Onium salt composition, method for producing cellulose hydrolysate, and method for producing alcohol and / or organic acid

Abstract

The present invention relates to an onium salt composition, a method for producing a cellulose hydrolysate, and a method for producing an alcohol and / or an organic acid. Provided is a composition containing an onium salt capable of smoothly performing an enzyme reaction and fermentation by a microorganism. An onium salt composition comprising an onium salt represented by formula (1), a cellulose-containing biomass, and an enzyme. Formula (1): # imgabs0 # (In formula (1), R1 to R4 are as defined in the description. ).

Description

Technical Field

[0001] The present invention relates to an onium salt composition and a method for producing a cellulose hydrolyzate, an alcohol and / or an organic acid in the presence of the onium salt composition. Background Art

[0002] As an alternative to petroleum resources, the use of plant-derived biomass is expected, and attempts have been made to use biomass for energy, various materials, etc. In order to effectively use biomass as energy, other raw materials, etc., it is preferred to decompose and saccharify biomass into a carbon source that can be easily used by animals or microorganisms.

[0003] As for the decomposition and saccharification, it is known to dissolve cellulose contained in biomass with an ionic liquid, decompose it into glucose with an enzyme such as cellulase, and ferment the glucose with microorganisms to produce alcohol and / or organic acid.

[0004] For example, Patent Document 1 describes the following method: a method of treating a cellulose-containing material with an ionic liquid whose cationic species is a pyridinium substitute, allowing cellulase to react with the treated liquid to saccharify the cellulose; and a method of further mixing the reaction liquid obtained by reacting the cellulase with an ethanol-producing microorganism, culturing the microorganism, and producing ethanol from the cellulose-containing material.

[0005] In addition, Non-Patent Document 1 describes ionic liquids having dialkylimidazolium as cations as ionic liquids that dissolve cellulose, and specifically describes 1-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1,3-dimethylimidazolium dialkyl phosphate. Prior art literature Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2013-135641 Non-patent literature

[0007] Non-patent document 1: Green Chemistry, 2015, Vol. 17, p. 694-714. Summary of the invention Technical problem to be solved by the invention

[0008] The onium salts as ionic liquids described in the prior art documents inhibit both enzyme reactions and fermentation by microorganisms. Therefore, it is necessary to remove the onium salts after dissolving cellulose contained in biomass using the onium salts as ionic liquids.

[0009] Under the conditions of the prior art, the technical problem of the present invention is to provide a composition containing an onium salt that can smoothly carry out both enzyme reaction and fermentation using microorganisms. In addition, the technical problem of the present invention is to provide a method for producing a cellulose hydrolyzate by hydrolyzing cellulose using an enzyme in the presence of an onium salt that can smoothly carry out both enzyme reaction and fermentation using microorganisms. Furthermore, the technical problem of the present invention is to provide a method for producing alcohol and / or organic acid by fermenting cellulose hydrolyzate using microorganisms in the presence of the onium salt. Technical solutions for solving technical problems

[0010] The present inventors have intensively studied onium salts that can smoothly carry out both enzyme reactions and fermentations using microorganisms, and enzyme reactions and fermentations using microorganisms in the presence of onium salts, thereby completing the present invention.

[0011] That is, the present invention provides the following [1] to

[18] . [1] An onium salt composition comprises an onium salt represented by the following formula (1), a cellulose-containing biomass, and an enzyme. Formula (1): [Chemistry 1] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds. [2] The onium salt composition according to [1], wherein cellulose-containing biomass is dissolved in the onium salt represented by the formula (1). [3] The onium salt composition according to [1] or [2], wherein the onium salt composition further contains water. [4] The onium salt composition according to [3], wherein the concentration of the onium salt represented by formula (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition. [5] An onium salt composition comprising an onium salt represented by the following formula (1), glucose and a microorganism. Formula (1): [Chemistry 2] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds. [6] The onium salt composition according to [5], wherein glucose is dissolved in the onium salt represented by the formula (1). [7] The onium salt composition according to [5] or [6], wherein the onium salt composition further contains water. [8] The onium salt composition according to [7], wherein the concentration of the onium salt represented by formula (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition. [9] An onium salt composition comprising an onium salt represented by the following formula (1), a cellulose-containing biomass, an enzyme, glucose, and a microorganism. Formula (1): [Chemistry 3] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds.

[10] The onium salt composition according to [9], further comprising water.

[11] The onium salt composition according to

[10] , wherein the concentration of the onium salt represented by formula (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition.

[12] A method for producing a cellulose hydrolyzate, comprising hydrolyzing cellulose contained in a cellulose-containing biomass using an enzyme in the presence of an onium salt represented by the following formula (1) and water. Formula (1): [Chemistry 4] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds.

[13] The method for producing a cellulose hydrolysate according to

[12] , comprising the following steps (1) to (3). Step (1): a step of dissolving cellulose-containing biomass in the presence of the onium salt represented by the formula (1). Step (2): a step of adding water and an enzyme to the dissolved solution obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolyzate.

[14] A method for producing an alcohol and / or an organic acid, comprising fermenting a cellulose hydrolyzate using a microorganism in the presence of an onium salt represented by the following formula (1) and water. Formula (1): [Chemistry 5] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds.

[15] The method for producing an alcohol and / or an organic acid according to

[14] , comprising the following steps (1) to (3). Step (1): A step of mixing the onium salt represented by the formula (1), a cellulose hydrolyzate, water and a microorganism. Step (2): A step of fermenting the cellulose hydrolyzate with microorganisms in the solution to which the microorganisms were added obtained in step (1) to produce alcohol and / or organic acid. Step (3): a step of separating alcohol and / or organic acid from the solution containing alcohol and / or organic acid obtained in step (2).

[16] The method for producing an alcohol and / or an organic acid according to

[14] or

[15] , wherein the alcohol is ethanol.

[17] A method for producing an alcohol and / or an organic acid, which is a method for producing an alcohol and / or an organic acid from a cellulose-containing biomass in the presence of an onium salt represented by the following formula (1) and water, comprising the following steps (1) to (6). Formula (1): [Chemistry 6] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds. Step (1): a step of dissolving cellulose-containing biomass in the presence of the onium salt represented by the formula (1). Step (2): a step of adding water and an enzyme to the dissolved solution obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolyzate. Step (4): a step of adding microorganisms to the solution containing the cellulose hydrolysate obtained in step (3). Step (5): A step of fermenting cellulose hydrolyzate with microorganisms in the solution to which microorganisms have been added obtained in step (4) to produce alcohol and / or organic acid. Step (6): A step of separating alcohol and / or organic acid from the solution containing alcohol and / or organic acid obtained in step (5).

[18] The production method according to

[14] or

[17] , wherein the solution containing the onium salt represented by the formula (1) is recovered, the onium salt is separated from the recovered solution, and the onium salt is recycled. Effects of the Invention

[0012] According to the present invention, a composition containing an onium salt that can smoothly carry out an enzyme reaction and fermentation using a microorganism can be provided. In addition, according to the present invention, a method for producing a cellulose hydrolyzate by hydrolyzing cellulose using an enzyme in the presence of an onium salt that can smoothly carry out an enzyme reaction and fermentation using a microorganism can be provided. Furthermore, according to the present invention, a method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolyzate using a microorganism in the presence of the onium salt can be provided. DETAILED DESCRIPTION

[0013] One embodiment of the present invention relates to an onium salt represented by the following formula (1) (hereinafter referred to as onium salt (1)) and an onium salt composition comprising a cellulose-containing biomass and an enzyme (hereinafter referred to as onium salt composition (1)).

[0014] Formula (1): [Chemistry 7] (In formula (1), R 1 ~R 3 Same or different, R 1 and R 2represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom. 1 ~R 3 may contain branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, branches and / or ring structures and / or double bonds.

[0015] In formula (1), R 1 and R 2 In the above, the "hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms" may be a straight chain, or may contain a branched chain and / or a ring structure and / or a double bond. The number of heteroatoms is preferably 1 to 3, more preferably 1 to 2. The number of carbon atoms in the hydrocarbon group is preferably 3 to 10, more preferably 4 to 7.

[0016] In formula (1), R 1 and R 2 In the above, examples of the "hetero atom" include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0017] In formula (1), R 1 and R 2 In the above, the “hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms” means a hydrocarbon group having 2 to 12 carbon atoms and not containing heteroatoms, wherein (i) a bond between two adjacent carbon atoms and / or (ii) one hydrogen atom of a -CH2-(methylene) group and another hydrogen atom of a -CH2-(methylene) group are bonded to each other by -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-, - The hydrocarbon groups after structural substitution such as 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-)-, -C(=NH)-, etc., can use the number and combination of these structural substitutions as long as R 1 , R 2 There is no particular limitation as long as the number of heteroatoms in the reaction mixture is within a range of 1 to 5.

[0018] Preferably, the hydrocarbon group is a hydrocarbon group in which (i) the bond between two adjacent carbon atoms and / or (ii) one hydrogen atom of -CH2-(methylene) and the hydrogen atoms of other -CH2-(methylene) are replaced by the structure of -O- or -S-, and more preferably a hydrocarbon group is a hydrocarbon group replaced by the structure of -O-.

[0019] In the present invention, as a hydrocarbon group, (i) a bond between two adjacent carbon atoms and / or (ii) a structure in which one hydrogen atom of -CH2-(methylene) and another hydrogen atom of -CH2-(methylene) are replaced by -O- or -S- may form an ether structure or a thioether structure, for example, an epoxy structure or a thioepoxy structure such as an epoxy group, a thioepoxy group, a glycidyl ether group, an epoxycyclohexyl group, or the like. In this case, R 1 or R 2 It may be an epoxy group, a thioepoxy group, or the like.

[0020] In R 1 and R 2 In the case where two or more structures of -O- or / and -S- are contained, the number of carbon atoms between the structures of -O- or / and -S- is preferably 2 or more.

[0021] More preferably R 1 and R 2 The nitrogen atoms on the imidazole rings bonded to each other are 1 or R 2 The number of carbon atoms between the heteroatom closest to the nitrogen atom on the imidazole ring is 2 or more.

[0022] In formula (1), R 1 and R 2 In the above, the "hydrocarbon group having 2 to 12 carbon atoms and not containing heteroatoms" may be a straight chain, or may contain a branched chain and / or a ring structure and / or a double bond. Examples of the hydrocarbon group having 2 to 12 carbon atoms and not containing heteroatoms include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, etc., without particular limitation.

[0023] In formula (1), as R 1 and R 2The “hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms” includes, for example, a straight-chain or branched alkyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, a straight-chain or branched alkynyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, a cycloalkyl group having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms and optionally branched, a cycloalkenyl group having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms and optionally branched, an aryl group having 6 to 12 carbon atoms and containing 1 to 5 heteroatoms and optionally branched, and an aralkyl group having 7 to 12 carbon atoms and containing 1 to 5 heteroatoms and optionally branched. Preferred are linear or branched alkyl groups having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, linear or branched alkenyl groups having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, and cycloalkyl groups having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms which may be branched. As the "straight-chain or branched alkyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms", a straight-chain or branched alkyl group having 3 to 10 carbon atoms and containing 1 to 3 heteroatoms is preferred. As another embodiment, a straight-chain or branched alkyl group having 3 to 10 carbon atoms and containing 1 to 2 heteroatoms is preferred, and a straight-chain or branched alkyl group having 4 to 7 carbon atoms and containing 1 to 2 heteroatoms is more preferred. As the "straight-chain or branched alkenyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms", a straight-chain or branched alkenyl group having 3 to 10 carbon atoms and containing 1 to 3 heteroatoms is preferred. In another embodiment, a straight-chain or branched alkenyl group having 3 to 10 carbon atoms and containing 1 to 2 heteroatoms is preferred, and a straight-chain or branched alkenyl group having 4 to 7 carbon atoms and containing 1 to 2 heteroatoms is more preferred. As the "cycloalkyl group having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms which may have a branch", a cycloalkyl group having 3 to 10 carbon atoms and containing 1 to 3 heteroatoms which may have a branch is preferred. As another embodiment, a cycloalkyl group having 3 to 10 carbon atoms and containing 1 to 2 heteroatoms which may have a branch is preferred, and a cycloalkyl group having 4 to 7 carbon atoms and containing 1 to 2 heteroatoms which may have a branch is more preferred.

[0024] In formula (1), as R 1 and R 2The hydrocarbon group having 2 to 12 carbon atoms and not containing a hetero atom in the above-mentioned group may specifically 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, 2,4,6-trimethylphenyl, and the like, without particular limitation. In a hydrocarbon group having 2 to 12 carbon atoms and not containing a heteroatom, (i) a bond between two adjacent carbon atoms and / or (ii) a hydrogen atom of a -CH2-(methylene) group and a hydrogen atom of another -CH2-(methylene) group are replaced by -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-, -OS(=O)2-O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)-, -C(=NH)-, etc., become "a hydrocarbon group having 2 to 12 carbon atoms containing 1 to 5 heteroatoms".

[0025] As R shown in formula (1) 1 and R 2, specifically, 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 -neopentoxypropyl, 3-hexyloxypropyl, 3-cyclohexyloxypropyl, 3-heptyloxypropyl, 3-octyloxypropyl, 3-nonyloxypropyl, 3-(2-ethylhexan-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-cyclohexyloxybutyl, 4-heptyloxybutyl, 4-octyloxybutyl, 4-(2-ethylhexan-1-yl)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-allyloxy hexyl, 6-butoxyhexyl, 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)hexyl1-(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., preferably 2-methoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-isopropoxypropyl, 3-butoxypropyl, 3-(2-methoxyethoxy)propyl, 3-methylthiopropyl, 3-(dimethylamino)propyl, more preferably 2-methoxyethyl, 3-methoxypropyl, 3-(2-methoxyethoxy)propyl, but the present invention is not limited to these. ,

[0026] In formula (1), preferably R 1 and R 2 same.

[0027] In formula (1), R 3 represents a hydrogen atom or a hydrocarbon group that may contain a hetero atom. The "hydrocarbon group that may contain a hetero atom" may be a straight chain, or may contain a branched chain and / or a ring structure and / or a double bond. 3 In the above, the hydrocarbon group may contain no heteroatoms or may contain heteroatoms.

[0028] In formula (1), R 3 In the case of a hydrocarbon group not containing a hetero atom, 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 hydrocarbon group containing a heteroatom, the number of carbon atoms is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.

[0029] In formula (1), R 3 When hetero atoms are contained, the number of hetero atoms is preferably 1 to 5, more preferably 1 to 2. The hydrocarbon group has 2 or more carbon atoms, preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.

[0030] In formula (1), 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.

[0031] As in R 3In the case of a hydrocarbon group containing a hetero atom, the "hetero atom" includes a nitrogen atom, an oxygen atom, a sulfur atom, etc. The number of hetero atoms is preferably 1 to 5, and more preferably 1 to 2.

[0032] In formula (1), R 3 In the above, the term "hydrocarbon group containing a heteroatom" means a hydrocarbon group not containing a heteroatom in which (i) a bond between two adjacent carbon atoms and / or (ii) one hydrogen atom of a -CH2-(methylene) group and another hydrogen atom of a -CH2-(methylene) group are connected by -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-, -OS(=O)2-O-, >NC(=S)-N<, >NC(=S)-NH-, -HN-C(=S)-NH-, -C(=N-)-, -C(=NH)-, etc., and the number and combination of these structural substitutions are not particularly limited, and R 3 The number of heteroatoms in is preferably 1 to 5, more preferably 1 to 2.

[0033] Preferably, the hydrocarbon group is a hydrocarbon group in which (i) the bond between two adjacent carbon atoms and / or (ii) one hydrogen atom of -CH2-(methylene) and the hydrogen atoms of other -CH2-(methylene) are replaced by the structure of -O- or -S-, and more preferably a hydrocarbon group is a hydrocarbon group replaced by the structure of -O-.

[0034] In the present invention, as a hydrocarbon group, (i) a bond between two adjacent carbon atoms and / or (ii) a structure in which one hydrogen atom of -CH2-(methylene) and another hydrogen atom of -CH2-(methylene) are replaced by -O- or -S- may form an ether structure or a thioether structure, for example, an epoxy structure or a thioepoxy structure such as an epoxy group, a thioepoxy group, a glycidyl ether group, an epoxycyclohexyl group, or a thioepoxy structure. In this case, R 3 It may be an epoxy group, a thioepoxy group, or the like.

[0035] R 3 In the case of containing two or more structures of -O- or / and -S-, the number of carbon atoms between the structures of -O- or / and -S- is preferably 2 or more.

[0036] In formula (1), as R 3The “hydrocarbon group which may contain a heteroatom” includes: a straight chain or branched alkyl group which may contain a heteroatom, a straight chain or branched alkenyl group which may contain a heteroatom, a straight chain or branched alkynyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, a cycloalkenyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an aralkyl group which may contain a heteroatom, etc. Preferably, it is a straight chain or branched alkyl group which may contain a heteroatom, a straight chain or branched alkenyl group which may contain a heteroatom, and a cycloalkyl group which may contain a heteroatom. As the “straight-chain or branched alkyl group which may contain a heteroatom”, a straight-chain or branched alkyl group having 1 to 12 carbon atoms which may contain 1 to 5 heteroatoms is preferred. As another embodiment, a straight-chain or branched alkyl group having 1 to 12 carbon atoms which may contain 1 to 2 heteroatoms is preferred, a straight-chain or branched alkyl group having 1 to 8 carbon atoms which may contain 1 to 2 heteroatoms is more preferred, and a straight-chain or branched alkyl group having 1 to 4 carbon atoms which may contain 1 to 2 heteroatoms is further preferred. Furthermore, as another embodiment, a straight-chain or branched alkyl group having 1 to 12 carbon atoms is preferred, a straight-chain or branched alkyl group having 1 to 8 carbon atoms is more preferred, and a straight-chain or branched alkyl group having 1 to 3 carbon atoms is further preferred. As the “straight-chain or branched alkenyl group which may contain a heteroatom”, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms which may contain 1 to 5 heteroatoms is preferred. As another embodiment, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms which may contain 1 to 2 heteroatoms is preferred, a straight-chain or branched alkenyl group having 2 to 8 carbon atoms which may contain 1 to 2 heteroatoms is more preferred, and a straight-chain or branched alkenyl group having 2 to 4 carbon atoms which may contain 1 to 2 heteroatoms is further preferred. Furthermore, as another embodiment, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms is preferred, a straight-chain or branched alkenyl group having 2 to 8 carbon atoms is more preferred, and a straight-chain or branched alkenyl group having 2 to 3 carbon atoms is further preferred. The “cycloalkyl group which may contain a heteroatom and may have a branch” is preferably a cycloalkyl group having 3 to 12 carbon atoms and may contain 1 to 5 heteroatoms and may have a branch. As another embodiment, a cycloalkyl group having 3 to 12 carbon atoms and may contain 1 to 2 heteroatoms and may have a branch, more preferably a cycloalkyl group having 3 to 8 carbon atoms and may contain 1 to 2 heteroatoms and may have a branch, and further preferably a cycloalkyl group having 3 to 4 carbon atoms and may contain 1 to 2 heteroatoms and may have a branch. Furthermore, as another embodiment, a cycloalkyl group having 3 to 12 carbon atoms and may have a branch, more preferably a cycloalkyl group having 3 to 8 carbon atoms and may have a branch, and further preferably a cycloalkyl group having 3 carbon atoms.

[0037] In formula (1), R 3 In the above, the “hydrocarbon group not containing a hetero atom” specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a vinyl group, an ethynyl group, a propenyl group, an isopropenyl group, an allyl group, a propargyl group, a butenyl group, a crotyl group, a butadienyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a phenyl group, a benzyl group, a tolyl group, a styryl group, a 2,4,6-trimethylphenyl group, and the like. Preferably, it is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and more preferably, it is a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group.

[0038] In formula (1), R 3 In the above, the “hydrocarbon group containing a heteroatom” is preferably 3-indolyl, p-methoxyphenyl, 7-oxabicyclo[2,2,1]hept-5-en-2-yl, 1,2-epoxyethyl, 1-methyl-2-methoxyvinyl, 2-furanyl, 2-pyridyl, 4-imidazolyl, benzyloxymethyl, and more preferably 1-methyl-2-methoxyvinyl and 2-furanyl, but the present invention is not limited thereto.

[0039] In formula (1), as R 3 , preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0040] In formula (1), R 1 ~R 3 A part or all of may be bonded to each other together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. Specifically, the ring structure includes 1 and R 2 , R 1 and R 3 , or R 2 and R 3 The structure is not particularly limited and is formed by cross-linking with hydrocarbons having 2 to 24 carbon atoms and containing 2 to 10 hetero atoms to form a ring.

[0041] In formula (1), R 4 represents a hydrocarbon group, which may be a straight chain or may contain a branched chain and / or a ring structure and / or a double bond, and is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and still more preferably a hydrocarbon group having 1 to 3 carbon atoms.

[0042] In formula (1), as R 4Examples of the “hydrocarbon group” include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, and aralkyl. Preferably, the group is a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a branch, a cycloalkenyl group having 3 to 12 carbon atoms which may have a branch, an aryl group having 6 to 12 carbon atoms which may have a branch, and an aralkyl group having 7 to 12 carbon atoms which may have a branch. More preferably, the group is a linear or branched alkyl group having 1 to 3 carbon atoms, and a linear or branched alkenyl group having 1 to 3 carbon atoms.

[0043] In formula (1), as R 4 The “hydrocarbon group” specifically includes, but is not particularly limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a vinyl group, an ethynyl group, a propenyl group, an isopropenyl group, an allyl group, a propargyl group, a 1-propynyl group, a butenyl group, a crotyl group, a butadienyl group, a pentadienyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a phenyl group, a benzyl group, a tolyl group, a styryl group, a 2,4,6-trimethylphenyl group, a naphthyl group, and a 2,6-dimethyl-1,5-heptadienyl group.

[0044] In formula (1), as R 4 -CO-O - The anions shown in the formula include, specifically, acetate ion, propionate ion, acrylate ion, propargyl ion, butyrate ion, isobutyrate ion, methacrylate ion, crotonate ion, butynoate ion, cyclopropanecarboxylate ion, valerate ion, isovalerate ion, pivalate ion, angelate ion, tiglate ion, cyclobutanecarboxylate ion, hexanoate ion, cyclopentanecarboxylate ion, heptanoate ion, sorbate ion, cyclohexanecarboxylate ion, benzoate ion, octanoate ion, 2-ethylhexylcarboxylate ion, toluate ion The present invention is preferably an ion such as an acetate ion, a propionate ion, an acrylate ion, a propargyl ion, a butyrate ion, an isobutyrate ion, a methacrylate ion, a crotonate ion, a butynoate ion, a valerate ion, an isovalerate ion, or a pivalate ion; particularly preferably an acetate ion, an acrylate ion, or a methacrylate ion; however, the present invention is not limited thereto.

[0045] As the onium salt represented by formula (1) ImidazoliumSpecific examples of the cation 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, and 1,3-bis(3-propoxypropyl)imidazolium. 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-dimethylethyl)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-ethylhexane-1-yl)oxy]propyl}imidazolium, 1,3-bis[3-(2,4,6-trimethylphenoxy)propyl]imidazolium, 1,3-bis[3-(2-methoxyethoxy)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, 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-butoxybutyl)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-ethylhexane-1-yl)oxy]butyl}imidazolium, 1,3-bis(5-methoxypentyl)imidazolium, 1,3-bis(5-ethoxypentyl)imidazolium, 1,3- Bis(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, 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-heptyloxypentyl)imidazolium, 1,3-bis(6-methoxy 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-(1-methylpropoxy)hexyl]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, 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, 1,3-bis[(2-pentyl 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]heptane-2-yl)methyl}imidazolium, 1-methoxypropyl-3-methylthiopropylimidazolium, 1,3-bis(3-methoxypropyl)-2-methylimidazolium, 1,3-bis(2-methoxyethyl)-2-methylimidazolium 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 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, 1,3-bis(2-methyl The present invention is preferably 1,3-bis(3-methoxypropyl)imidazolium, 1,3-bis(3-ethoxypropyl)imidazolium, 1-methoxypropyl-3-methylthiopropylimidazolium, 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium, 1,3-bis(2-methoxyethyl)-2-methylimidazolium, and 1,3-bis(3-methoxypropyl)-2-methylimidazolium, but the present invention is not limited thereto.

[0046] The onium salt represented by formula (1) is preferably an onium salt composed of a combination of one cation selected from 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 one anion selected from acetate ion, acrylate ion, and methacrylate ion.

[0047] More specifically, 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-methylthiopropylimidazolium acetate, 1,3-bis(3-methylthiopropyl)imidazolium acetate, 1,3-bis(2-methoxyethyl)-2-methylimidazolium acetate, 1,3-bis(2-methoxyethyl)-2-methylimidazolium acrylate, and 1,3-bis(2-methoxyethyl)-2-methylimidazolium methacrylate. The present invention is preferably 1,3-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 preferably 1,3-bis(3-methoxypropyl)imidazolium acetate, 1,3-bis(3-methoxypropyl)imidazolium acrylate, and 1,3-bis(3-methoxypropyl)imidazolium methacrylate, but the present invention is not limited thereto.

[0048] The onium salt (1) of the present invention can be obtained, for example, by the production method (Production Method 1) shown in the following Reaction Scheme 1. Specifically, referring to the production method of 1,3-bis(3-methoxypropyl)imidazolium acetate shown in [Production Example 1], a person skilled in the art can easily produce it.

[0049] Reaction 1: [Chemistry 8] (In reaction formula 1, R 1 , R 2 , R 3 and R 4 As defined above, respectively.)

[0050] Production method 1 is described. Glyoxal, R 1 -NH2 (Formula (2)) and / or R 2 -NH2 (Formula (3)) represented by an amine compound, R 3 -CHO aldehyde compound (formula (4)) and R 4 The carboxylic acid represented by -COOH (Formula (5)) reacts.

[0051] As R1 -NH2 (Formula (2)) or R 2The amine compound represented by -NH2 (formula (3)) specifically includes: 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-ethylhexane-1-yl)oxyethylamine, 2-(2 ,4,6-trimethylphenoxy)ethylamine, 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, 3-(2-ethylhexane-1-yl)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-ethylhexane- 1-yl)oxybutylamine, 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-methoxycyclohexane-1-ylmethylamine, (2-ethoxycyclohexane-1-yl)methylamine, (2-propoxycyclohexane-1-yl)methylamine, (2-isopropoxycyclohexane-1-yl)methylamine, (2-butoxycyclohexane-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 R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, 1 -NH2 or R 2 The amine compounds represented by -NH2 may be the same or different.

[0052] As R 3 -CHO (Formula (4)) aldehyde compounds include, specifically, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, etc., preferably formaldehyde and acetaldehyde, but the present invention is not limited thereto. Formaldehyde can be a cyclic oligomer or polymer such as paraformaldehyde, triformaldehyde, tetraformaldehyde, etc. that can generate formaldehyde in the reaction system.

[0053] R 3 The aldehyde compound represented by -CHO (Formula (4)) can be used directly in the form of an aqueous solution or an alcohol solution such as methanol, butanol, or 2-ethylhexanol.

[0054] As R 4The carboxylic acid represented by -COOH (formula (5)) includes acetic acid, propionic acid, acrylic acid, propargyl acid, butyric acid, isobutyric acid, methacrylic acid, crotonic acid, butynoic acid, cyclopropanecarboxylic 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-norbornanecarboxylic acid, nonanoic acid, cubanecarboxylic acid, cinnamic acid, decanoic acid, 3-noradamantanecarboxylic acid, geranic acid, undecanoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, and 1-adamantanecarboxylic acid. Acetic acid, propionic acid, acrylic acid, propargyl acid, butyric acid, isobutyric acid, methacrylic acid, crotonic acid, butynoic acid, valeric acid, isovaleric acid, and pivalic acid are preferred. Acetic acid, acrylic acid, or methacrylic acid is particularly preferred, but the present invention is not limited thereto.

[0055] Glyoxal may be used directly in the form of an aqueous solution or in an alcohol solution such as methanol, butanol, or 2-ethylhexanol.

[0056] As R 1 -NH2 (Formula (2)) and R 2 -NH2 (Formula (3)) is used in an amount of amine compound, relative to 1 mol of glyoxal, R 1 -NH2 and R 2 The total amount of -NH2 is preferably 0.1 to 10 mol, more preferably 0.5 to 3 mol. 1 With R 2 In different cases, two amine compounds (R 1 -NH2 and R 2 -NH2) ratio (molar ratio) is not particularly limited, and is R 1 -NH2∶R 2 -NH2=0∶100~100∶0. 1 -NH2∶R 2 -NH2=0∶100 or 100∶0, it becomes R 1 =R 2 . In the absence of R 1 -NH2∶R 2 When -NH2=0:100 or 100:0, the onium salt (1) obtained by the production method 1 is a mixture of compounds represented by the following formula. The compounds represented by the following formula (1′) and formula (1″) are both included in the onium salt represented by formula (1), and the mixture can also be used as the onium salt composition described later. In addition, optionally, the mixture can also be purified to obtain the desired single compound and used as the onium salt (1).

[0057] [Chemistry 9]

[0058] R3 The aldehyde compound represented by -CHO (Formula (4)) can be used directly in an aqueous solution or in an alcohol solution such as methanol, butanol, or 2-ethylhexanol. The amount of the aldehyde compound used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, per 1 mol of glyoxal.

[0059] As R 4 The amount of the carboxylic acid represented by -COOH (Formula (5)) used is preferably 0.1 to 10 mol, more preferably 0.5 to 2 mol, per 1 mol of glyoxal.

[0060] In the manufacturing method 1, a solvent may be used or not. 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., preferably alcohol solvents and water.

[0061] In addition, the onium salt (1) produced in advance can also be used as the reaction solvent of the production method 1. The solvent can be used by mixing two or more kinds of solvents as desired. The amount of the solvent used is preferably 50 parts by mass or less, more preferably 0.1 to 10 parts by mass, per 1 part by mass of glyoxal.

[0062] In the production method 1, the reaction may be optionally carried out in an inert gas atmosphere such as nitrogen, argon, helium, etc. which does not affect the reaction.

[0063] When the production method 1 is carried out, the reaction pressure is usually atmospheric pressure. However, depending on the raw materials and / or solvents used, the reaction system may be pressurized to a pressure of atmospheric pressure to 1 MPa to allow the reaction to proceed.

[0064] The optimum reaction temperature varies depending on the raw materials, solvent, etc. used, but is preferably -10°C or higher, more preferably 0°C to 100°C.

[0065] After the reaction of Production Method 1 is completed, the onium salt (1) may be purified by a known purification method or may not be purified. Examples of the purification method include concentration, liquid separation, recrystallization, dialysis, adsorption, filtration, etc., but are not particularly limited.

[0066] The cellulose-containing biomass contained in the onium salt composition (1) is not particularly limited. Specifically, biomass containing natural fiber products such as pulp, cotton, and hemp, regenerated fiber products such as rayon, cuprammonium fiber, and cellulose acetate, various straws such as straw, bagasse, and agricultural wastes such as wood chips, waste paper, and various wastes such as construction waste can be cited. When dissolving the biomass containing the above-mentioned natural fiber products such as pulp, cotton, and hemp, rayon, cuprammonium fiber, and cellulose acetate, various straws such as straw, bagasse, and agricultural wastes such as wood chips, waste paper, and various wastes such as construction waste in the onium salt (1), it is preferred to cut them before use in order to shorten the time before dissolution.

[0067] In the present invention, cellulose refers to a polymer formed by polymerization of glucose through β-1,4-glucosidic bonds and its derivatives. The degree of polymerization of glucose in cellulose is not particularly limited, but is preferably 200 or more. In addition, derivatives such as carboxymethylation, hydroformylation, and esterification can be cited. In addition, cellulose can contain cellooligosaccharides and cellobiose as partial decomposition products thereof. Furthermore, cellulose can also be β-glucoside as a glycoside, lignocellulose as a complex with lignin and / or hemicellulose, and a complex with pectin, etc. The onium salt of the present invention can dissolve cellulose at 10°C to 50°C even if it is lignocellulose and a complex with pectin, etc. Cellulose can be crystalline cellulose or non-crystalline cellulose, preferably crystalline cellulose. Furthermore, cellulose can be cellulose of natural origin or artificially synthesized cellulose. The source of cellulose is also not particularly limited. It can be cellulose of plant origin, cellulose of fungal origin, or cellulose of bacterial origin.

[0068] The enzyme contained in the onium salt composition (1) is a cellulose hydrolase, and cellulase can be mentioned. Cellulase hydrolyzes the β-1,4-glucosidic bonds of cellulose. Representative types of cellulase include endo-β-1,4-glucanase (hereinafter referred to as "endo-glucanase"), cellobiohydrolase, and β-glucosidase, but are not limited to these.

[0069] In the present specification, cellulose hydrolysis means that the β-1,4-glucosidic bonds of cellulose are hydrolyzed to generate reducing sugars such as glucose and cellobiose. In addition, cellulose hydrolyzate means reducing sugars such as glucose and cellobiose generated by hydrolyzing cellulose.

[0070] Endoglucanase is an enzyme generally called cellulase, and cuts cellulose from the inside of the molecule to produce glucose, cellobiose, and cellooligosaccharides (having a degree of polymerization of 3 or more and usually 10 or less, but not limited thereto). Endoglucanase is a typical example of an enzyme that hydrolyzes amorphous cellulose. Examples of endoglucanase include endoglucanase derived from Trichoderma reesei (particularly EGII), but are not limited thereto.

[0071] Cellobiohydrolase decomposes from either the reducing end or the non-reducing end of cellulose to free cellobiose. Cellobiohydrolase is a representative example of an enzyme that hydrolyzes crystalline cellulose. There are two types of cellobiohydrolases, referred to as cellobiohydrolase 1 and cellobiohydrolase 2. As cellobiohydrolases, for example, cellobiohydrolase (particularly CBH2) derived from Trichoderma reesei can be cited, but it is not limited thereto.

[0072] β-glucosidase is an exo-type hydrolase that cleaves glucose units from non-reducing ends in cellulose. β-glucosidase cuts the β-1,4-glucosidic bond between aglycones or sugar chains and β-D-glucose, and hydrolyzes cellobiose or cellooligosaccharides to produce glucose. β-glucosidase is a representative example of an enzyme that hydrolyzes cellobiose or cellooligosaccharides. One type of β-glucosidase is referred to as β-glucosidase 1. As β-glucosidase, for example, β-glucosidase (particularly BGL1) derived from Aspergillus aculeatus can be cited, but is not limited thereto.

[0073] As cellulase, it can be cellulase of natural origin, cellulase manufactured by recombinant DNA technology, or commercially available cellulase. It can be purified cellulase, or enzyme-producing microorganisms, etc. It can be an enzyme preparation, or a microorganism expressing cellulase, etc. For example, cellulase derived from Clostridium genus such as Clostridium thermocellum, Trichoderma genus such as Trichoderma reesei, or Aspergillus genus such as Aspergillus oryzae and Aspergillus niger can be cited. It can also be cellulase derived from hyperthermophilic archaea represented by Pyrococcus genus.

[0074] As the cellulase, two or more types may be used in combination, and a combination capable of hydrolyzing cellulose into glucose is preferred.

[0075] The onium salt composition (1) is preferably one in which cellulose-containing biomass is dissolved in the onium salt (1).

[0076] The onium salt composition (1) is preferably an onium salt composition (1) comprising an onium salt (1), a cellulose-containing biomass, an enzyme, and water. More preferably, it is an onium salt composition (1) comprising an onium salt (1), a cellulose-containing biomass, an enzyme, and water, wherein the cellulose-containing biomass is dissolved in the onium salt (1).

[0077] The onium salt composition (1) is preferably an onium salt composition (1) comprising an onium salt (1), a cellulose-containing biomass, an enzyme, and water, wherein the concentration of the onium salt (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition (1). The concentration of the onium salt (1) is more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

[0078] One example of the present invention relates to an onium salt composition (hereinafter referred to as onium salt composition (2)) comprising an onium salt (1) represented by the above formula (1), glucose and a microorganism. The onium salt (1) contained in the onium salt composition (2) is the same as the onium salt (1) described above.

[0079] The glucose contained in the onium salt composition (2) is a compound having the molecular formula C6H 12 O6 monosaccharide molecules are the substances that constitute cellulose.

[0080] The microorganism contained in the onium salt composition (2) is a microorganism that produces alcohol and / or organic acid using glucose as a carbon source. For example, an ethanol-producing microorganism can be cited. The ethanol-producing microorganism can produce organic acids such as acetic acid while producing ethanol by promoting fermentation.

[0081] The ethanol-producing microorganism is not particularly limited, and examples thereof include yeast, ethanol-producing filamentous fungi, and ethanol-producing bacteria. Yeast is preferred. The yeast is not particularly limited, and examples thereof include yeasts of the genus Saccharomyces such as Saccharomyces cerevisiae, yeasts of the genus Schizosaccharomyces such as Schizosaccharomyces pombe, yeasts of the genus Candida such as Candida krusei and Candida shehatae, yeasts of the genus Pichia such as Pichia pastoris and Pichia stipitis, yeasts of the genus Hansenula, yeasts of the genus Trichosporon, yeasts of the genus Brettanomyces, yeasts of the genus Pachysolen, yeasts of the genus Yamadazyma, yeasts of the genus Kluyveromyces marxianus, and yeasts of the genus Saccharomyces cerevisiae. Yeasts of the genus Kluyveromyces, such as Kluyveromyces marxianus and Kluyveromyces lactis, are preferred. Among them, from the viewpoint of industrial applicability, yeasts of the genus Saccharomyces are preferred, and Saccharomyces cerevisiae is more preferred. As yeast, raw yeast and dry yeast can be used. As ethanol-producing filamentous fungi, there are no particular limitations, and examples include filamentous fungi of the genus Mucor. As ethanol-producing bacteria, there are no particular limitations, and examples include Zymomonas mobilis and genetically recombinant Escherichia coli transformed with the trait of producing ethanol.

[0082] The onium salt composition (2) is preferably an onium salt composition (2) in which glucose is dissolved in the onium salt (1).

[0083] The onium salt composition (2) is preferably an onium salt composition (2) comprising an onium salt (1), glucose, a microorganism, and water. More preferably, it is an onium salt composition (2) comprising an onium salt (1), glucose, a microorganism, and water, or glucose dissolved in the onium salt (1).

[0084] The onium salt composition (2) is preferably an onium salt composition (2) comprising an onium salt (1), glucose, a microorganism, and water, wherein the concentration of the onium salt (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition (2). The concentration of the onium salt (1) is more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

[0085] One example of the present invention relates to an onium salt composition comprising the onium salt (1) represented by the formula (1), a cellulose-containing biomass, an enzyme, glucose, and a microorganism (hereinafter referred to as the onium salt composition (3)). The onium salt (1), the cellulose-containing biomass, the enzyme, glucose, and the microorganism contained in the onium salt composition (3) are the same as the onium salt (1), the cellulose-containing biomass, the enzyme, glucose, and the microorganism described above, respectively.

[0086] The onium salt composition (3) is preferably an onium salt composition (3) comprising the onium salt (1), cellulose-containing biomass, enzyme, glucose, microorganisms, and water.

[0087] The onium salt composition (3) is preferably an onium salt composition (3) comprising an onium salt (1), a cellulose-containing biomass, an enzyme, glucose, a microorganism, and water, wherein the concentration of the onium salt (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition (3). The concentration of the onium salt (1) is more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

[0088] One example of the present invention relates to a method for producing a cellulose hydrolyzate, comprising hydrolyzing cellulose contained in a cellulose-containing biomass using an enzyme in the presence of an onium salt (1) represented by the above formula (1) and water.

[0089] As a method for producing a cellulose hydrolyzate, a method for producing a cellulose hydrolyzate comprising the following steps (1) to (3) is preferred. Step (1): a step of dissolving cellulose-containing biomass in the presence of the onium salt (1) represented by the above formula (1). Step (2): a step of adding water and an enzyme to the dissolved solution obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolyzate.

[0090] The ratio of the onium salt (1) to the cellulose-containing biomass used in step (1) of the method for producing a cellulose hydrolyzate is preferably 1 to 30% by mass, more preferably 10 to 28% by mass, and particularly preferably 15 to 25% by mass, in terms of the content of the cellulose-containing biomass [{cellulose-containing biomass (g) / (cellulose-containing biomass (g) + onium salt (1))}×100].

[0091] In the step (1), the temperature when dissolving the cellulose-containing biomass in the presence of the onium salt (1) is preferably 0 to 120°C, particularly preferably 20 to 100°C, or 25 to 80°C.

[0092] The amount of water added in step (2) of the method for producing a cellulose hydrolyzate is preferably 4 to 999 kg, more preferably 6 to 150 kg, and particularly preferably 19 to 99 kg, per 1 kg of the dissolved solution obtained in step (1).

[0093] The amount of the enzyme added in the step (2) is preferably 0.1 to 50 g, more preferably 1 to 10 g, and particularly preferably 2 to 5 g, relative to 1 kg of the dissolved solution obtained in the step (1).

[0094] The water and enzyme added in the step (2) may be added separately or simultaneously. Alternatively, the water and enzyme may be mixed in advance and then added.

[0095] The temperature when adding water and the enzyme in the step (2) is preferably 10 to 60°C, more preferably 25 to 50°C, based on the temperature of the solution obtained in the step (1).

[0096] The enzymatic hydrolysis of cellulose in step (3) of the method for producing a cellulose hydrolyzate is carried out by stirring the solution obtained in step (2). The temperature during the hydrolysis is preferably 10 to 60° C., more preferably 25 to 50° C. The hydrolysis time or stirring time is preferably 4 to 100 hours, more preferably 12 to 96 hours, and particularly preferably 24 to 72 hours.

[0097] After the step (3) is completed, the solution obtained in the step (3) is filtered to separate the residue of the cellulose-containing biomass by filtration, thereby obtaining a solution containing a cellulose hydrolyzate as a filtrate.

[0098] One embodiment of the present invention relates to a method for producing an alcohol and / or an organic acid, comprising fermenting a cellulose hydrolyzate using a microorganism in the presence of an onium salt (1) represented by the above formula (1) and water.

[0099] As the method for producing an alcohol and / or an organic acid, a method for producing an alcohol and / or an organic acid comprising the following steps (1) to (3) is preferred. Step (1): A step of mixing the onium salt represented by the formula (1), a cellulose hydrolyzate, water and a microorganism. Step (2): A step of fermenting the cellulose hydrolyzate with microorganisms in the solution to which the microorganisms were added obtained in step (1) to produce alcohol and / or organic acid. Step (3): a step of separating alcohol and / or organic acid from the solution containing alcohol and / or organic acid obtained in step (2).

[0100] As the method for producing an alcohol and / or an organic acid, a method for producing an alcohol is more preferred, and a method for producing ethanol is further preferred.

[0101] As the cellulose hydrolyzate used in step (1) of the method for producing an alcohol and / or an organic acid by fermenting the cellulose hydrolyzate with a microorganism, a cellulose hydrolyzate obtained by the above-mentioned method for producing a cellulose hydrolyzate can be used.

[0102] The ratio of the amount of the onium salt, cellulose hydrolyzate, water and microorganism mixed in the step (1) is 0.1 to 100 kg of cellulose hydrolyzate, 4 to 999 kg of water and 0.01 to 10 kg of microorganism per 1 kg of onium salt.

[0103] The temperature when the onium salt, cellulose hydrolyzate, water and microorganism are mixed in the step (1) is preferably 5 to 60°C, more preferably 10 to 50°C, and particularly preferably 25 to 40°C.

[0104] The fermentation of the cellulose hydrolyzate by microorganisms in step (2) of the method for producing alcohol and / or organic acid by fermenting the cellulose hydrolyzate by microorganisms may be carried out by stirring the solution to which the microorganisms are added, or may be carried out by leaving it still (without stirring).

[0105] The fermentation temperature of the cellulose hydrolyzate by the microorganism in the step (2) is more preferably 5 to 60°C, more preferably 10 to 50°C, and particularly preferably 25 to 40°C.

[0106] The fermentation time of the cellulose hydrolyzate by the microorganism in the step (2) is preferably 1 to 48 hours, more preferably 8 to 36 hours, and particularly preferably 12 to 24 hours.

[0107] In the step (2), the cellulose hydrolyzate is fermented by microorganisms to produce alcohol and / or organic acid. For example, the alcohol is methanol, ethanol, etc., and the organic acid is formic acid, acetic acid, etc.

[0108] The separation of alcohol and / or organic acid in step (3) of the method for producing alcohol and / or organic acid by fermenting cellulose hydrolyzate using microorganisms can be carried out by heating the solution containing alcohol and / or organic acid obtained in the above step (2) to separate the alcohol and / or organic acid by distillation.

[0109] One example of the present invention relates to a method for producing alcohol and / or organic acid from cellulose-containing biomass in the presence of an onium salt (1) represented by the above formula (1) and water, comprising the following steps (1) to (6). Step (1): a step of dissolving cellulose-containing biomass in the presence of the onium salt (1) represented by the above formula (1). Step (2): a step of adding water and an enzyme to the dissolved solution obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolyzate. Step (4): a step of adding microorganisms to the solution containing the cellulose hydrolysate obtained in step (3). Step (5): A step of fermenting cellulose hydrolyzate with microorganisms in the solution to which microorganisms have been added obtained in step (4) to produce alcohol and / or organic acid. Step (6): A step of separating alcohol and / or organic acid from the solution containing alcohol and / or organic acid obtained in step (5).

[0110] The ratio of the onium salt (1) to the cellulose-containing biomass used in step (1) of the method for producing alcohols and / or organic acids from cellulose-containing biomass is preferably 1 to 30% by mass, more preferably 10 to 28% by mass, and particularly preferably 15 to 25% by mass, in terms of the content of the cellulose-containing biomass [{cellulose-containing biomass (g) / (cellulose-containing biomass (g) + onium salt (1))}×100].

[0111] In the step (1), the temperature is preferably 0 to 120°C, more preferably 20 to 100°C, and particularly preferably 25 to 80°C.

[0112] The amount of water added in step (2) of the method for producing alcohol and / or organic acid from cellulose-containing biomass is preferably 4 to 999 kg, more preferably 6 to 150 kg, and particularly preferably 19 to 99 kg, based on 1 kg of the dissolved liquid obtained in step (1).

[0113] The amount of the enzyme added in the step (2) is preferably 0.1 to 50 g, more preferably 1 to 10 g, and particularly preferably 2 to 5 g, relative to 1 kg of the dissolved solution obtained in the step (1).

[0114] The water and enzyme added in the step (2) may be added separately or simultaneously. Alternatively, the water and enzyme may be mixed in advance and then added.

[0115] The temperature when adding water and the enzyme in the step (2) is preferably 10 to 60°C, more preferably 25 to 50°C, based on the temperature of the solution obtained in the step (1).

[0116] The cellulose hydrolysis by enzyme in step (3) of the method for producing alcohol and / or organic acid from cellulose-containing biomass is carried out by stirring the solution obtained in step (2). The temperature during the hydrolysis is preferably 10 to 60° C., more preferably 25 to 50° C. The hydrolysis time or stirring time is preferably 4 to 100 hours, more preferably 12 to 96 hours, and particularly preferably 24 to 72 hours.

[0117] The amount of the microorganism added in step (4) of the method for producing alcohol and / or organic acid from cellulose-containing biomass is preferably 0.01 to 10 g, more preferably 0.1 to 5 g, per 1 kg of the solution containing the cellulose hydrolyzate obtained in step (3).

[0118] The temperature when adding the microorganism in the step (4) is preferably 5 to 60°C, more preferably 10 to 50°C, and particularly preferably 25 to 40°C, based on the temperature of the solution containing the cellulose hydrolyzate obtained in the step (3).

[0119] The fermentation of the cellulose hydrolyzate by microorganisms in step (5) of the method for producing alcohol and / or organic acid from cellulose-containing biomass may be carried out by stirring the solution to which the microorganisms have been added obtained in step (4) or by leaving it to stand (without stirring).

[0120] The fermentation temperature of the cellulose hydrolyzate by the microorganism in the step (5) is particularly preferably 5 to 60°C, more preferably 10 to 50°C, and particularly preferably 25 to 40°C.

[0121] The fermentation time of the cellulose hydrolyzate by the microorganism in the step (5) is preferably 1 to 48 hours, more preferably 8 to 36 hours, and particularly preferably 12 to 24 hours.

[0122] In the step (5), the cellulose hydrolyzate is fermented by microorganisms to produce alcohol and / or organic acid. For example, the alcohol is methanol, ethanol, etc., and the organic acid is formic acid, acetic acid, etc.

[0123] The separation of alcohol and / or organic acid in step (6) of the method for producing alcohol and / or organic acid from cellulose-containing biomass can be carried out by heating the solution containing alcohol and / or organic acid obtained in the step (5) to separate the alcohol and / or organic acid by distillation.

[0124] One example of the present invention relates to: in a method for producing alcohol and / or organic acid by fermenting the cellulose hydrolyzate using microorganisms or a method for producing alcohol and / or organic acid from the cellulose-containing biomass, a solution containing the onium salt (1) represented by the formula (1) is recovered, the onium salt (1) is separated from the recovered solution, and the onium salt (1) is recycled.

[0125] By distilling and separating the alcohol and / or organic acid from the solution containing the alcohol and / or organic acid obtained in step (2) of the method for producing the alcohol and / or organic acid by fermenting the cellulose hydrolyzate using a microorganism, the onium salt (1) or a liquid containing the onium salt (1) can be recovered. The onium salt (1) or a liquid containing the onium salt (1) is recovered as a residue in the distillation of the alcohol and / or organic acid.

[0126] By distilling and separating the alcohol and / or organic acid from the solution containing the alcohol and / or organic acid obtained in step (5) of the method for producing an alcohol and / or an organic acid from a cellulose-containing biomass, the onium salt (1) or a liquid containing the onium salt (1) can be recovered. The onium salt (1) or a liquid containing the onium salt (1) is recovered as a residue in the distillation of the alcohol and / or organic acid.

[0127] The recovered onium salt (1) or the liquid containing the onium salt (1) can be recycled and utilized in the onium salt composition of the present invention, the method for producing a cellulose hydrolyzate, the method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolyzate using a microorganism, or the method for producing an alcohol and / or an organic acid from a cellulose-containing biomass. In addition, it can be used in other compositions, production methods or uses using an onium salt. Example

[0128] Next, the present invention will be specifically described based on Examples, but the present invention is not limited thereto.

[0129] 1,3-bis(3-methoxypropyl)imidazolium acetate ([(MeOPr)2Im][AcO]) used in Examples and Reference Examples was produced as described in [Production Example 1] below.

[0130] [Production Example 1] A 5L three-mouth reactor after nitrogen substitution was charged with 260g (3.22mol) of 37wt% formaldehyde aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.), 290g (4.83mol) of acetic acid (manufactured by Junsei Chemical Co., Ltd.), 573g (6.43mol) of 3-methoxypropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 461g (3.22mol) of 40wt% glyoxal aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.). The obtained mixture was heated to 40°C and stirred for 3 hours to synthesize 811g of 1,3-bis(3-methoxypropyl)imidazolium acetate ([(MeOPr)2Im][AcO]). The yield was 93%. [(MeOPr)2Im][AcO] 1 The results of H NMR data are shown below. 1 H NMR (DMSO-d6) 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)

[0131] 1-ethyl-3-methylimidazolium acetate used in Comparative Examples and Comparative Reference Examples was a product manufactured by Tokyo Chemical Industry Co., Ltd.

[0132] [Example 1] 5.00 g of 1,3-bis(3-methoxypropyl)imidazolium acetate was added to the flask and maintained at 50°C. 1.00 g of microcrystalline cellulose (Avicel (registered trademark) PH-101) was added at 50°C and stirred until the microcrystalline cellulose was completely dissolved by visual observation. 95.0 g of ultrapure water and 10 μL of cellulase (Sigma) were added and stirred for 4 days. The remaining cellulose residue was obtained by filtration and the glucose conversion rate was calculated. The results are shown in Table 1.

[0133] [Comparative Example 1] The results are shown in Table 1.

[0134] [Example 2] 0.20 g of 1,3-bis(3-methoxypropyl)imidazolium acetate, 0.5 g of glucose (manufactured by Tokyo Chemical Industry Co., Ltd., β-D-glucose (including α-D-glucose)), and 9.6 g of ultrapure water were added to the sample tube and stirred until the glucose was completely dissolved. After the glucose was completely dissolved, 0.05 g of dry yeast was added and the mixture was left to stand overnight. After filtering the insoluble matter, the amount of ethanol generated was quantified by GC (gas chromatography) to calculate the ethanol yield. The results are shown in Table 2.

[0135] [Example 3] 0.20 g of 1,3-bis(methoxyethoxypropyl)imidazolium acetate ([(MeOEtOPr)2Im][AcO]), 0.5 g of glucose (manufactured by Tokyo Chemical Industry Co., Ltd., β-D-glucose (including α-D-glucose)), and 9.6 g of ultrapure water were added to the sample tube, and stirred until the glucose was completely dissolved. After the glucose was completely dissolved, 0.05 g of dry yeast was added and allowed to stand overnight. After filtering the insoluble matter, the amount of ethanol generated was quantified by GC (gas chromatography) to calculate the ethanol yield. The results are shown in Table 2.

[0136] [Example 4] 0.20 g of 1,3-bis(ethoxypropyl)imidazolium acetate ([(EtOPr)2Im][AcO]), 0.5 g of glucose (manufactured by Tokyo Chemical Industry Co., Ltd., β-D-glucose (including α-D-glucose)), and 9.6 g of ultrapure water were added to the sample tube and stirred until the glucose was completely dissolved. After the glucose was completely dissolved, 0.05 g of dry yeast was added and the mixture was allowed to stand overnight. After filtering the insoluble matter, the amount of ethanol generated was quantified by GC (gas chromatography) to calculate the ethanol yield. The results are shown in Table 2.

[0137] [Comparative Example 2] The results are shown in Table 2.

[0138] [Reference Example 1] and [Comparative Reference Example 1] Antibacterial test (measurement of minimum inhibitory concentration (MIC value)) was performed on yeast (Saccharomycs cerevisiae) of 1,3-bis(3-methoxypropyl)imidazolium acetate and 1-ethyl-3-methylimidazolium acetate. The smaller the MIC value, the greater the degree of inhibition of enzyme and / or microbial activity. The results are shown in Table 3.

[0139] [Table 1]

[0140] [Table 2] Onium Salt (1) Ethanol yield (%) Example 2 <![CDATA[[(MeOPr)2Im][AcO]]]> 66.64 Example 3 <![CDATA[[(MeOEtOPr)2Im][AcO]]]> 53.77 Example 4 <![CDATA[[(EtOPr)2Im][AcO]]]> 46.38 Comparative Example 2 1-Ethyl-3-methylimidazolium acetate 14.2

[0141] [Table 3] Onium Salt (1) MIC value (%) Reference Example 1 <![CDATA[[(MeOPr)2Im][AcO]]]> 5 Comparative Reference Example 1 1-Ethyl-3-methylimidazolium acetate 0.5

[0142] [Example 5] Add 2.00 g of 1,3-bis(3-methoxypropyl)imidazolium acetate to the sample tube, add 0.50 g of microcrystalline cellulose (Avicel (registered trademark) PH-101), and heat and stir at 80°C for 3 hours. After visually confirming that the microcrystalline cellulose is completely dissolved, add 38.0 g of ultrapure water and 20 μL of cellulase (Sigma), and stir at 50°C for 10 hours. Then, add 0.50 g of dry yeast and stir slowly at 30°C. After 7 hours, filter out the insoluble matter, quantify the amount of ethanol generated by GC (gas chromatography), and calculate the ethanol yield. The results are shown in Table 4.

[0143] [Comparative Example 3] The results are shown in Table 4, except that 1,3-bis(3-methoxypropyl)imidazolium acetate used in Example 5 was replaced with 1-ethyl-3-methylimidazolium acetate.

[0144] [Comparative Example 4] The same procedure as in Example 5 was performed except that 1,3-bis(3-methoxypropyl)imidazolium acetate used in Example 5 was not added and 2.00 g of 1,3-bis(3-methoxypropyl)imidazolium acetate was replaced with 2.00 g of ultrapure water. In this case, microcrystalline cellulose was not dissolved. The results are shown in Table 4.

[0145] [Table 4] Onium Salt (1) Ethanol yield (%) Example 5 <![CDATA[[(MeOPr)2Im][AcO]]]> 51.5 Comparative Example 3 1-Ethyl-3-methylimidazolium acetate 16.0 Comparative Example 4 none 27.3 Industrial Applicability

[0146] According to the present invention, a composition containing an onium salt that can smoothly carry out an enzyme reaction and fermentation using a microorganism can be provided. In addition, according to the present invention, a method for producing a cellulose hydrolyzate by hydrolyzing cellulose using an enzyme in the presence of an onium salt that can smoothly carry out an enzyme reaction and fermentation using a microorganism can be provided. Furthermore, according to the present invention, a method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolyzate using a microorganism in the presence of the onium salt can be provided.

Claims

1. An onium salt composition, characterized in that The onium salt composition comprises an onium salt represented by the following formula (1), a cellulose-containing biomass, and an enzyme. Formula (1): In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom, or a hydrocarbon group containing or not containing heteroatoms; R 1 ~R 3 Containing or not containing branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure or do not form a ring structure; R 4 It refers to a hydrocarbon group which may or may not contain heteroatoms, and may or may not contain branching and / or ring structures and / or double bonds.

2. The onium salt composition according to claim 1, wherein The cellulose-containing biomass is dissolved in the onium salt represented by the above formula (1).

3. The onium salt composition according to claim 1 or 2, wherein The onium salt composition further contains water.

4. The onium salt composition according to claim 3, wherein The concentration of the onium salt represented by the formula (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition.

5. An onium salt composition, characterized in that The onium salt composition comprises an onium salt represented by the following formula (1), glucose and a microorganism. Formula (1): In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom, or a hydrocarbon group containing or not containing heteroatoms; R 1 ~R 3 Containing or not containing branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure or do not form a ring structure; R 4 It refers to a hydrocarbon group which may or may not contain heteroatoms, and may or may not contain branching and / or ring structures and / or double bonds.

6. The onium salt composition according to claim 5, wherein Glucose is dissolved in the onium salt represented by the above formula (1).

7. The onium salt composition according to claim 5 or 6, wherein The onium salt composition further contains water.

8. The onium salt composition according to claim 7, wherein The concentration of the onium salt represented by the formula (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition.

9. An onium salt composition, characterized in that: The onium salt composition comprises an onium salt represented by the following formula (1), cellulose-containing biomass, enzymes, glucose and microorganisms. Formula (1): In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom, or a hydrocarbon group containing or not containing heteroatoms; R 1 ~R 3 Containing or not containing branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure or do not form a ring structure; R 4 It refers to a hydrocarbon group which may or may not contain heteroatoms, and may or may not contain branching and / or ring structures and / or double bonds.

10. The onium salt composition according to claim 9, wherein The onium salt composition further contains water.

11. The onium salt composition according to claim 10, wherein The concentration of the onium salt represented by the formula (1) is 0.1% by mass or more and 20% by mass or less relative to 100% by mass of the total amount of the onium salt composition.

12. A method for producing a cellulose hydrolyzate, characterized in that: In the presence of an onium salt represented by the following formula (1) and water, cellulose contained in cellulose-containing biomass is hydrolyzed by an enzyme, Formula (1): In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom, or a hydrocarbon group containing or not containing heteroatoms; R 1 ~R 3 Containing or not containing branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure or do not form a ring structure; R 4 It refers to a hydrocarbon group which may or may not contain heteroatoms, and may or may not contain branching and / or ring structures and / or double bonds.

13. The method for producing a cellulose hydrolyzate according to claim 12, comprising the following steps (1) to (3): Step (1): a step of dissolving cellulose-containing biomass in the presence of the onium salt represented by the formula (1); Step (2): a step of adding water and an enzyme to the solution obtained in step (1), and Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolyzate.

14. A method for producing an alcohol and / or an organic acid, characterized in that: The cellulose hydrolyzate is fermented by microorganisms in the presence of an onium salt represented by the following formula (1) and water. Formula (1): In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom, or a hydrocarbon group containing or not containing heteroatoms; R 1 ~R 3 Containing or not containing branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure or do not form a ring structure; R 4 It refers to a hydrocarbon group which may or may not contain heteroatoms, and may or may not contain branching and / or ring structures and / or double bonds.

15. The method for producing an alcohol and / or an organic acid according to claim 14, comprising the following steps (1) to (3): Step (1): a step of mixing the onium salt represented by the formula (1), a cellulose hydrolyzate, water and a microorganism, Step (2): a step of fermenting the cellulose hydrolyzate with microorganisms in the solution to which the microorganisms are added obtained in step (1) to produce alcohol and / or organic acid, and Step (3): a step of separating alcohol and / or organic acid from the solution containing alcohol and / or organic acid obtained in step (2).

16. The method for producing an alcohol and / or an organic acid according to claim 14 or 15, wherein: The alcohol is ethanol.

17. A method for producing an alcohol and / or an organic acid, characterized in that: The production method is a method for producing alcohol and / or organic acid from cellulose-containing biomass in the presence of an onium salt represented by the following formula (1) and water, and comprises the following steps (1) to (6): Formula (1): In formula (1), R 1 ~R 3 Same or different, R 1 and R 2 represents a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, R 3 represents a hydrogen atom, or a hydrocarbon group containing or not containing heteroatoms; R 1 ~R 3 Containing or not containing branched chains and / or ring structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 The nitrogen atom and the carbon atom to which they are bonded are bonded together to form a ring structure or do not form a ring structure; R 4 denotes a hydrocarbon group containing or not containing heteroatoms, containing or not containing branches and / or ring structures and / or double bonds, Step (1): a step of dissolving cellulose-containing biomass in the presence of the onium salt represented by the formula (1); Step (2): a step of adding water and an enzyme to the solution obtained in step (1), Step (3): stirring the solution obtained in step (2) and hydrolyzing cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolyzate. Step (4): a step of adding microorganisms to the solution containing the cellulose hydrolyzate obtained in step (3), Step (5): a step of fermenting the cellulose hydrolyzate with microorganisms in the solution to which the microorganisms are added obtained in step (4) to produce alcohol and / or organic acid, and Step (6): a step of separating alcohol and / or organic acid from the solution containing alcohol and / or organic acid obtained in step (5).

18. The manufacturing method according to claim 14 or claim 17, wherein: The solution containing the onium salt represented by the formula (1) is recovered, the onium salt is separated from the recovered solution, and the onium salt is recycled.

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