Onium salt composition, and method for producing hydrolysate of cellulose, alcohol, and / or organic acid in the presence of onium salt composition

Abstract

To provide a composition containing an onium salt that enables the successful execution of enzymatic reactions and microbial fermentation.SOLUTION: An onium salt composition comprises an onium salt represented by the formula (1), cellulose-containing biomass and an enzyme. Formula (1) (where R1-R4 are as defined in the specifications).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] The use of biomass derived from plants is expected to be an alternative to petroleum resources, and attempts are being made to use biomass as energy, various materials, etc. In order to effectively use biomass as an energy source or other raw material, it is desirable to decompose and saccharify the biomass into a carbon source that can be easily utilized by animals or microorganisms.

[0003] One known method of decomposition and saccharification is to dissolve the cellulose contained in biomass in an ionic liquid, decompose it into glucose using enzymes such as cellulase, and then ferment the glucose using microorganisms to produce alcohol and / or organic acids.

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

[0005] Furthermore, Non-Patent Document 1 describes, as ionic liquids that dissolve cellulose, ionic liquids having dialkylimidazolium as the cation, specifically, 1-ethyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1,3-dimethylimidazolium dialkyl phosphate. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2013-135641 A [Non-patent literature]

[0007] [Non-Patent Document 1] Green Chemistry, 2015, Vol. 17, pp. 694-714. Summary of the Invention [Problem to be solved by the invention]

[0008] The onium salt, which is an ionic liquid described in the prior art documents, inhibits both enzymatic reactions and fermentation by microorganisms, and therefore, after dissolving the cellulose contained in the biomass with the onium salt, which is an ionic liquid, the onium salt must be removed.

[0009] In the context of such prior art, an objective of the present invention is to provide a composition containing an onium salt that can be successfully subjected to both an enzymatic reaction and fermentation by a microorganism.Another objective of the present invention is to provide a method for producing a cellulose hydrolysate by enzymatically hydrolyzing cellulose in the presence of an onium salt that can be successfully subjected to both an enzymatic reaction and fermentation by a microorganism.A further objective of the present invention is to provide a method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolysate with a microorganism in the presence of the onium salt. [Means for solving the problem]

[0010] The present inventors have conducted extensive research into onium salts that can successfully carry out both enzymatic reactions and microbial fermentation, and into enzymatic reactions and microbial fermentation in the presence of onium salts, and have completed the present invention.

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

[18] . [1] An onium salt composition comprising an onium salt represented by the following formula (1), a cellulose-containing biomass, and an enzyme: Formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different, R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 may be bonded together with the nitrogen atom and carbon atom to which R is bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond. [2] The onium salt composition according to [1], wherein a cellulose-containing biomass is dissolved in an onium salt represented by the formula (1). [3] The onium salt composition according to [1] or [2], further comprising water. [4] The onium salt composition according to [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 comprising an onium salt represented by the following formula (1), glucose, and a microorganism. Formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different, R 1 and R 2is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 may be bonded together with the nitrogen atom and carbon atom to which R is bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond. [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], further comprising water. [8] The onium salt composition according to [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 comprising an onium salt represented by the following formula (1), a cellulose-containing biomass, an enzyme, glucose, and a microorganism: Formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different, R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3may be bonded together with the nitrogen atom and carbon atom to which R is bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

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

[11] The onium salt composition according to

[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 hydrolysate, comprising enzymatically hydrolyzing cellulose contained in a cellulose-containing biomass in the presence of an onium salt represented by the following formula (1) and water: Formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different, R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 may be bonded together with the nitrogen atom and carbon atom to which R is bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

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

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

[14] A method for producing alcohol and / or organic acid, comprising fermenting a cellulose hydrolysate with a microorganism in the presence of an onium salt represented by the following formula (1) and water: Formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different, R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 may be bonded together with the nitrogen atom and carbon atom to which R is bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

[15] A method for producing the alcohol and / or 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 hydrolysate, water, and a microorganism. Step (2): A step of producing alcohol and / or organic acid by fermenting the cellulose hydrolysate with the microorganisms in the solution obtained in step (1) to which the microorganisms have been added. Step (3): A step of separating the alcohol and / or organic acid from the solution containing the alcohol and / or organic acid obtained in step (2).

[16] The method for producing an alcohol according to

[14] or

[15] , wherein the alcohol is ethanol.

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

[18] A method for producing the onium salt according to

[14] or

[17] , comprising recovering a solution containing the onium salt represented by formula (1), separating the onium salt from the recovered solution, and recycling the onium salt. Effect of the Invention

[0012] According to the present invention, a composition containing an onium salt capable of successfully carrying out an enzymatic reaction and fermentation by a microorganism can be provided. According to the present invention, a method for producing a cellulose hydrolysate can be provided by enzymatically hydrolyzing cellulose in the presence of an onium salt capable of successfully carrying out an enzymatic reaction and fermentation by a microorganism. According to the present invention, a method for producing an alcohol and / or an organic acid can be provided by fermenting a cellulose hydrolysate with a microorganism in the presence of the onium salt. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. One embodiment of the present invention relates to an onium salt composition (hereinafter referred to as onium salt composition (1)) containing an onium salt represented by the following formula (1) (hereinafter referred to as onium salt (1)), a cellulose-containing biomass, and an enzyme.

[0014] Formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different, R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom.1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of R 1 ~R 3 may be bonded together with the nitrogen atom and carbon atom to which R is bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

[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 linear or may contain a branched and / or cyclic 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, "a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms" refers to 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) The hydrogen atom of one -CH2- (methylene group) and the hydrogen atom of another -CH2- (methylene group) are -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 substitutions by these structures are determined by R 1 , R 2 There is no particular limitation as long as the number of heteroatoms therein is within the range of 1 to 5.

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

[0019] In the present invention, the structure in which (i) the bond between two adjacent carbon atoms and / or (ii) the hydrogen atom of one -CH2- (methylene group) of a hydrocarbon group is replaced with a -O- or -S- structure may be an ether structure, a thioether structure, or an epoxy structure or 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 may be an epoxy group, a thioepoxy group, or the like.

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

[0021] R 1 and R 2 and the nitrogen atom on the imidazole ring to which each of 1 or R 2 It is more preferable that 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 linear or may contain a branched and / or cyclic structure and / or a double bond. Examples of the hydrocarbon group having 2 to 12 carbon atoms and not containing heteroatoms include, but are not limited to, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group.

[0023] In formula (1), R 1 and R 2 In the above, examples of the "hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms" include a linear or branched alkyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, a linear or branched alkenyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms, a linear 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, which may be branched, a cycloalkenyl group having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms, which may be branched, an aryl group having 6 to 12 carbon atoms and containing 1 to 5 heteroatoms, and an aralkyl group having 7 to 12 carbon atoms and containing 1 to 5 heteroatoms, which may be 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 optionally branched cycloalkyl groups having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms. The "linear or branched alkyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms" is preferably a linear or branched alkyl group having 3 to 10 carbon atoms and containing 1 to 3 heteroatoms. In another embodiment, it is preferably a linear or branched alkyl group having 3 to 10 carbon atoms and containing 1 or 2 heteroatoms, more preferably a linear or branched alkyl group having 4 to 7 carbon atoms and containing 1 or 2 heteroatoms. The "linear or branched alkenyl group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms" is preferably a linear or branched alkenyl group having 3 to 10 carbon atoms and containing 1 to 3 heteroatoms. In another embodiment, it is preferably a linear or branched alkenyl group having 3 to 10 carbon atoms and containing 1 to 2 heteroatoms, more preferably a linear or branched alkenyl group having 4 to 7 carbon atoms and containing 1 to 2 heteroatoms. The "cycloalkyl group having 3 to 12 carbon atoms and containing 1 to 5 heteroatoms, which may have a branch" is preferably a cycloalkyl group having 3 to 10 carbon atoms and containing 1 to 3 heteroatoms. In another embodiment, it is preferably a cycloalkyl group having 3 to 10 carbon atoms and containing 1 to 2 heteroatoms, which may have a branch, and more preferably a cycloalkyl group having 4 to 7 carbon atoms and containing 1 to 2 heteroatoms.

[0024] In formula (1), R 1 and R 2In the above, examples of the hydrocarbon group having 2 to 12 carbon atoms and not containing a heteroatom include, but are not limited to, 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 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, and a 2,4,6-trimethylphenyl group. In the above, the hydrocarbon group having 2 to 12 carbon atoms and not containing a heteroatom (i) a bond between two adjacent carbon atoms, and / or (ii) The hydrogen atom of one -CH2- (methylene group) and the hydrogen atom of another -CH2- (methylene group) are -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)- When substituted with structures such as >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., it becomes a "hydrocarbon group having 2 to 12 carbon atoms and 1 to 5 heteroatoms".

[0025] 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-heptyloxypropyl, 3-octyloxypropyl, 3-nonyloxypropyl, and 3-(2-ethylhexyl-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-ne 4-pentyloxybutyl, 4-hexyloxybutyl, 4-cyclohexyloxybutyl, 4-heptyloxybutyl, 4-octyloxybutyl, 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-allyloxyhexyl, 6-butoxyhexyl, 6-(1-methylpropoxy)hexyl, 6-(2-methylpropoxy)hexyl, 6-(1,1-dimethylethoxy)hexyl, 6-pentyloxyhexyl, 6-neo Pentyloxyhexyl, 6-hexyloxyhexyl, 6-cyclohexyloxyhexyl, (2-methoxycyclohexan-1-yl)methyl, (2-ethoxycyclohexan-1-yl)methyl, (2-propoxycyclohexan-1-yl)methyl, (2-isopropoxycyclohexan-1-yl)methyl, (2-butoxycyclohexan-1-yl)methyl, [2-(1-methylpropoxy)cyclohexan-1-yl]methyl, [2-(2-methylpropoxy)cyclohexan-1-yl]methyl, [2-(1,1-di 2-[(furan-2-yl)methylthio]ethyl, 2-(methylsulfonyl)ethyl, (thiophen-2-yl)methyl, p-methoxyphenyl, p-ethoxyphenyl, 3,4-methylenedioxyphenyl, 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-methylenedioxyphenyl, Examples of the aryl group include phenyl, 3,4-methylenedioxybenzyl, and (7-oxabicyclo[2,2,1]heptan-2-yl)methyl. Preferred are 2-methoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-isopropoxypropyl, 3-butoxypropyl, 3-(2-methoxyethoxy)propyl, 3-methylthiopropyl, and 3-(dimethylamino)propyl. More preferred are 2-methoxyethyl, 3-methoxypropyl, and 3-(2-methoxyethoxy)propyl, but the present invention is not limited to these.

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

[0027] In formula (1), R 3 represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. The "hydrocarbon group which may contain a heteroatom" may be linear, branched and / or containing a ring structure and / or a double bond. R 3 In the above formula, the hydrocarbon group may contain or not contain a heteroatom.

[0028] In formula (1), R 3 When R is a hydrocarbon group containing no heteroatom, it preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 3 carbon atoms. 3 When is a hydrocarbon group containing a hetero atom, it preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0029] In formula (1), R 3 When it contains a heteroatom, the number of heteroatoms is preferably 1 to 5, and more preferably 1 to 2. The number of carbon atoms in the hydrocarbon group is 2 or more, preferably 2 to 12, more preferably 2 to 8, and further preferably 2 to 4.

[0030] In formula (1), R 3 When is a hydrocarbon group containing a hetero atom, examples of the "hetero atom" include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.

[0031] R 3 When is a hydrocarbon group containing a hetero atom, examples of the "hetero atom" include 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 3In the above, the "hydrocarbon group containing a heteroatom" refers to a hydrocarbon group that does not contain a heteroatom, and / or (i) a bond between two adjacent carbon atoms, (ii) The hydrogen atom of one -CH2- (methylene group) and the hydrogen atom of another -CH2- (methylene group) are -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)-, >N C(=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)-, and the like are substituted with structures such as these. The number and combination of substitutions with these structures are not particularly limited. 3 The number of heteroatoms therein is preferably 1 to 5, and more preferably 1 or 2.

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

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

[0035] R 3 In the case where the compound contains two or more -O- and / or -S- structures, the number of carbon atoms between the -O- and / or -S- structures is desirably two or more.

[0036] In formula (1), R 3 In the above, examples of the "hydrocarbon group which may contain a heteroatom" include a linear or branched alkyl group which may contain a heteroatom, a linear or branched alkenyl group which may contain a heteroatom, a linear or branched alkynyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom and may be branched, a cycloalkenyl group which may contain a heteroatom and may be branched, an aryl group which may contain a heteroatom and may be branched, an aralkyl group which may contain a heteroatom and may be branched, etc. Preferred are a linear or branched alkyl group which may contain a heteroatom, a linear or branched alkenyl group which may contain a heteroatom, and a cycloalkyl group which may contain a heteroatom and may be branched. The "linear or branched alkyl group which may contain a heteroatom" is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may contain 1 to 5 heteroatoms. In another embodiment, it is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may contain 1 to 2 heteroatoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms which may contain 1 to 2 heteroatoms, and even more preferably a linear or branched alkyl group having 1 to 4 carbon atoms which may contain 1 to 2 heteroatoms. In yet another embodiment, it is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms. The "linear or branched alkenyl group which may contain a heteroatom" is preferably a linear or branched alkenyl group having 2 to 12 carbon atoms which may contain 1 to 5 heteroatoms. In another embodiment, it is preferably a linear or branched alkenyl group having 2 to 12 carbon atoms which may contain 1 to 2 heteroatoms, more preferably a linear or branched alkenyl group having 2 to 8 carbon atoms which may contain 1 to 2 heteroatoms, and even more preferably a linear or branched alkenyl group having 2 to 4 carbon atoms which may contain 1 to 2 heteroatoms. In yet another embodiment, it is preferably a linear or branched alkenyl group having 2 to 12 carbon atoms, more preferably a linear or branched alkenyl group having 2 to 8 carbon atoms, and even more preferably a linear or branched alkenyl group having 2 to 3 carbon atoms. The "cycloalkyl group which may contain a heteroatom or may have a branch" is preferably a cycloalkyl group having 3 to 12 carbon atoms which may contain 1 to 5 heteroatoms and which may have a branch. In another embodiment, it is preferably a cycloalkyl group having 3 to 12 carbon atoms which may contain 1 to 2 heteroatoms and which may have a branch, more preferably a cycloalkyl group having 3 to 8 carbon atoms which may contain 1 to 2 heteroatoms and which may have a branch, and even more preferably a cycloalkyl group having 3 to 4 carbon atoms which may contain 1 to 2 heteroatoms. In yet another embodiment, it is preferably a cycloalkyl group having 3 to 12 carbon atoms which may have a branch, more preferably a cycloalkyl group having 3 to 8 carbon atoms which may have a branch, and even more preferably a cycloalkyl group having 3 carbon atoms.

[0037] In formula (1), R 3In the above, specific examples of the "hydrocarbon group not containing a hetero atom" include 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 ... Examples of the aryl group include a methyl group, an ethyl 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, and a 2,4,6-trimethylphenyl group. Of these, 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, and a hexyl group are preferred, and a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group are more preferred.

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

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

[0040] In formula (1), R 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are attached to form a ring structure. 1 and R 2 , R 1 and R 3 , or R 2and R 3 Examples of such structures include, but are not limited to, a cyclic structure formed by linking the ring structure with a hydrocarbon having 2 to 24 carbon atoms and containing 2 to 10 heteroatoms.

[0041] In formula (1), R 4 represents a hydrocarbon group, which may be linear or may contain a branched and / or cyclic 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 further preferably a hydrocarbon group having 1 to 3 carbon atoms.

[0042] In formula (1), R 4 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. Preferred are a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 1 to 12 carbon atoms, a linear or branched alkynyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may be branched, a cycloalkenyl group having 3 to 12 carbon atoms which may be branched, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms which may be branched, and more preferred are 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), R 4Specific examples of the "hydrocarbon group" include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a 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, a undecyl group, a dodecyl group, a vinyl group, an ethynyl group, a propenyl group, a 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), R 4 -CO-O - Specific examples of the anion represented by the formula (I) include acetate ion, propionate ion, acrylate ion, propargyl ion, butyrate ion, isobutyrate ion, methacrylate ion, crotonate ion, tetrolate ion, cyclopropane carboxylate ion, valerate ion, isovalerate ion, pivalate ion, angelic acid ion, tiglic acid ion, cyclobutane carboxylate ion, caproate ion, cyclopentane carboxylate ion, enanthate ion, sorbic acid ion, cyclohexane carboxylate ion, benzoate ion, caprylate ion, 2-ethylhexyl carboxylate ion, and toluate ion. Examples of the cation ion include 2-norbornanecarboxylate ion, pelargonate ion, cinnamate ion, caprate ion, adamantanecarboxylate ion, geranate ion, undecylate ion, laurate ion, and naphthalenecarboxylate ion. Of these, preferred are acetate ion, propionate ion, acrylate ion, propargylate ion, butyrate ion, isobutyrate ion, methacrylate ion, crotonate ion, tetrolate ion, valerate ion, isovalerate ion, and pivalate ion. Particularly preferred are acetate ion, acrylate ion, and methacrylate ion, although the present invention is not limited to these.

[0045] 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-methoxy 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[(oxolan-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)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 )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 imidazolium, 1,3-bis(4-heptyloxybutyl)imidazolium, 1,3-bis(4-octyloxybutyl)imidazolium, 1,3-bis{4-[(2-ethylhexyl)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-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-(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-methoxycyclohexan-1-yl)methyl]imidazolium, 1,3-bis[(2-ethoxycyclohexan-1-yl)methyl]imidazolium, 1,3- Bis[(2-propoxycyclohexan-1-yl)methyl]imidazolium, 1,3-bis[(2-isopropoxycyclohexan-1-yl)methyl]imidazolium, 1,3-bis[(2-butoxycyclohexan-1-yl)methyl]imidazolium, 1,3-bis{[2-(1-methylpropoxy)cyclohexan-1-yl]methyl}imidazolium, 1,3-bis{[2-(2-methylpropoxy)cyclohexan-1-yl]methyl}imidazolium, 1,3-bis{[2-(1,1-dimethylethoxy)cyclohexan-1-yl] methyl}imidazolium, 1,3-bis[(2-pentyloxycyclohexan-1-yl)methyl]imidazolium, 1,3-bis[(2-neopentyloxycyclohexan-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]heptan-2-yl)methyl}imidazolium, 1-methoxypropyl-3-methylthiopropylimidazolium, 1,3-bis(3-methoxypropyl)-2-methylimidazolium, 1,3-bis(2-methoxyethyl)-2-methylimidazolium, and the like are included, and 1,3-bis(3-methoxypropyl)-2-methylimidazolium is preferable. 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, 1,3-bis(2-methoxyethyl)-2-methylimidazolium Imidazolium, more 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 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 one anion selected from the group consisting of an acetate ion, an acrylate ion, and a methacrylate ion.

[0047] More specifically, the onium salt represented by formula (1) includes 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, 1,3-bis(2-methoxyethyl)-2-methylimidazolium methacrylate, 1, Examples of the imidazolium methacrylate include 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, and 1,3-bis[3-(2-methoxyethoxy)propyl]imidazolium methacrylate. Preferred are 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 a production method (production method 1) shown in the following reaction formula 1. Specifically, a person skilled in the art can easily produce it by referring to the production method of 1,3-bis(3-methoxypropyl)imidazolium acetate shown in [Production Example 1].

[0049] Reaction Scheme 1: [ka] (In reaction scheme 1, R 1 , R 2 , R 3 and R 4 are each as defined above.)

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

[0051] R 1 -NH2 (Formula (2)) or R 2Specific examples of the amine compound represented by -NH2 (formula (3)) 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-ethylhexyl-1-yl)oxyethylamine, 2-(2,4,6-trimethylphenoxy)ethylamine, 2-(benzyloxy)ethylamine, amine, 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-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)oxybutylamine, 5-methoxypentylamine, 5-ethoxypentylamine amine, 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)hexylamine, 6-Pentyloxyhexylamine, 6-Neopentyloxyhexylamine, 6-Hexyloxyhexylamine, 6-Cyclohexyloxyhexylamine, 2-Methoxycyclohexyl-1-ylmethylamine, (2-Ethoxycyclohexan-1-yl)methylamine, (2-Propoxycyclohexan-1-yl)methylamine, (2-Isopropoxycyclohexan-1-yl)methylamine, (2-Butoxycyclohexyl -1-yl)methylamine, [2-(1-methylpropoxy)cyclohexan-1-yl]methylamine, [2-(2-methylpropoxy)cyclohexan-1-yl]methylamine, [2-(1,1-dimethylethoxy)cyclohexan-1-yl]methylamine, (2-pentyloxycyclohexan-1-yl)methylamine, (2-neopentyloxycyclohexan-1-yl)methylamine, 2-methylthioethylamine, 3-methylthiopropylamine, 1-(methoxy) Examples of suitable amines include (dimethyl)propylamine, (oxolan-2-yl)methylamine, (furan-2-yl)methylamine, 2-[(furan-2-yl)methylthio]ethylamine, 2-(methylsulfonyl)ethylamine, (thiophen-2-yl)methylamine, p-methoxyphenylamine, p-ethoxyphenylamine, 3,4-methylenedioxyaniline, 3,4-methylenedioxybenzylamine, and (7-oxabicyclo[2,2,1]heptan-2-yl)methylamine. Preferred are 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-(2-methoxyethoxy)propylamine, 3-methylthiopropylamine, and 3-(dimethylamino)propylamine. More preferred are 2-methoxyethylamine, 3-methoxypropylamine, and 3-(2-methoxyethoxy)propylamine, but the present invention is not limited thereto. 1 -NH2 or R 2 The amine compounds represented by -NH2 may be the same or different.

[0052] R 3Specific examples of the aldehyde compound represented by -CHO (formula (4)) include formaldehyde, acetaldehyde, propionaldehyde, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaaldehyde, vanillin, etc., and are preferably formaldehyde and acetaldehyde, but the present invention is not limited thereto. As the formaldehyde, a cyclic oligomer or polymer capable of generating formaldehyde in the reaction system, such as paraformaldehyde, trioxane, or tetraoxane, may be used.

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

[0054] R 4 Examples of the carboxylic acid represented by -COOH (formula (5)) include acetic acid, propionic acid, acrylic acid, propargylic acid, butyric acid, isobutyric acid, methacrylic acid, crotonic acid, tetrolic acid, cyclopropanecarboxylic acid, valeric acid, isovaleric acid, pivalic acid, angelic acid, tiglic acid, cyclobutanecarboxylic acid, caproic acid, cyclopentanecarboxylic acid, enanthic acid, sorbic acid, cyclohexanecarboxylic acid, benzoic acid, caprylic acid, 2-ethylhexylcarboxylic acid, toluic acid, 2-norbornanecarboxylic acid, and peralic acid. Examples of the acidic acid include acetic acid, propionic acid, acrylic acid, propargylic acid, butyric acid ion, isobutyric acid, methacrylic acid, crotonic acid, tetrolic acid, valeric acid, isovaleric acid, and pivalic acid. However, the present invention is not limited to these.

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

[0056] R 1 -NH2 (Formula (2)) and R 2 The amount of the amine compound represented by —NH2 (formula (3)) used is 1 mole of glyoxal per mole of 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 and R 2 When R 1 -NH2 and R 2 The ratio (molar ratio) of R 1 -NH2:R 2 -NH2=0:100~100:0. 1 -NH2:R 2 -NH2=0:100 or 100:0, R 1 =R 2 It becomes. R 1 -NH2:R 2 When the -NH2 ratio is not 0:100 or 100:0, the onium salt (1) obtained by production method 1 will be a mixture of compounds represented by the following formulas. Both of the compounds represented by the following formulas (1') and (1'') are included in the onium salt represented by formula (1), and the mixture may be used as an onium salt composition described below. Optionally, the mixture may be purified to obtain a single desired compound and then used as onium salt (1).

[0057] [ka]

[0058] R 3The aldehyde compound represented by -CHO (formula (4)) may be used as it is in the form of an aqueous solution or an alcohol solution such as methanol, butanol, 2-ethylhexanol, etc. 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] 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 production method 1, a solvent may or may not be used. When a solvent is used, the solvent to be 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, and water, and preferably alcohol solvents and water.

[0061] Also, a previously prepared onium salt (1) can be used as a reaction solvent in the production method 1. Two or more kinds of solvents can be mixed and used 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 part by mass of glyoxal.

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

[0063] When carrying out Production Method 1, the reaction pressure is usually atmospheric pressure, but depending on the raw materials and / or solvent used, the reaction may be carried out by pressurizing the reaction system to a pressure of atmospheric pressure to 1 MPa.

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

[0065] After completion of the reaction in the production method 1, the onium salt (1) may be purified by a known purification method or may not be purified. Examples of the purification method include, but are not limited to, concentration, separation, recrystallization, dialysis, adsorption, filtration, etc.

[0066] The cellulose-containing biomass contained in the onium salt composition (1) is not particularly limited. Specific examples include biomass containing natural fiber products such as pulp, cotton, and hemp, regenerated fiber products such as rayon, cupra, and acetate, various straws such as rice straw, bagasse, and agricultural waste such as wood chips, waste paper, and various waste materials such as construction waste, etc. When biomass containing the above-mentioned natural fiber products such as pulp, cotton, and hemp, regenerated fiber products such as rayon, cupra, and acetate, various straws such as rice straw, bagasse, and agricultural waste such as wood chips, waste paper, and various waste materials such as construction waste, etc. is dissolved in the onium salt (1), it is preferable to use cut pieces of these in order to shorten the time until dissolution.

[0067] In the present invention, cellulose refers to a polymer in which glucose is polymerized by β-1,4-glucoside bonds and its derivatives. The degree of polymerization of glucose in cellulose is not particularly limited, but is preferably 200 or more. Examples of the derivatives include carboxymethylated, aldehyded, esterified, and other derivatives. Cellulose may also contain cellooligosaccharides and cellobiose, which are partial decomposition products of cellulose. Cellulose may also be a complex with lignocellulose, which is a complex with β-glucoside, lignin, and / or hemicellulose, or a complex with pectin or the like. The onium salt of the present invention can dissolve cellulose at 10°C to 50°C, even if it is a complex with lignocellulose, pectin, or the like. Cellulose may be crystalline cellulose or noncrystalline cellulose, but is preferably crystalline cellulose. Cellulose may be naturally derived or artificially synthesized. The origin of cellulose is not particularly limited. It may be derived from plants, fungi, or bacteria.

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

[0069] In this specification, cellulose hydrolysis refers to the hydrolysis of β-1,4-glucosidic bonds in cellulose to produce reducing sugars such as glucose and cellobiose. Also, cellulose hydrolysates are reducing sugars such as glucose and cellobiose produced by hydrolysis of cellulose.

[0070] Endoglucanases are enzymes commonly referred to as cellulases that cleave cellulose from the interior of the molecule to produce glucose, cellobiose, and cellooligosaccharides (with a degree of polymerization of 3 or more and usually, but not limited to, 10 or less). Endoglucanases are representative examples of enzymes that hydrolyze amorphous cellulose, including, but not limited to, endoglucanases derived from Trichoderma reesei (particularly, EGII).

[0071] Cellobiohydrolase decomposes cellulose from either the reducing or non-reducing end to release cellobiose. Cellobiohydrolase is a representative example of an enzyme that hydrolyzes crystalline cellulose. There are two types of cellobiohydrolase, called cellobiohydrolase 1 and cellobiohydrolase 2. Examples of cellobiohydrolases include, but are not limited to, cellobiohydrolase derived from Trichoderma reesei (particularly, CBH2).

[0072] β-Glucosidase is an exo-type hydrolase that cleaves glucose units from the non-reducing end of cellulose. β-Glucosidase cleaves the β1,4-glucosidic bond between the aglycone or sugar chain 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 called β-glucosidase 1. Examples of β-glucosidase include, but are not limited to, β-glucosidase derived from Aspergillus aculeatus (particularly, BGL1).

[0073] The cellulase may be naturally derived, produced by recombinant DNA technology, or commercially available. It may be purified or may be an enzyme-producing microorganism as it is. It may be an enzyme preparation or a cellulase-expressing microorganism. For example, cellulases derived from the genus Clostridium such as Clostridium thermocellum, the genus Trichoderma such as Trichoderma reesei, or the genus Aspergillus such as Aspergillus oryzae and Aspergillus niger may be included. It may also be cellulases derived from hyperthermophilic archaea such as the genus Pyrococcus.

[0074] Two or more types of cellulases may be used in combination, preferably in a combination capable of hydrolyzing cellulose to glucose.

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

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

[0077] The onium salt composition (1) is preferably an onium salt composition (1) containing an onium salt (1), a cellulose-containing biomass, an enzyme, and water, in which the concentration of the onium salt (1) is 0.1% by mass or more and 20% by mass or less, based on the total amount (100% by mass) 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 aspect of the present invention relates to an onium salt composition (hereinafter referred to as onium salt composition (2)) containing 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 above onium salt (1).

[0079] The glucose contained in the onium salt composition (2) has the molecular formula CH 12 It is a monosaccharide molecule containing O6 and is a component of 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 produce organic acids such as acetic acid as well as 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 preferable. 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 Candida such as Pichia pastoris and Pichia stipitis, and yeasts of the genus Saccharomyces such as Saccharomyces cerevisiae and Schizosaccharomyces pombe. Examples of yeasts that can be used include yeasts of the genus Pichia, such as 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, and yeasts of the genus Kluyveromyces, such as Kluyveromyces marxianus and Kluyveromyces lactis. Among these, yeasts of the genus Saccharomyces are preferred from the viewpoint of industrial applicability, and Saccharomyces cerevisiae is more preferred. As the yeast, live yeast and dry yeast can be used. As the ethanol-producing filamentous fungus, there is no particular limitation, and examples thereof include filamentous fungi of the genus Mucor. The ethanol-producing bacterium is not particularly limited, and examples thereof include Zymomonas mobilis and recombinant Escherichia coli transformed to produce 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) containing the onium salt (1), glucose, a microorganism, and water, and more preferably an onium salt composition (2) containing the onium salt (1), glucose, a microorganism, and water, in which the glucose is dissolved in the onium salt (1).

[0084] The onium salt composition (2) is preferably an onium salt composition (2) containing an onium salt (1), glucose, a microorganism, and water, in which the concentration of the onium salt (1) is 0.1% by mass or more and 20% by mass or less, based on the total amount (100% by mass) 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 aspect of the present invention relates to an onium salt composition (hereinafter referred to as onium salt composition (3)) containing the onium salt (1) represented by the above-mentioned formula (1), a cellulose-containing biomass, an enzyme, glucose, and a microorganism. The onium salt (1), the cellulose-containing biomass, the enzyme, the glucose, and the microorganism contained in the onium salt composition (3) are the same as the above-mentioned onium salt (1), the cellulose-containing biomass, the enzyme, the glucose, and the microorganism, respectively.

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

[0087] The onium salt composition (3) is preferably an onium salt composition (3) containing an onium salt (1), a cellulose-containing biomass, an enzyme, glucose, a microorganism, and water, in which the concentration of the onium salt (1) is 0.1% by mass or more and 20% by mass or less, based on the total amount (100% by mass) 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 aspect of the present invention relates to a method for producing a cellulose hydrolysate, which comprises enzymatically hydrolyzing cellulose contained in a cellulose-containing biomass in the presence of an onium salt (1) represented by the above-mentioned formula (1) and water.

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

[0090] The ratio of the onium salt (1) to the cellulose-containing biomass used in step (1) of the method for producing a cellulose hydrolysate is preferably 1 to 30 mass%, more preferably 10 to 28 mass%, and particularly preferably 15 to 25 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 at which the cellulose-containing biomass is dissolved 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 hydrolysate 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, per 1 kg of the lysate obtained in the step (1).

[0094] The water and the enzyme to be added in the step (2) may be added separately or simultaneously, or a mixture of water and the enzyme may be added in advance.

[0095] The temperature at which water and the enzyme are added in the step (2) is preferably 10 to 60°C, more preferably 25 to 50°C, as 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 hydrolysate is carried out by stirring the solution obtained in step (2). The temperature during hydrolysis is preferably 10 to 60° C., and more preferably 25 to 50° C. The time for hydrolysis or stirring is preferably 4 to 100 hours, more preferably 12 to 96 hours, and particularly preferably 24 to 72 hours.

[0097] After completion of the step (3), the solution obtained in the step (3) can be filtered to separate the cellulose-containing biomass residue, thereby obtaining a solution containing a cellulose hydrolysate as a filtrate.

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

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

[0100] The method for producing an alcohol and / or an organic acid is more preferably a method for producing an alcohol, and even more preferably a method for producing ethanol.

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

[0102] The amounts of the onium salt, cellulose hydrolysate, water, and microorganisms mixed in the step (1) are 0.1 to 100 kg of the cellulose hydrolysate, 4 to 999 kg of water, and 0.01 to 10 kg of the microorganism, relative to 1 kg of the onium salt.

[0103] The temperature when the onium salt, cellulose hydrolysate, water and microorganisms 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 hydrolysate by the microorganism in step (2) of the method for producing alcohol and / or organic acid by fermenting the cellulose hydrolysate with the microorganism may be carried out by stirring the solution to which the microorganism has been added, or by leaving it to stand (without stirring).

[0105] The fermentation temperature of the microbial cellulose hydrolysate 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 hydrolysate by the microorganism in the step (2) is preferably from 1 to 48 hours, more preferably from 8 to 36 hours, and particularly preferably from 12 to 24 hours.

[0107] In the step (2), the cellulose hydrolysate is fermented with a microorganism 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] In the step (3) of the method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolysate with a microorganism, the alcohol and / or the organic acid can be separated by heating the solution containing the alcohol and / or the organic acid obtained in the step (2) and distilling the alcohol and / or the organic acid.

[0109] One aspect of the present invention is a method for producing an alcohol and / or an organic acid from a cellulose-containing biomass in the presence of an onium salt (1) represented by the above formula (1) and water, which comprises the following steps (1) to (6): Step (1): A step of dissolving a cellulose-containing biomass in the presence of an onium salt (1) represented by the above formula (1). Step (2): Adding water and an enzyme to the lysate obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing the cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolysate. Step (4): adding microorganisms to the solution containing the cellulose hydrolysate obtained in step (3). Step (5): A step of producing alcohol and / or organic acid by fermenting the cellulose hydrolysate with the microorganisms in the solution obtained in step (4) to which the microorganisms have been added. Step (6): A step of separating the alcohol and / or organic acid from the solution containing the 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 an alcohol and / or an organic acid from a cellulose-containing biomass is preferably 1 to 30 mass%, more preferably 10 to 28 mass%, and particularly preferably 15 to 25 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 from 0 to 120°C, more preferably from 20 to 100°C, and particularly preferably from 25 to 80°C.

[0112] The amount of water added in step (2) of the method for producing an alcohol and / or an 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, per 1 kg of the dissolved solution 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, per 1 kg of the lysate obtained in the step (1).

[0114] The water and the enzyme to be added in the step (2) may be added separately or simultaneously, or a mixture of water and the enzyme may be added in advance.

[0115] The temperature at which water and the enzyme are added in the step (2) is preferably 10 to 60°C, and more preferably 25 to 50°C, as the temperature of the solution obtained in the step (1).

[0116] The enzymatic hydrolysis of cellulose carried out in step (3) of the method for producing an alcohol and / or an organic acid from cellulose-containing biomass is carried out by stirring the solution obtained in step (2). The temperature during hydrolysis is preferably 10 to 60° C., and more preferably 25 to 50° C. The time for hydrolysis or stirring 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 an alcohol and / or an organic acid from cellulose-containing biomass is preferably 0.01 to 10 g, and more preferably 0.1 to 5 g, per 1 kg of the solution containing the cellulose hydrolysate obtained in step (3).

[0118] The temperature at which the microorganisms are added in step (4) is the temperature of the solution containing the cellulose hydrolysate obtained in step (3), and is preferably 5 to 60°C, more preferably 10 to 50°C, and particularly preferably 25 to 40°C.

[0119] The fermentation of the cellulose hydrolysate by the microorganism 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 microorganism obtained in step (4) has been added, or by leaving it to stand (without stirring).

[0120] The fermentation temperature of the cellulose hydrolysate 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 hydrolysate by the microorganism in the step (5) is preferably from 1 to 48 hours, more preferably from 8 to 36 hours, and particularly preferably from 12 to 24 hours.

[0122] In the step (5), the cellulose hydrolysate is fermented with a microorganism 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] In the step (6) of the method for producing an alcohol and / or an organic acid from a cellulose-containing biomass, the alcohol and / or the organic acid can be separated by heating the solution containing the alcohol and / or the organic acid obtained in the step (5) and distilling the alcohol and / or the organic acid.

[0124] One aspect of the present invention relates to a method for producing an alcohol and / or an organic acid by fermenting the aforementioned cellulose hydrolysate with a microorganism, or a method for producing an alcohol and / or an organic acid from a cellulose-containing biomass, in which a solution containing an onium salt (1) represented by the aforementioned formula (1) is recovered and the onium salt (1) is separated from the recovered solution, thereby recycling the onium salt (1).

[0125] The onium salt (1) or a liquid containing the onium salt (1) can be recovered 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 aforementioned method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolysate with a microorganism. The onium salt (1) or a liquid containing the onium salt (1) is recovered as a residue from the distillation of the alcohol and / or organic acid.

[0126] The onium salt (1) or a liquid containing the onium salt (1) can be recovered 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 above-mentioned method for producing an alcohol and / or an organic acid from cellulose-containing biomass. The onium salt (1) or a liquid containing the onium salt (1) is recovered as a residue from the distillation of the alcohol and / or organic acid.

[0127] The recovered onium salt (1) or a liquid containing the onium salt (1) can be recycled for use in the onium salt composition of the present invention, the method for producing a cellulose hydrolysate, the method for producing an alcohol and / or an organic acid by fermenting a cellulose hydrolysate with a microorganism, or the method for producing an alcohol and / or an organic acid from a cellulose-containing biomass. The recovered onium salt (1) or a liquid containing the onium salt (1) can also be used in other compositions, production methods, or applications that use an onium salt. EXAMPLES

[0128] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

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

[0130] [Production Example 1] In a nitrogen-purged 5L three-necked reactor, 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.) were charged. The resulting 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 H NMR data results 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] The 1-ethyl-3-methylimidazolium acetate used in the Comparative Examples and Comparative Reference Examples was manufactured by Tokyo Chemical Industry Co., Ltd.

[0132] [Example 1] 5.00 g of 1,3-bis(3-methoxypropyl)imidazolium acetate was placed in a 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 as determined 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 filtered and the glucose conversion rate was calculated. The results are shown in Table 1.

[0133] [Comparative Example 1] The same procedure as in Example 1 was repeated, except that 1-ethyl-3-methylimidazolium acetate was used instead of 1,3-bis(3-methoxypropyl)imidazolium acetate. 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 (Tokyo Chemical Industry Co., Ltd., β-D-glucose (including α-D-glucose)), and 9.6 g of ultrapure water were placed in a 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 out the insoluble matter, the amount of ethanol produced 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 (Tokyo Chemical Industry Co., Ltd., β-D-glucose (including α-D-glucose)), and 9.6 g of ultrapure water were placed in a 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 out the insoluble matter, the amount of ethanol produced 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 (Tokyo Chemical Industry Co., Ltd., β-D-glucose (containing α-D-glucose)), and 9.6 g of ultrapure water were placed in a 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 out the insoluble matter, the amount of ethanol produced was quantified by GC (gas chromatography) to calculate the ethanol yield. The results are shown in Table 2.

[0137] [Comparative Example 2] The same procedure as in Example 2 was repeated, except that 1-ethyl-3-methylimidazolium acetate was used instead of 1,3-bis(3-methoxypropyl)imidazolium acetate. The results are shown in Table 2.

[0138] [Reference Example 1] and [Comparative Reference Example 1] Antibacterial tests (measurement of minimum inhibitory concentration (MIC value)) were carried out on 1,3-bis(3-methoxypropyl)imidazolium acetate and 1-ethyl-3-methylimidazolium acetate against yeast (Saccharomycs cerevisiae). 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]

[0141] [Table 3]

[0142] [Example 5] 2.00 g of 1,3-bis(3-methoxypropyl)imidazolium acetate was placed in a sample tube, 0.50 g of microcrystalline cellulose (Avicel (registered trademark) PH-101) was added, and the mixture was heated and stirred at 80 ° C for 3 hours. After visual observation confirmed that the microcrystalline cellulose was completely dissolved, 38.0 g of ultrapure water and 20 μL of cellulase (Sigma) were added, and the mixture was stirred at 50 ° C for 10 hours. Then, 0.50 g of dry yeast was added, and the mixture was gently stirred at 30 ° C. After 7 hours, the insoluble matter was filtered, and the amount of ethanol produced was quantified by GC (gas chromatography), and the ethanol yield was calculated. The results are shown in Table 4.

[0143] [Comparative Example 3] The same procedure as in Example 5 was repeated, except that 1-ethyl-3-methylimidazolium acetate was used instead of 1,3-bis(3-methoxypropyl)imidazolium acetate. The results are shown in Table 4.

[0144] [Comparative Example 4] The same procedure as in Example 5 was carried out except that the 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. At this time, the microcrystalline cellulose did not dissolve. The results are shown in Table 4.

[0145] [Table 4] [Industrial Applicability]

[0146] According to the present invention, a composition containing an onium salt capable of successfully carrying out an enzymatic reaction and fermentation by a microorganism can be provided. According to the present invention, a method for producing a cellulose hydrolysate can be provided by enzymatically hydrolyzing cellulose in the presence of an onium salt capable of successfully carrying out an enzymatic reaction and fermentation by a microorganism. According to the present invention, a method for producing an alcohol and / or an organic acid can be provided by fermenting a cellulose hydrolysate with a microorganism in the presence of the onium salt.

Claims

1. An onium salt composition comprising an onium salt represented by the following formula (1), a cellulose-containing biomass, and an enzyme: Formula (1): 【Chemistry 1】 (In the formula, R 1 ~R 3 are the same or different, and R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

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

3. The onium salt composition according to claim 1 or 2, further comprising 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 comprising an onium salt represented by the following formula (1), glucose, and a microorganism: Formula (1): 【Chemistry 2】 (In the formula, R 1 ~R 3 are the same or different, and R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

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

7. The onium salt composition according to claim 5 or 6, further comprising 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 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 the formula, R 1 ~R 3 are the same or different, and R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

10. The onium salt composition of claim 9 further comprising 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 hydrolysate, comprising enzymatically hydrolyzing cellulose contained in cellulose-containing biomass in the presence of an onium salt represented by the following formula (1) and water: Formula (1): 【Chemistry 4】 (In the formula, R 1 ~R 3 are the same or different, and R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

13. The method for producing a cellulose hydrolysate according to claim 12, comprising the following steps (1) to (3): Step (1): A step of dissolving a 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 lysate obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing the cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolysate.

14. A method for producing an alcohol and / or an organic acid, comprising fermenting a cellulose hydrolysate with a microorganism in the presence of an onium salt represented by the following formula (1) and water: Formula (1): 【Chemistry 5】 (In the formula, R 1 ~R 3 are the same or different, and R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond.

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 hydrolysate, water, and a microorganism. Step (2): A step of producing alcohol and / or organic acid by fermenting the cellulose hydrolysate with the microorganism in the solution obtained in step (1) to which the microorganism has been added. Step (3): A step of separating the alcohol and / or organic acid from the solution containing the alcohol and / or organic acid obtained in step (2).

16. The method for producing an alcohol according to claim 14 or 15, wherein the alcohol is ethanol.

17. 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, the method comprising the following steps (1) to (6): Formula (1): 【Chemistry 6】 (In the formula, R 1 ~R 3 are the same or different, and R 1 and R 2 is a hydrocarbon group having 2 to 12 carbon atoms and containing 1 to 5 heteroatoms; R 3 R represents a hydrogen atom or a hydrocarbon group which may contain a heteroatom. 1 ~R 3 may contain branched and / or cyclic structures and / or double bonds, R 1 ~R 3 Part or all of 1 ~R 3 may be bonded together with the nitrogen atom and the carbon atom to which they are bonded to form a ring structure. 4 represents a hydrocarbon group which may contain heteroatoms, and which may contain a branched and / or cyclic structure and / or a double bond. Step (1): A step of dissolving a 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 lysate obtained in step (1). Step (3): A step of stirring the solution obtained in step (2) and hydrolyzing the cellulose contained in the cellulose-containing biomass with an enzyme to obtain a cellulose hydrolysate. Step (4): Adding microorganisms to the solution containing the cellulose hydrolysate obtained in step (3). Step (5): A step of fermenting the cellulose hydrolysate with the microorganisms in the solution obtained in step (4) to which the microorganisms have been added, thereby producing alcohol and / or organic acid. Step (6): A step of separating the alcohol and / or organic acid from the solution containing the alcohol and / or organic acid obtained in step (5).

18. 18. The method according to claim 14 or 17, further comprising recovering a solution containing the onium salt represented by formula (1), separating the onium salt from the recovered solution, and recycling the onium salt.

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