In Reaction Formula 5, examples of the halogen atom represented by Y include chlorine, bromine and iodine atoms, and examples of the halogen atom represented by Y include chlorine, bromine and iodine anions, but are not particularly limited thereto.

[0123] In one embodiment of the present invention, the onium salt composition contains two or more onium salts (1).

[0124] Hereinafter, the cation of the onium salt represented by formula (1) is referred to as “imidazolium cation (C + )”, and the anion of the onium salt represented by formula (1) is referred to as “carboxylate anion (A - The onium salt composition can contain two or more imidazolium cations (C + ) and two or more carboxylate anions (A - ), can contain two or more imidazolium cations (C + ) and a carboxylate anion (A - ), or may contain an imidazolium cation (C + ) and two or more carboxylate anions (A - ).

[0125] The onium salt composition can be prepared, for example, by mixing two or more onium salts (1). Examples of the method of mixing two or more onium salts (1) include direct mixing at any temperature, and salt exchange using a cosolvent, by dialysis or using an ion exchange resin, etc., but are not particularly limited thereto.

[0126] Furthermore, for example, two or more onium salts (1) can be prepared by the following method (i) or (ii) to obtain an onium salt composition. (i) In preparation method 1, the reaction is carried out by any one or a combination of the following (a), (b) and (c): (a) Use the 1 -NH 2 and R 2 -NH 2 (Different from R 1 and R2 ) as the amine compound, (b) Use of 3 -CHO as the aldehyde compound, (c) Use of two or more 4 As the carboxylic acid, a carboxylic acid represented by -COOH(4) (ii) In the preparation method 1, the onium salt (1) prepared in advance is used as a reaction solvent, and the onium salt (1) as a reaction solvent is not removed after the reaction is completed. In this case, the onium salt (1) prepared in advance is different from the onium salt (1) obtained by the preparation method 1 using the onium salt (1) prepared in advance as a solvent.

[0127] The polysaccharide in the present invention is a substance composed of a large number of monosaccharide molecules polymerized by glycosidic bonds. Examples of the monosaccharide molecules include glucose, fructose, glucosamine, N-acetylglucosamine, etc. Glucose-derived polysaccharides include glycogen, starch, cellulose, dextrin and curdlan, fructose-derived polysaccharides include levan, and glucose-derived polysaccharides include chitin and chitosan. In particular, poorly soluble cellulose, curdlan, chitin, chitosan, etc. are suitable for the present invention.

[0128] Cellulose refers to glucose polymers polymerized by β-1,4-glucose bonds and their derivatives. The degree of polymerization of glucose in cellulose is not particularly limited, but is preferably 200 or higher. Examples of derivatives include carboxymethyl, hydroformylation and esterification derivatives. Cellulose may also contain cellooligosaccharides and cellobiose, which are partial decomposition products of cellulose. In addition, cellulose may be a composite material with β-glucoside (glycoside), lignocellulose of lignin and / or hemicellulose, or a composite material with pectin, etc. The onium salt described in the present invention can dissolve cellulose at 10°C to 50°C, even if it is lignocellulose or a composite with pectin, etc. Cellulose may be crystalline cellulose or non-crystalline cellulose, but preferably crystalline cellulose. In addition, cellulose may be naturally derived or artificially synthesized. The source of cellulose is also not limited. Cellulose may be of plant, fungal or bacterial origin.

[0129] Cellulose also includes cellulose-containing materials. Specific examples of cellulose-containing materials include pulp, natural fibers such as cotton and hemp, regenerated fibers such as rayon, copper and acetate, straw and other types of stalks, agricultural wastes such as bagasse and wood chips, and biomass including waste paper, construction waste and other various wastes. When various wastes such as pulp, cotton, hemp and other natural fibers, rayon, copper, acetate and other regenerated fibers, straw and other types of stalks, bagasse, wood chips and other agricultural wastes, waste paper and other biomass, construction waste and other wastes are dissolved in the onium salt of the present invention, it is preferred to use slices of these materials to shorten the time required for dissolution.

[0130] Curdlan is an almost pure linear polymer of glucose polymerized by β-1,3-glucose bonds. Curdlan is produced from glucose by Agrobacterium sp. and is used as a food additive, primarily as a gelling agent, stabilizer and thickener.

[0131] Chitin is a polymer of N-acetyl-D-glucosamine, which is polymerized by β-1,4-glycosidic bonds. It is a component of the exoskeleton of arthropods, especially the shells of crustaceans, the shells of molluscs, especially the shells of shellfish, and the cell walls of fungi (molds) and basidiomycetes (molds), and is the second most abundant natural product after cellulose. Chitin as a natural product is a polysaccharide containing not only N-acetylglucosamine but also glucosamine as a component, and the ratio of N-acetylglucosamine to glucosamine is said to be about 9:1.

[0132] Chitosan is a deacetylated product of chitin and a cationic polysaccharide containing primary amino groups.

[0133] The polysaccharide-containing liquid composition of the present invention contains a polysaccharide and an onium salt (1) or an onium salt composition, and the polysaccharide is dissolved in the onium salt (1) or the onium salt composition. The liquid composition consisting of the polysaccharide and the onium salt (1) or the onium salt composition is referred to as a polysaccharide-containing liquid composition (a1).

[0134] In addition, the liquid composition (a1) containing polysaccharides can contain an organic solvent. When an organic solvent is included, it is referred to as a liquid composition (a2) containing polysaccharides. Examples of the organic solvent include dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, pyridine, methylimidazole, 3-methoxy-2-propanol, hexamethylphosphoric acid triamide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, etc., but are not particularly limited thereto. Two or more organic solvents may be included. The liquid composition (a2) containing polysaccharides is formed by dissolving polysaccharides in a medium containing the onium salt (1) or an onium salt composition and the organic solvent. The above-mentioned organic solvent itself hardly dissolves polysaccharides; however, when mixed with the onium salt (1) or the onium salt composition, it can help to increase the solubility of the polysaccharide, accelerate the dissolution rate of the polysaccharide by reducing the viscosity, improve the processability during the polysaccharide recovery process, and control the physical properties of the recovered polysaccharide.

[0135] The ratio of the onium salt (1) or the onium salt composition to the organic solvent in the polysaccharide-containing liquid composition (a2) medium {(mass of onium salt (1) or onium salt composition) / [(mass of onium salt (1) or onium salt composition)+mass of organic solvent]×100} is usually 0.5 to 99.5% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.

[0136] The polysaccharide-containing liquid composition (a1) or (a2) can contain a known onium salt other than the onium salt (1). Specific examples of such known onium salts other than the onium salt (1) include 1-ethyl-3-methylimidazolium acetate, etc., but are not particularly limited thereto.

[0137] In the liquid composition (a1) or (a2) containing polysaccharide, additives can be used to their effective extent. The example of additives includes spices, dyes, color pigments, water repellents, oil repellents, antioxidants, hydrolysis inhibitors, flame retardants, ultraviolet light absorbers, light stabilizers, antistatic agents, conductive agents, stress relievers, mold release agents, crystallization promoters, lubricants, impact agents, sliding properties modifiers, nucleating agents, reinforcing agents, reinforcing agents, flow regulators, thickeners, antibacterial agents, antifungal agents, rust inhibitors, anti-settling agents, anti-sagging agents, defoamers, coupling agents, fillers, etc. These additives can be used alone or in combination of two or more.

[0138] When the polysaccharide-containing liquid composition (a1) contains not only the polysaccharide and the onium salt (1) or the onium salt combination but also optionally contains a known onium salt and additives, it is referred to as a polysaccharide-containing liquid composition (a3).

[0139] When the polysaccharide-containing liquid composition (a2) contains not only the polysaccharide, the onium salt (1) or the onium salt combination and the organic solvent but also optionally contains a known onium salt and additives, it is referred to as a polysaccharide-containing liquid composition (a4).

[0140] In the polysaccharide-containing liquid compositions (a1) to (a4), the ratio of the onium salt (1) or the onium salt composition in the medium {(mass of the onium salt (1) or the onium salt composition) / [(mass of the onium salt (1) or the onium salt composition) + mass of the organic solvent + mass of the known onium salt + mass of the additive] × 100} is generally 0.5 to 99.5% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.

[0141] Next, the polysaccharide dissolving method of the present invention is described. First, a medium containing an onium salt (1) or an onium salt composition and optionally an organic solvent, a known onium salt and an additive is mixed with a polysaccharide to dissolve, thereby obtaining any polysaccharide-containing liquid composition (a1) to (a4).

[0142] The temperature at which the polysaccharide is dissolved in the medium is not particularly limited as long as it is within the temperature range at which the medium is liquid and sufficient to keep the liquid at a specific temperature. The temperature is preferably 100°C or lower, more preferably 10°C or higher and 50°C or lower.

[0143] In the step of dissolving the polysaccharide in the medium, the dissolution of the polysaccharide may be promoted by adding stimulation, such as stirring, shaking or ultrasonic irradiation, to the mixture of the polysaccharide and the medium.

[0144] The content ratio of the polysaccharide in the polysaccharide-containing liquid composition (a1) and (a4) [{polysaccharide mass / (polysaccharide-containing liquid composition (a1) and (a4))}×100] is not particularly limited, and is generally 0.5 to 99.5% by mass, preferably 1 to 50% by mass, and more preferably 5 to 30% by mass.

[0145] When the polysaccharide in the polysaccharide-containing liquid compositions (a1) to (a4) is cellulose, the medium other than cellulose can dissolve the cellulose by stirring at 25°C, preferably with a solubility of 10% by mass or more, more preferably 14% by mass or more, even more preferably 18% by mass or more, and particularly preferably 20% by mass or more.

[0146] The higher the solubility of cellulose, the better; however, the solubility under stirring at 25° C. is generally 50% by mass or less, 45% by mass or less, or 40% by mass or less. The solubility can be measured, for example, by stirring for 24 hours using Avicel (registered trademark) PH-101 (microcrystalline cellulose) manufactured by Sigma-Aldrich.

[0147] When the polysaccharide in the polysaccharide-containing liquid composition (a1) to (a4) is curd polysaccharide, the medium other than curd polysaccharide can be stirred to dissolve the curd polysaccharide at 50°C, preferably with a solubility of 10% by mass or more, more preferably 14% by mass or more, even more preferably 18% by mass or more, and particularly preferably 20% by mass or more.

[0148] When the polysaccharide in the polysaccharide-containing liquid compositions (a1) to (a4) is chitosan, the medium other than chitosan can dissolve chitosan by stirring at 50°C, preferably with a solubility of 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

[0149] In the step of dissolving the polysaccharide in the medium, there is no particular restriction on the order of dissolving the polysaccharide, the onium salt (1) and other optional components, i.e., known onium salts, organic solvents and additives. The known onium salts, organic solvents or additives can be mixed before the polysaccharide is dissolved in the onium salt (1) or the onium salt composition, or can be mixed during or after the polysaccharide is dissolved in the onium salt (1) or the onium salt composition.

[0150] In the present invention, "recovery of polysaccharide" means extracting polysaccharide or polysaccharide derivatives from any of the polysaccharide-containing liquid compositions (a1) to (a4) as a composition in an industrially useful form. For example, as a form of polysaccharide, it can be extracted as recycled fiber, nanofiber, film, etc., but is not particularly limited thereto.

[0151] In addition, chemical and physical treatments can be performed in the polysaccharide-containing liquid composition (a1) to (a4) to modify the polysaccharide or cleave the polysaccharide chain to make the recovered composition functional. These treatments can be performed before or during the recovery of the polysaccharide from the polysaccharide-containing liquid composition (a1) to (a4). Examples of chemical and physical treatments include oxidation, reduction, pyrolysis, hydrolysis, isomerization, esterification, alkoxylation, acetylation, deacetylation, ion exchange, copolymerization, surface coating, saccharification, shearing and application of voltage. Examples of recovered compositions with functional groups include, but are not particularly limited to, cellulose-saccharification compositions for biomass fuel production, composite compositions with organic / inorganic materials, and the like.

[0152] It is not necessary to completely remove the onium salt (1) or onium salt composition used for dissolution from the recovered polysaccharide or polysaccharide derivative. The recovered composition can be used while the onium salt (1) or onium salt composition remains therein.

[0153] Next, the polysaccharide recovery method of the present invention is described. Any one of the polysaccharide-containing liquid compositions (a1) to (a4) obtained by the above method can be brought into contact with a poor solvent to precipitate the polysaccharide in the mixed solution. The precipitated polysaccharide and the mixed solution are separated by filtration, etc., thereby recovering the polysaccharide. The mixed solution from which the polysaccharide is separated contains the onium salt (1) or the onium salt composition and the poor solvent. In addition, when a known onium salt, organic solvent or additive is used, a mixed solution from which the polysaccharide is separated (hereinafter, the mixed solution from which the polysaccharide is separated is referred to as "mixed solution").

[0154] Examples of the poor solvent for recovering polysaccharides include water, methanol, ethanol, acetone, and a mixed solvent of two or more thereof, but are not particularly limited thereto. The amount of the poor solvent used is not particularly limited, as long as its amount is sufficient to recover the polysaccharide from any of the polysaccharide-containing liquid compositions (a1) to (a4). Those skilled in the art will be able to determine the appropriate amount used.

[0155] The method for contacting the polysaccharide-containing liquid composition (a1) to (a4) with a poor solvent is not particularly limited. Examples include a method of dropping a poor solvent into any of the polysaccharide-containing liquid compositions (a1) to (a4), a method of placing any of the polysaccharide-containing liquid compositions (a1) to (a4) in a mold or applying to a sheet and then immersing the sheet in the poor solvent, and a method of spraying any of the polysaccharide-containing liquid compositions (a1) to (a4) into a poor solvent.

[0156] The onium salt (1) or the onium salt composition can be recovered from the mixed solution and reused. For reuse, the recovered onium salt (1) or the onium salt composition can contain polysaccharide-derived components. If necessary, the polysaccharide-derived components can be removed from the recovered onium salt (1) or the onium salt composition by purification. Examples of methods for recovering the onium salt (1) or the onium salt composition from the separated mixed solution include concentration, liquid separation, recrystallization, dialysis, adsorption, filtration, etc., but are not particularly limited thereto.

[0157] Furthermore, the organic solvent and the poor solvent used for dissolving the polysaccharide can be easily recovered from the mixed solution by distillation, concentration, liquid separation, etc., and reused. Example

[0158] The present invention is described in detail below based on Examples; however, the present invention is not limited thereto.

[0159] In Table 1, "solubility" indicates the maximum mass % of the polysaccharide dissolved in the onium salt [(maximum mass of the polysaccharide dissolved in the onium salt / mass of the onium salt)×100].

[0160] In Table 2, "onium salt concentration" indicates the mass % of the onium salt relative to the mixed medium of the onium salt and the organic solvent [(mass of the onium salt / mass of the mixed medium of the onium salt and the organic solvent)×100].

[0161] Further, in Table 2, "solubility" represents the mass % of the polysaccharide dissolved in the mixed medium of the onium salt and the organic solvent or the organic solvent [(mass of the polysaccharide dissolved in the mixed medium of the onium salt and the organic solvent or the organic solvent / mass of the mixed medium of the onium salt and the organic solvent or the organic solvent)×100].

[0162] In the examples, the dissolution state of the polysaccharide was evaluated using a zoom stereo microscope and a polarization observation lens filter manufactured by Wraymer Co. The polysaccharide-containing liquid component (a1) or (a2) was observed using this microscope, and if no undissolved polysaccharide showed birefringence, it was judged to be in a completely dissolved state.

[0163] Example 1-1 260 g (3.22 mol) of 37 wt% aqueous formaldehyde solution (produced by Tokyo Chemical Industry Co., Ltd.), 290 g (4.83 mol) of acetic acid (produced by Junsei Chemical Co., Ltd.), 573 g (6.43 mol) of 3-methoxypropylamine (produced by Tokyo Chemical Industry Co., Ltd.) and 461 g (3.22 mol) of 40 wt% aqueous glyoxal solution (produced by Tokyo Chemical Industry Co., Ltd.) were placed in a 5 L three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 811 g of 1,3-bis(3-methoxypropyl)imidazolium acetate ([(Me OPr) 2 Im][AcO]). The yield is 93%. [(MeOPr) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.41(s,1H),7.78(d,2H),4.22(t,4H),3.33(t,4H),3.22(s,6H),2.07-2.00(m,4H),1.56(s,3H)

[0164] Example 1-2 4.11 g (50.8 mmol) of 37 wt%, 4.55 g (75.8 mmol) of acetic acid (manufactured by Junsei Chemical Co., Ltd.), 12.9 g (96.7 mmol) of 3-(2-methoxyethoxy)propylamine (manufactured by Combi-Blocks) and 7.24 g (50.5 mmol) of 40 wt% aqueous glyoxal solution (manufactured by Junsei Chemical Co., Ltd.) were placed in a 100 mL three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 13.9 g of 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium acetate ([(MeOEtOPr) 2 Im][AcO]). The yield is 80%. [(MeOEtOPr) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.42(s,1H),7.80(d,2H),4.23(t,4H),3.49-3.47(m,4H),3.44-3.40(m,8H),3.25(s,6H),2.08-2.01(m,4H),1.52(s,3H)

[0165] Examples 1-3 40 g of a strongly basic ion exchange resin (manufactured by Fuji Wako Pure Chemicals, Inc., DOWEX (registered trademark) MONOSPHERE 550A (OH)) was mixed with ion exchange water, and the mixture was filled in a column tube. 14.0 g of [(MeOPr)] obtained in Example 1-1 was added to the column tube. 2 Im][AcO] was dissolved in ion exchange water to prepare a 0.6 M aqueous solution. The aqueous solution was passed through a column filled with an ion exchange resin, and then 120 g of ion exchange water was passed through the column to obtain 204 g of 1,3-bis(3-methoxypropyl)imidazolium hydroxide ([(MeOPr) 2 Im]OH) aqueous solution. To the obtained [(MeOPr) 2 35.3 g of a 10 wt% acrylic acid aqueous solution (produced by Tokyo Chemical Industry Co., Ltd.) prepared in advance was added to the 1,3-bis(3-methoxypropyl)imidazolium acrylic acid ([(MeOPr) 2 Im][Acr]). The yield was 98%. [(MeOPr) 2 Im][OH] 1 The H NMR data results are shown below. 1 H NMR (D 2 O)δ(ppm)=7.5(s,2H),4.28(t,4H),3.47(t,4H),3.31(s,6H),2.13(m,4H) [(MeOPr) 2 Im][Acr] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.72(s,1H),7.83(d,2H),5.93(dd,1H),5.62(dd,1H),5.09(dd,1H),4.25(t,4H),3.33(t,4H),3.21(s,6H),2.08-2.01(m,4H)

[0166] Examples 1-4 1.86 g (23.0 mmol) of 37 wt% aqueous formaldehyde solution (produced by Tokyo Chemical Industry Co., Ltd.), 2.34 g (38.9 mmol) of acetic acid (produced by Junsei Chemical Co., Ltd.), 3.64 g (48.5 mmol) of 2-methoxyethylamine (produced by Tokyo Chemical Industry Co., Ltd.) and 3.59 g (24.9 mmol) of 40 wt% aqueous glyoxal solution (produced by Junsei Chemical Co., Ltd.) were placed in a 30 mL three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 5.03 g of 1,3-bis(2-methoxyethyl)imidazolium acetate ([(MeOEt) 2 Im][AcO]). The yield is 89%. [(MeOEt) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.44(s,1H),7.78(s,2H),4.39(t,4H),3.70(t,4H),3.27(s,6H),1.53(s,3H)

[0167] Example 2-1 6.46 g (79.8 mmol) of a 37 wt% aqueous formaldehyde solution (produced by Tokyo Chemical Industry Co., Ltd.), 7.02 g (117 mmol) of acetic acid (produced by Junsei Chemical Co., Ltd.), 16.5 g (160 mmol) of 3-ethoxypropylamine (produced by Tokyo Chemical Industry Co., Ltd.) and 11.8 g (81.8 mmol) of a 40 wt% aqueous glyoxal solution (produced by Junsei Chemical Co., Ltd.) were placed in a 100 mL three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 17.7 g of 1,3-bis(3-ethoxypropyl)imidazolium acetate ([(EtOPr) 2 Im][AcO]). The yield is 74%. [(EtOPr) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.97(s,1H),7.86(d,2H),4.25(t,4H),3.39-3.34(m,8H),2.06-2.00(m,4H),1.56(s,3H),1.07(t,6H)

[0168] Example 2-2 7.19 g (88.8 mmol) of a 37 wt% aqueous formaldehyde solution (produced by Tokyo Chemical Industry Co., Ltd.), 8.09 g (135 mmol) of acetic acid (produced by Junsei Chemical Co., Ltd.), 8.19 g (91.9 mmol) of 3-methoxypropylamine (produced by Tokyo Chemical Industry Co., Ltd.), 9.17 g (88.8 mmol) of 3-ethoxypropylamine (produced by Kanto Chemical Co., Ltd.) and 12.9 g (89.3 mmol) of a 40 wt% aqueous glyoxal solution (produced by Junsei Chemical Co., Ltd.) were placed in a 180 mL three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 21.7 g of 1-(3-ethoxypropyl)-3-(3-methoxypropyl)imidazolium acetate ([(EtOPr)(MeOPr)Im][AcO]), [(MeOPr) 2 Im][AcO] and [(EtOPr) 2 Im][AcO]([(EtOPr / MeOPr) 2 The yield was 88%. [(EtOPr / MeOPr) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.75(s,1H),7.82(d,2H),4.24(t,4H),3.40-3.31(m,6H),3.21(s,3H),2.07-2.00(m,4H),1.58(s,3H),1.07(t,3H)

[0169] Example 2-3 5.63 g (69.6 mmol) of a 37 wt% aqueous formaldehyde solution (produced by Tokyo Chemical Industry Co., Ltd.), 6.17 g (103 mmol) of acetic acid (produced by Junsei Chemical Co., Ltd.), 17.9 g (136 mmol) of 3-butoxypropylamine (produced by Tokyo Chemical Industry Co., Ltd.) and 9.85 g (68.4 mmol) of a 40 wt% aqueous glyoxal solution (produced by Junsei Chemical Co., Ltd.) were placed in a 180 mL three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 17.1 g of 1,3-bis(3-butoxypropyl)imidazolium acetate ([(BuOPr) 2 Im][AcO]). The yield is 70%. [(BuOPr) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.53(s,1H),7.80(d,2H),4.23(t,4H),3.37(t,4H),3.33(t,4H),2.0 7-2.00(m,4H),1.56(s,3H),1.48-1.41(m,4H),1.33-1.24(m,4H),0.87(t,6H)

[0170] Embodiment 2-4 In the same manner as in Example 1-4, 13.0 g of 1,3-bis(3-methoxypropyl)imidazolium propionate ([(MeOPr) 2 Im][PrO]), except that 35.3 g of a 10 wt% aqueous solution of acrylic acid (produced by Tokyo Chemical Industry Co., Ltd.) in Example 1-3 was replaced by 36.9 g of a 10 wt% aqueous solution of propionic acid (produced by Junsei Chemical Co., Ltd.). The yield was 87%. 1 H NMR (CDCl 3 )δ(ppm)=11.91(s,1H),7.10(d,2H),4.43(t,4H),3.39(t,4H),3.29(t,6H),2.26-2.20(m,2H),2.19-2.12(m,4H),1.15-1.10(m,3H)

[0171] Embodiment 2-5 In the same manner as in Example 1-4, 15.0 g of 1,3-bis(3-methoxypropyl)imidazolium methacrylate ([(MeOPr) 2 Im][MeAcr]), except that 35.3 g of 10 wt% acrylic acid (produced by Tokyo Chemical Industry Co., Ltd.) aqueous solution in Example 1-3 was replaced by 42.4 g of 10 wt% methacrylic acid (produced by Tokyo Chemical Industry Co., Ltd.) aqueous solution. The yield was 97%. [(MeOPr) 2 Im][MeAcr] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.72(s,1H),7.83(d,2H),5.43-5.42(m,1H),4.85-4.83(m,1H) ,4.25(t,4H),3.33(t,4H),3.22(s,6H),2.08-2.01(m,4H),1.73(dd,3H)

[0172] Embodiment 2-6 6.70 g (82.8 mmol) of a 37 wt% aqueous formaldehyde solution (produced by Tokyo Chemical Industry Co., Ltd.), 7.64 g (127 mmol) of acetic acid (produced by Junsei Chemical Co., Ltd.), 17.3 g (165 mmol) of 3-methylthiopropylamine (produced by Tokyo Chemical Industry Co., Ltd.) and 12.3 g (85.5 mmol) of a 40 wt% aqueous glyoxal solution (produced by Junsei Chemical Co., Ltd.) were placed in a 100 mL three-necked reactor purged with nitrogen. The resulting mixture was heated to 40° C. and stirred for 3 hours to synthesize 19.3 g of 1,3-bis(3-methylthiopropyl)imidazolium acetate ([(MeSPr) 2 Im][AcO]). The yield is 77%. [(MeSPr) 2 Im][AcO] 1 The H NMR data results are shown below. 1 H NMR (DMSO-d 6 )δ(ppm)=9.93(s,1H),7.87(d,2H),4.27(t,4H),2.46(t,4H),2.09-2.04(m,4H),2.04(s,6H),1.59(s,3H)

[0173] Evaluation Example 1-1 1.00 g [(MeOPr) 2 Im][AcO] was placed in a sample tube and maintained at 25 °C. Microcrystalline cellulose (Avicel (registered trademark) PH-101, manufactured by Sigma-Aldrich) was added in 0.01 g increments at 25°C and stirred. This operation was repeated until the microcrystalline cellulose was no longer completely dissolved after 10 minutes to 24 hours. The solubility results are shown in Table 1.

[0174] Evaluation Examples 1-2, 1-3 and 2-1 to 2-3 and Comparative Example 1-1 The same operation as in Evaluation Example 1-1 was performed except that the onium salt of Evaluation Example 1-1 was changed to the onium salt listed in Table 1. The results of solubility are shown in Table 1. 1-Ethyl-3-methylimidazolium acetate used in Comparative Example 1-1 was produced by Tokyo Chemical Industry Co., Ltd.

[0175] Table 1

[0176] The onium salts shown in Evaluation Examples 1-1 to 1-3 and 2-1 to 2-3 showed excellent cellulose solubility at 25° C., compared with the onium salt shown in Comparative Example 1-1.

[0177] Evaluation Examples 1-4 0.63 g of [(MeOPr) 2 1m][AcO] and 0.44g of dimethyl sulfoxide (hereinafter abbreviated as DMSO) were placed in a sample tube to prepare a mixture. The same operation as in Evaluation Example 1-1 was performed except that the onium salt of Evaluation Example 1-1 was changed to 1.0g of the mixture. The results of solubility are shown in Table 2.

[0178] Evaluation of Examples 1-5 and 2-4 to 2-6 The same operation as in Evaluation Example 1-4 was performed except that the onium salt of Evaluation Example 1-4 was changed to the onium salt listed in Table 2. The results of solubility are shown in Table 2.

[0179] Comparative Example 1-2 The same operation as in Evaluation Example 1-4 was performed except that the mixture of Evaluation Example 1-4 was changed to DMSO.

[0180] Table 2

[0181] Evaluation Examples 2-7 1.00 g [(MeOPr) 2 Im][AcO] was placed in a sample tube and maintained at 50 °C. Curdlan (produced by Fuji Wako Pure Chemicals Co., Ltd.) was added in 0.01 g increments at 50°C and stirred. This operation was repeated until the curdlan was no longer completely dissolved after 10 minutes to 24 hours. The results of solubility are shown in Table 3.

[0182] Table 3

[0183] The onium salts shown in Evaluation Examples 2-7 showed excellent curdlan solubility at 0°C.

[0184] Evaluation Examples 2-8 1.00 g [(MeOPr) 2 Im][AcO] was placed in a sample tube and maintained at 50 °C. Chitosan (produced by Fuji Wako Pure Chemicals Co., Ltd.) was added in 0.01 g increments at 50°C and stirred. This operation was repeated until chitosan was no longer completely dissolved after 10 minutes to 24 hours. The results of solubility are shown in Table 4.

[0185] Comparative Example 2-1 The same operation as in Evaluation Example 2-8 was performed except that the onium salt of Evaluation Example 2-8 was changed to the onium salt listed in Table 4. The results of solubility are shown in Table 4.

[0186] Table 4

[0187] The onium salt shown in Evaluation Example 2-8 showed excellent chitin solubility at 50° C. compared to the onium salt shown in Comparative Example 2-1.

[0188] Evaluation Examples 1-6 2.00 g [(MeOPr) 2 Im][AcO] and 0.20 g of microcrystalline cellulose were placed in a sample tube and stirred at 25° C. to prepare a cellulose-containing liquid composition. The cellulose-containing liquid composition was placed in a plastic syringe and extruded into a water bath at 15 to 20° C., followed by washing and drying, thereby confirming that fibrous cellulose could be recovered.

[0189] Evaluation Examples 2-9 10.00 g [(MeOPr) 2 1M [AcO] and 2.00 g of microcrystalline cellulose were placed in a sample tube and stirred at 25° C. to prepare a cellulose-containing liquid composition. The cellulose-containing liquid composition was applied to a glass plate and applied to a hot plate heated to 60° C. with an applicator. The applied cellulose-containing liquid composition was placed in a water bath at 15 to 20° C. together with the glass plate, followed by washing and drying, thereby confirming that film-like cellulose could be recovered. Industrial Applicability

[0190] According to the present invention, an onium salt having a very high solubility for polysaccharides at a temperature of 10 to 50° C., particularly at about room temperature (25° C.), can be provided. A liquid composition comprising the onium salt and polysaccharides as a composition suitable for recovering polysaccharides, and a method for effectively recovering polysaccharides using such a liquid composition comprising the onium salt and polysaccharides can also be provided.

Claims

1. An onium salt represented by the following formula (1): Formula (1): in, R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a): -O-R a (1a) Among them, R a It represents a C1-C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 Represents a hydrocarbon group, when R 1 and R 2 is methoxyethyl and R 3 When it is a hydrogen atom, R 4 It represents a hydrocarbon group having C2 or more carbon atoms.

2. The onium salt according to claim 1, wherein R in formula (1) 3 It is a hydrogen atom or a methyl group.

3. The onium salt according to claim 1 or 2, wherein R in formula (1) 1 and R 2 are the same or different, and each is represented by the formula (2): Formula (2): -R 5 -X-R 6 (2) Among them, R 5 represents a C2-C5 divalent hydrocarbon group, R 6 It represents a C1-C 10 Hydrocarbon, R 5 and R 6 The total number of carbon atoms in is 3 to 12, the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and X represents an oxygen atom or a sulfur atom.

4. The onium salt according to claim 3, wherein In formula (2), R 5 is propane-1,3-diyl, R 6 is a C1-C9 hydrocarbon group which may contain 1 to 4 heteroatoms, and X is an oxygen atom.

5. The onium salt according to claim 1, wherein R in formula (1) 1 and R 2 same.

6. The onium salt according to claim 1, wherein R in formula (1) 4 It is methyl, CH2=CH-, or CH2=C(CH3)-.

7. An onium salt composition comprising two or more onium salts represented by the following formula (1): Formula (1): in, R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a): -O-R a (1a) Among them, R a It represents a C1-C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 It represents a hydrocarbon group.

8. An onium hydroxide salt represented by the following formula (3): Formula (3): in, R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a): -O-R a (1a) Among them, R a It represents a C1-C 12 a hydrocarbon group; and R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, wherein the hetero atom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.

9. A method for preparing an onium salt represented by formula (1), comprising reacting glyoxal, an amine compound represented by formula (6a), an amine compound represented by formula (6b), an aldehyde compound represented by formula (7), and a carboxylic acid represented by formula (4): Formula (6a): R 1 -NH2 (6a) Formula (6b): R 2 -NH2 (6b) in, In formulas (6a) and (6b), R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a); -O-R a (1a) Among them, R a It represents a C1-C 12 Hydrocarbon; Formula (7): R 3 -GIVE (7) Among them, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; Formula (4): R 4 -COOH (4) Among them, R 4 represents a hydrocarbon group; and Formula (1): Among them, R 1 To R 4 As defined above.

10. A method for preparing an onium salt represented by formula (1), comprising ion-exchanging a compound represented by formula (3) with a compound represented by formula (4): Formula (3): in, R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a): -O-R a (1a) Among them, R a It represents a C1-C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; Formula (4): R 4 -COOH (4) Among them, R 4 represents a hydrocarbon group; and Formula (1): Among them, R 1 To R 4 As defined above.

11. A polysaccharide-containing liquid composition comprising at least one polysaccharide and an onium salt represented by the following formula (1) or the onium salt composition according to claim 7, wherein: The polysaccharide is dissolved in the onium salt: Formula (1): Among them, R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a): -O-R a (1a) Among them, R a It represents a C1-C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 Represents a hydrocarbon group, when R 1 is (2-methoxyethoxy)methyl, R 2 is 2-[2-(2-methoxyethoxy)ethoxy]ethyl, and R 3 When it is a hydrogen atom, R 4 It represents a hydrocarbon group of C2 or more carbon atoms.

12. The polysaccharide-containing liquid composition according to claim 11, further comprising at least one organic solvent, wherein The polysaccharide is dissolved in a medium containing the onium salt or the onium salt combination and the organic solvent.

13. The polysaccharide-containing liquid composition according to claim 12, wherein The organic solvent is at least one organic solvent selected from the group consisting of dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

14. The polysaccharide-containing liquid composition according to claim 11, wherein The polysaccharide is cellulose.

15. A method for preparing a polysaccharide-containing liquid composition according to claim 11, comprising dissolving a polysaccharide using an onium salt represented by the following formula (1) or an onium salt composition according to claim 7: Formula (1): in, R 1 and R 2 are the same or different and each represents a C2-C 12 A hydrocarbon group or a group represented by the following formula (1a): -O-R a (1a) Among them, R a It represents a C1-C 12 Hydrocarbon; R 3 represents a hydrogen atom or a hydrocarbon group that can contain a heteroatom, wherein the heteroatom is at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; and R 4 It represents a hydrocarbon group.

16. The method for preparing a liquid composition containing polysaccharides according to claim 15, wherein: The temperature for dissolving the polysaccharide is 50°C or lower.

17. The method for preparing a liquid composition containing polysaccharides according to claim 15 or 16, wherein: The polysaccharide is cellulose.

18. A polysaccharide recovery method comprising contacting the polysaccharide-containing liquid composition according to any one of claims 11 to 14 with at least one poor solvent.

19. The polysaccharide recovery method according to claim 18, wherein: The poor solvent is selected from the group consisting of water, methanol, ethanol, acetone and mixed solvents thereof.

20. The polysaccharide recovery method according to claim 18, wherein: The polysaccharide is cellulose.

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